Home Cart 0 Sign in  

[ CAS No. 25440-14-6 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
Chemical Structure| 25440-14-6
Chemical Structure| 25440-14-6
Structure of 25440-14-6 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Quality Control of [ 25440-14-6 ]

Related Doc. of [ 25440-14-6 ]

Alternatived Products of [ 25440-14-6 ]

Product Details of [ 25440-14-6 ]

CAS No. :25440-14-6 MDL No. :MFCD00010032
Formula : C44H10F20N4 Boiling Point : -
Linear Structure Formula :- InChI Key :VJEVAXUMNMFKDT-UHFFFAOYSA-N
M.W : 974.55 Pubchem ID :135401562
Synonyms :

Calculated chemistry of [ 25440-14-6 ]

Physicochemical Properties

Num. heavy atoms : 68
Num. arom. heavy atoms : 34
Fraction Csp3 : 0.0
Num. rotatable bonds : 4
Num. H-bond acceptors : 22.0
Num. H-bond donors : 2.0
Molar Refractivity : 202.63
TPSA : 56.3 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : Yes
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -3.43 cm/s

Lipophilicity

Log Po/w (iLOGP) : 5.13
Log Po/w (XLOGP3) : 12.42
Log Po/w (WLOGP) : 18.42
Log Po/w (MLOGP) : 11.92
Log Po/w (SILICOS-IT) : 18.67
Consensus Log Po/w : 13.31

Druglikeness

Lipinski : 2.0
Ghose : None
Veber : 0.0
Egan : 1.0
Muegge : 4.0
Bioavailability Score : 0.17

Water Solubility

Log S (ESOL) : -13.81
Solubility : 0.0 mg/ml ; 0.0 mol/l
Class : Insoluble
Log S (Ali) : -13.62
Solubility : 0.0 mg/ml ; 0.0 mol/l
Class : Insoluble
Log S (SILICOS-IT) : -20.46
Solubility : 3.38e-18 mg/ml ; 3.47e-21 mol/l
Class : Insoluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 7.47

Safety of [ 25440-14-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 25440-14-6 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 25440-14-6 ]

[ 25440-14-6 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 109-97-7 ]
  • [ 653-37-2 ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
61% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane for 4h; Reflux; Inert atmosphere; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane for 12h; Reflux; 1.1 (1) Preparation of H2TFPP (Synthesis of tetrakis(pentafluorophenyl)porphyrin derivative) Pentafluorobenzaldehyde (5 g) and pyrrole (2 mL) were dissolved in dichloromethane (1.2 L) under substitution with nitrogen. To the resultant solution was added boron trifluoride ether complex (1 mL) and heated under reflux for 4 hours, followed by addition of chloranil (6.9 g), and heated under reflux for another 12 hours. The resulting reaction mixture was cooled, concentrated under reduced pressure, and then loaded onto a silica gel column, and eluted with chloroform for preparative isolation to give 5, 10, 15, 20-tetrakis(pentafluorophenyl)porphyrin (abbr. H2TFPP). After concentration under reduced pressure, it was recrystallized from the mixture of chloroform and methanol (yield: 3.8 g; 61%).
41% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 16h; Inert atmosphere; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane for 3h; Inert atmosphere;
41% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 4.5h; Inert atmosphere; Darkness; Molecular sieve; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane at 45℃; for 2h; Inert atmosphere; 1.1; 4.1 Dry methylene chloride was placed in a three-necked flask, and nitrogen gas was passed through magnetic stirring for 10 min. Subsequently, pentafluorobenzaldehyde (0.5 mL, 4 mmol) and freshly steamed pyrrole (0.28 mL, 4 mmol) were added to the reaction flask at a molar ratio of 1:1, and stirring was continued for 30 min under nitrogen.Then, under the protection of nitrogen, activated molecular sieves were used as a water-removing agent, and boron trifluoride etherate (0.3 mL, 0.4 mml) was used as a catalyst under nitrogen atmosphere for 4 hours at room temperature in the dark.Then, a porphyrin equivalent of p-tetrachlorophenylhydrazine (983.52 mg, 4 mmol) was added as an oxidizing agent to the reaction system, and the mixture was refluxed at 45 ° C for 2 hours and then cooled to room temperature. After concentration by distillation under reduced pressure, silica gel column chromatography was carried out using petroleum ether/dichloromethane (2:1, v/v) as eluent.(pentafluorophenyl)porphyrin. The yield was 41%.
41% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In diethyl ether; dichloromethane at 20℃; for 4h; Inert atmosphere; Molecular sieve; Darkness; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In diethyl ether; dichloromethane at 50℃; for 1h; Inert atmosphere; Molecular sieve; Darkness;
41% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In diethyl ether; dichloromethane at 20℃; for 4h; Inert atmosphere; Molecular sieve; Darkness; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In diethyl ether; dichloromethane at 50℃; for 1h; Inert atmosphere; Molecular sieve; Darkness;
40% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 18h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 2h; Inert atmosphere; Reflux; 1.1.1 1.1.1 Preparation of 5,10,15,20-tetrakis(pentafluorophenyl)-porphyrin In a typical experiment, dry DCM (1500 ml) was placed in a three-necked flask equipped with a magnetic stirrer and argon gas inlet. After pyrrole (0.88 ml, 12.7 mmol) and pentafluorobenzaldehyde (1.58 ml, 12.7 mmol) were added, the flask was shielded from ambient light and BFs(OEt2) (0.45 ml, 3.6 mmol) was added and the reaction mixture was stirred at room temperature for 18 h. Then, DDQ (2.90 g, 12.8 mmol) suspended in dry DCM (100 ml) was added, the mixture was refluxed for 2 hours, after cooling down to room temperature filtered over silica and the solvent was evaporated. After column chromatography (DCM/hexane = 1 : 1) and recrystallization (DCM/MeOH) the product was obtained as purple crystals (1.23 g, 1.26 mmol, 40%). ^-NMR (250 MHz, CDC13): δ = -2.92 (s, 2H, NH), 8.92 (s, 8H, ^-HPyirol) ppm. 19F-NMR (376 MHz, CDC13): δ = -136.4 (dd, J = 23.4, 7.7 Hz, 8F, Ar-Fort0), -151.10 (t, J = 20.8 Hz, 4F, Ar-F^J, -161.20 (td, J = 22.9, 7.6 Hz, 8F, Ar-FM). HRMS (ESI-TOF): m/z calc. for C44H„F2oN4 [M + H]+: 975.0659; found: 975.0624.
38% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 40h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 2h;
37% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 37℃; for 40h; Inert atmosphere; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane at 37℃; for 3h; Inert atmosphere;
31% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 3h; Inert atmosphere; Darkness; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane at 20℃; for 12h; Inert atmosphere;
24.3% Stage #1: pyrrole; perfluorobenzaldehyde In dichloromethane for 0.25h; Inert atmosphere; Stage #2: With boron trifluoride diethyl ether complex In dichloromethane for 2h; Inert atmosphere; Stage #3: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 0.5h;
20% With propionic acid for 3h; Reflux; Darkness; Synthesis of F20TPP General procedure: Benzaldehyde (40 mmol) and pyrrole (2.77 mL, 40 mmol) were stirred in propionic acid (300 mL) and heated to reflux for 3 h in darkness. Vacuum distillation removes propionic acid, extracted with dichloromethane (DCM) and washed with saturated Na2CO3, brine, dried (Na2SO4), and concentrated in vacuum, and the residue was purified by flash column chromatography on silica gel. The porphyrin was obtained 3.0 g violet solid for 49% yield.
15% With glacial acetic acid In nitrobenzene Heating;
15% With propionic acid at 20℃; for 2.5h;
15.4% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 24h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 2h; Reflux; Inert atmosphere;
14% In propionic acid for 2.5h; Inert atmosphere; Schlenk technique; Reflux;
11.1% With propionic acid for 5h; Reflux;
11% Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 16h; Inert atmosphere; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane at 20℃; for 3h; Inert atmosphere;
10% With propionic acid for 3h; Reflux; Inert atmosphere;
10% Stage #1: pyrrole; perfluorobenzaldehyde In dichloromethane at 20℃; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 3h;
9% With propionic acid In nitrobenzene at 140℃; for 0.45h; Flow reactor;
9.1% With glacial acetic acid In nitromethane at 120 - 130℃; for 2h; 4.3 Synthesis of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (1) The porphyrin 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (1) was synthesized accordingly to our recent methodology [35]. In a typical experiment, 18 g of catalyst (NaY) was introduced into a 1l round flask, previously filled with a glacial acetic acid/nitrobenzene mixture (340 ml/190 ml) and pentafluorobenzaldehyde (0.04 mol). Addition of equimolar amount of pyrrole (0.04 mol) was carried out drop wise under stirring and heating of the suspension (≈120°C). After complete addition, the suspension was heated further to attain the reflux temperature (≈130°C) and maintained at this temperature for ca. 2 h. The hot suspension was filtered and the resulting solid material washed with chloroform and tetrahydrofuran until no colored material was collected on the supernatant. The volume of supernatant was then reduced by rotoevaporation (enough volume to remove the added washing solvents). The crude was purified by silica gel column chromatography using hexane/ dichloromethane (10:1) as eluent and successive precipitations. The resulting crystals were dried under vacuum (yield=9.1%, 0.953 g). (0027) 1H NMR (400 MHz, CDCl3): ppm, δ -2.91 (s, 2H), 8.92 (s, 8H); 19F NMR (376 MHz, CDCl3) ppm, δ -160.14 to -160.28 (m, J=22.7, 7.6 Hz, 8F), -150.06 to -150.16 (t, J=20.8 Hz, 4F), -135.35 to -135.43 (dd, J=23.3, 7.7 Hz, 8F); the data is in agreement with the literature [35].
9% Stage #1: perfluorobenzaldehyde With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: With 2-(2-nitro-1-(1H-pyrrol-2-yl)ethyl)-5-(phenyl(1H-pyrrol-2-yl)methyl)-1H-pyrrole In dichloromethane at 20℃; for 0.166667h; Inert atmosphere; Stage #3: pyrrole Further stages;
8% In glacial acetic acid; nitrobenzene at 120℃; for 1h;
8% With glacial acetic acid In nitrobenzene for 1.25h; Reflux; 5,10,15,20-Tetrakis[2,3,5,6-tetrafluoro-4-(N-methylpyridinium-4-ylsulfanyl)phenyl] porphyrin tetra-iodide (porphyrin 11) Porphyrin 11 was prepared exactly as described by Gomes et al (2011). This synthesis was generally based on the nucleophilic displaycement of the four p-fluorine atoms of 5,10,15,20-tetraquis(pentafluorophenyl)porphyrin (TPPPF) with 4-mercatopyridine. Intermediate 5,10,15,20-tetraquis[2,3,5,6-tetrafluor-4-(4-pyridylsulfanyl)phenyl]porfirina (TPPPF-SPyr) was then submitted to pyridine nitrogen cationization to give porphyrin 11. Detailed procedure to synthesize porphyrin 11 was as follows: Firstly, TPPPF was prepared by adding pentafluorbenzaldehyde (4 mL, 32 mmol) on a refluxing mixture of glacial acetic acid (200 mL) and nitrobenzene (150 mL). Pyrrole (2,5 mL, 36 mmol) was then added dropwise for 15 min and the resulting mixture was kept under reflux for one hour. Reaction mixture was then cooled to room temperature and the acetic acid and nitrobenzene were disttilled with reduced pressure. Residue was resuspended in chloroform and applied to a silica gel column with chloroform: petroleum ether (1:1) as eluent. Porphyrin fraction was concentrated and recrystalized from dichloromethane/petroleum ether (8% yield). Secondly, TPPPF-SPyr was then prepared from TPPPF (100.0 mg; 0.1 mmol) in dry DMF (5 mL) by adding 47 mg of 4-mercatopyridine (4.1 equivalents) and 1 mL of diethylamine. The resulting mixture was stirred under room temperature for 4 h, under argon, in an ice bath. Reaction mixture was then vacuum dried and the residue was chromatographed by preparative TLC, first eluted with petroleum ether followed by dichloromethane (for DMF removal), with fractioning being performed with dichloromethane: methanol (98:2). The fraction containing TPPPF-SPyr was crystallyzed from n-hexane and dichloromethane with 44% yield. 5,10,15,20-Tetrakis[2,3,5,6-tetrafluoro-4-(N-methylpyridinium-4-ylsulfanyl)phenyl] (porphyrin 11) was finally synthesized from a suspension of TPPPF-SPyr (75.0 mg, 56 mmol) in DMF (15 mL) added by 3 mL (48 mmol) of methyl iodide. The resulting mixture was kept under stirring from 24 h at 40 oC. Reaction mixture was then cooled to room temperature and the product (porphyrin 11) was precipitated with added diethyl ether, and then washed with cold diethyl ether (68 mg, 64%). 1H-NMR (DMSOd6) 9.66 (s, 8H, pyrrole); 8.97 (d, 8H, m-Ar); 8.48 (d, 8H, o-Ar); 4.38 (12H, CH3); -3.06 (s, 2H, NH). NMR spectral data of porphyrin 11 is in accordance with the following reference: Gomes, M. C.; Barreira, S. M. W.; Faustino, M. A. F.; Fernandes, R; Neves, M. G.; Tom, A. C.; Gomes, N. C. M.; Almeida, A.; Cavaleiro, J. A. S.; Cunha, A.; Tom, J. P. C. Photochem. Photobiol. Sci. 2011, 10, 1735-1743.
With boron trifluoride diethyl ether complex; 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione 1.) CH2Cl2, 20 h, room t.; 2.) 1 h, reflux in the dark; Yield given. Multistep reaction;
With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione; trifluoroacetic acid 1.) CH2Cl2, r.t., 24 h; reflux, 1 h, 2.) CH2Cl2, reflux, 1h; Multistep reaction;
With boron trifluoride diethyl ether complex; 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione 1.) CH2Cl2, 23 h, 2.) reflux, 2 h; Yield given. Multistep reaction;
With boron trifluoride diethyl ether complex; 2,3-dicyano-5,6-dichloro-p-benzoquinone 1.) CH2Cl2, RT, 20 h, 2.) CH2Cl2, reflux, 2 h; Yield given. Multistep reaction;
23 % Spectr. Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 24h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane
Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane for 4h; Heating; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane for 12h; Heating;
With acetic anhydride In propionic acid for 3h; Reflux;
With propionic acid
Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride In dichloromethane for 4h; Inert atmosphere; Reflux; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane
Microwave irradiation;
With glacial acetic acid In nitrobenzene 2.3. Synthesis of the metalloporphyrins General procedure: The metalloporphyrin catalysts were prepared in accordance with literature procedures [30-32]. The free-base porphyrins were prepared by condensation of pyrrol and the appropriate benzaldehyde, 2,6-dichlorobenzaldehyde or pentafluorobenzaldehyde, in acidic and oxidizing media, namely in a mixture of acetic acid and nitrobenzene as reaction solvents. The free-base porphyrins were recovered from the reaction media by precipitation and obtained pure after recrystallization [30]. The nitration was performed on the β-pyrrolic position by reaction with zinc nitrate in acetic anhydride [31]. Removal of zinc as central atom was obtained by reaction with TFA and the complexation of the porphyrin free-bases was obtained by reaction with manganese chloride in reflux of DMF and in the presence of pyridine [32]. The reaction was controlled by UV-Vis spectroscopy following the bathochromic shift of the Soret band of the porphyrin until completeness of the complexation reaction. The spectroscopic data and yields obtained for pure free-base porphyrin nucleus and corresponding paramagnetic Mn(III) complexes are presented below (an asterisk is assigned to the Soret band on the UV-vis spectra).
With glacial acetic acid
With glacial acetic acid In nitrobenzene Reflux;
With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 20.25h; Inert atmosphere; Sealed tube;
In glacial acetic acid; nitrobenzene at 120℃; for 0.25h; Microwave irradiation; Green chemistry; 3.2. Preparation of Metaloporphyrin Catalysts Microwave syntheses were carried out using a Discover LabMate reactor (CEM Corporation,Matthews, NC, USA) with a temperature control system equipped with a reaction vessel of 10 mL.The reaction mixture was constantly irradiated in a closed system, at the desired temperature, usingup to 300W of power.For the studies on the synthesis of H2TPFPP, 6 mL of the reaction solvent were introduced into thereaction vessel, or when a solvent mixture was used, acetic acid (4 mL) and nitrobenzene (2 mL) wereadded to the reaction vessel. The reagents were added to the microwave reactor immediately beforethe reactions were heated. For the reactions performed at reagent concentrations of 0.1 moldm3,pyrrole (6.0 x 104 mol; 41.6 L) and pentafluorobenzaldehyde (6.0 x 104 mol; 74.1 L) were addedto the reaction vessel and the mixture agitated using a magnetic stirrer for the chosen temperature andtime (Figure 2). The completed reactions were promptly analyzed using UV-Vis spectroscopy usingsolutions diluted with chloroform.In the reactions performed in acetic acid, after 72 h a porphyrin precipitate was observed.The reaction mixture was filtered, the precipitate washed with n-hexane and recrystallized fromdichloromethane:n-hexane.For the studies of the preparation of the iron complex [Fe(TPFPP)Cl], the reaction vessel wascharged with 5 mL of the reaction solvent and 50 mg of H2TPFPP and the vessel irradiated usingthe conditions described in Table 1. For the reactions described in Entries 4 and 5, the initial reactionmixture was agitated for 1 h outside of the microwave apparatus prior to irradiation.The iron insertion reactions were evaluated by thin layer chromatography (TLC) using silicaplates with chloroform as eluent to determine if metalation was complete. The solvent was thenevaporated and the reaction mixture dissolved in chloroform and washed several times with deionizedwater. After evaporation of chloroform, the metaloporphyrin was dissolved in dichloromethane andreprecipitated by the addition of n-hexane. The precipitate was filtered and washed with n-hexane.
Acidic conditions;
Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex In dichloromethane at 20℃; for 3h; Inert atmosphere; Darkness; Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In dichloromethane at 20℃; for 3h; Inert atmosphere; Darkness; General procedure: Tetrakis(2, 6-dichlorophenyl)porphyrin (T(2, 6-diCl)PP), tetrakis(2,3, 6-trichlorophenyl)porphyrin (T(2, 3, 6-triCl)PP) and tetrakis(2, 3, 4,5, 6-pentafluorophenyl)porphyrin (T(2, 3, 4, 5, 6-pentaF)PP, TPFPP)were synthesized through condensation of the corresponding aromaticaldehyde with freshly distilled pyrrole in dichloromethane according tothe Lindsay method after some modifications (Eq. 2 in Scheme 1)[77-79]. In the synthesis process, aromatic aldehyde (6.0 mmol) andfreshly distilled pyrrole (6.0 mmol) were dissolved in dichloromethanedried over CaH2 (600 mL) and stirred under the atmosphere of nitrogenat room temperature for 15 min. BF3• OEt2 (2.0 mmol) was added quickly,and the resultant reaction mixture was stirred at room temperature for3.0 h shielded from ambient light. Then, p-chloranil (6.0 mmol) wasadded followed by stirring at room temperature for another 3.0 h, andtriethylamine (2.0 mL) was added to quench the reaction. The crudeproducts were obtained through rotary evaporation of solvent, andneutral alumina column chromatography was utilized for further purification with dichloromethane as eluent. It was collected of all theeluent from black to red. After concentration of the collected eluent,silica column chromatography was employed for further purification ofthe obtained crude products utilizing the eluent of cyclohexane anddichloromethane (Vcyclohexane :V dichloromethane = 4 : 1 1 : 1). All the obtained porphyrins were dried at 75 C for 12.0 h under reduced pressure and characterized through FT-IR, 1H NMR, 13C NMR andESI-MS. Details could be seen in the Electronic SupplementaryInformation.
Stage #1: pyrrole; perfluorobenzaldehyde With boron trifluoride diethyl ether complex Stage #2: With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione
With glacial acetic acid In nitrobenzene
With boron trifluoride diethyl ether complex

Reference: [1]Current Patent Assignee: REI MEDICAL CO LTD - EP2123664, 2009, A1 Location in patent: Page/Page column 13
[2]Peters, Morten K.; Röhricht, Fynn; Näther, Christian; Herges, Rainer [Organic Letters, 2018, vol. 20, # 24, p. 7879 - 7883]
[3]Current Patent Assignee: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN109651383, 2019, A Location in patent: Paragraph 0049; 0053; 0055; 0056; 0071; 0075-0077
[4]Liu, Zhiyong; Xue, Yudong; Wu, Mengsi; Yang, Guoliang; Lan, Minbo; Zhang, Weian [Biomacromolecules, 2019, vol. 20, # 12, p. 4563 - 4573]
[5]Liu, Zhiyong; Wu, Mengsi; Xue, Yudong; Chen, Chao; Wurm, Frederik R.; Lan, Minbo; Zhang, Weian [Chemical Communications, 2020, vol. 56, # 16, p. 2415 - 2418]
[6]Current Patent Assignee: BIOMED TECHNOLOGY HOLDINGS LTD.; FREIE UNIVERSITÄT BERLIN - WO2016/51361, 2016, A1 Location in patent: Page/Page column 10; 11
[7]Heredia, Daniel A.; Durantini, Javier E.; Ferreyra, Darío D.; Reynoso, Eugenia; Gonzalez Lopez, Edwin J.; Durantini, Andrés M.; Milanesio, María E.; Durantini, Edgardo N. [Journal of Photochemistry and Photobiology B: Biology, 2021, vol. 225]
[8]Dommaschk, Marcel; Gutzeit, Florian; Boretius, Susann; Haag, Rainer; Herges, Rainer [Chemical Communications, 2014, vol. 50, # 83, p. 12476 - 12478]
[9]Batista, Victor S.; Chaudhuri, Subhajyoti; D'Souza, Francis; Holzer, Noah; Poddutoori, Prashanth K.; Seetharaman, Sairaman; Van Der Est, Art; Zarrabi, Niloofar [Journal of the American Chemical Society, 2020, vol. 142, # 22, p. 10008 - 10024]
[10]Wu, Yanyu; Rodríguez-López, Nancy; Villagrán, Dino [Chemical Science, 2018, vol. 9, # 20, p. 4689 - 4695]
[11]Wang, Feng-Hua; Liu, Zheng-Yan; Yang, Shuang; Shi, Lei; Lin, Dong-Zi; Liu, Hai-Yang; Yuan, Gao-Qing [Synthetic Communications, 2021, vol. 51, # 13, p. 2053 - 2062]
[12]Tome, Joao P.C.; Neves, Maria G.P.M.S.; Tome, Augusto C.; Cavaleiro, Jose A.S.; Mendonca, Ana F.; Pegado, Ines N.; Duarte, Ricardo; Valdeira, Maria L. [Bioorganic and Medicinal Chemistry, 2005, vol. 13, # 12, p. 3878 - 3888]
[13]Han, Yongzhen; Fang, Huayi; Jing, Huize; Sun, Huiling; Lei, Haitao; Lai, Wenzhen; Cao, Rui [Angewandte Chemie - International Edition, 2016, vol. 55, # 18, p. 5457 - 5462][Angew. Chem., 2016, vol. 128, # 18, p. 5547 - 5552,6]
[14]Choi, E Tae; Choi, Hye Min; Kim, Ye Ji; Lee, Suk Joong; Lee, Tai Yong [Journal of Porphyrins and Phthalocyanines, 2022, vol. 26, # 4, p. 340 - 347]
[15]Lei, Haitao; Zhang, Qingxin; Wang, Yabo; Gao, Yimei; Wang, Yanzhi; Liang, Zuozhong; Zhang, Wei; Cao, Rui [Dalton Transactions, 2021, vol. 50, # 15, p. 5120 - 5123]
[16]Lim, Gary N.; Obondi, Christopher O.; D'Souza, Francis [Angewandte Chemie - International Edition, 2016, vol. 55, # 38, p. 11517 - 11521][Angew. Chem., 2016, vol. 128, p. 11689 - 11693,5]
[17]Han, Qi; Huang, Jia-Ying; Ji, Hong-Bing; Liu, Xiao-Hui; Tao, Lei-Ming; Xue, Can; Yu, Hai-Yang; Zhou, Xian-Tai; Zou, Wen [Chinese Journal of Chemistry, 2022, vol. 40, # 1, p. 115 - 122]
[18]Mondal, Baishakhi; Borah, Dibyajyoti; Mazumdar, Rakesh; Mondal, Biplab [Inorganic Chemistry, 2019, vol. 58, # 21, p. 14701 - 14707]
[19]Fujii, Hiroshi; Hada, Masahiko; Ishimizu, Yuri; Ma, Zhifeng [Inorganic Chemistry, 2021, vol. 60, # 23, p. 17687 - 17698]
[20]Momo, Patrícia B.; Bellete, Barbara S.; Brocksom, Timothy J.; De Souza, Rodrigo O. M. A.; De Oliveira, Kleber T. [RSC Advances, 2015, vol. 5, # 102, p. 84350 - 84355]
[21]Vinagreiro, Carolina S.; Gonçalves, Nuno P.F.; Calvete, Mário J.F.; Schaberle, Fábio A.; Arnaut, Luís G.; Pereira, Mariette M. [Journal of Fluorine Chemistry, 2015, vol. 180, p. 161 - 167]
[22]Seyitdanlioglu, Pinar; Altundal, Gulberil; Cinar, Seda; Unaleroglu, Canan [New Journal of Chemistry, 2018, vol. 42, # 17, p. 14163 - 14169]
[23]Grancho; Pereira; Miguel; Rocha, Gonsalves A M; Burrows [Photochemistry and photobiology, 2002, vol. 75, # 3, p. 249 - 256]
[24]Slomp, Amanda M.; Barreira, Sandra M.W.; Carrenho, Luise Z.B.; Vandresen, Camila C.; Zattoni, Ingrid F.; Ló, Stephanie M.S.; Dallagnol, Juliana C.C.; Ducatti, Diogo R.B.; Orsato, Alexandre; Duarte, M. Eugênia R.; Noseda, Miguel D.; Otuki, Michel F.; Gonçalves, Alan G. [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 2, p. 156 - 161]
[25]Collman, James P.; Kodadek, Thomas; Brauman, John I. [Journal of the American Chemical Society, 1986, vol. 108, # 10, p. 2588 - 2594]
[26]Made, A. W. van der; Hoppenbrouwer, E. J. H.; Nolte, R. J. M.; Drenth, W. [Recueil des Travaux Chimiques des Pays-Bas, 1988, vol. 107, # 1, p. 15 - 16]
[27]Ono, Noboru; Miyagawa, Hirokazu; Ueta, Takahiro; Ogawa, Takuji; Tani, Hiroyuki [Journal of the Chemical Society. Perkin transactions I, 1998, # 10, p. 1595 - 1601]
[28]Quast, Helmut; Dietz, Thomas; Witzel, Alexander [Liebigs Annalen, 1995, # 8, p. 1495 - 1502]
[29]Volz, Heinrich; Schneckenburger, Sylvia [Journal fur Praktische Chemie - Chemiker-Zeitung, 1993, vol. 335, # 3, p. 283 - 284]
[30]Geier III, G. Richard; Lindsey, Jonathan S. [Tetrahedron, 2004, vol. 60, # 50, p. 11435 - 11444]
[31]Kashiwagi, Yukiyasu; Imahori, Hiroshi; Araki, Yasuyuki; Ito, Osamu; Yamada, Koji; Sakata, Yoshiteru; Fukuzumi, Shunichi [Journal of Physical Chemistry A, 2003, vol. 107, # 29, p. 5515 - 5522]
[32]Location in patent: experimental part Nakanishi, Tatsuaki; Ohkubo, Kei; Kojima, Takahiko; Fukuzumi, Shunichi [Journal of the American Chemical Society, 2009, vol. 131, p. 577 - 584]
[33]Location in patent: body text Zhu, Xun-Jin; Zhang, Tao; Zhao, Shunsheng; Wong, Wai-Kwok; Wong, Wai-Yeung [European Journal of Inorganic Chemistry, 2011, # 22, p. 3314 - 3320]
[34]Lv, Hongbin; Yang, Boyan; Jing, Jing; Yu, Yi; Zhang, Jing; Zhang, Jun-Long [Dalton Transactions, 2012, vol. 41, # 11, p. 3116 - 3118]
[35]Location in patent: body text Pedrosa, Leandro F.; De Souza, Marcos C.; Faustino, Maria A.F.; Neves, Maria G.P.M.S.; Silva, Artur M. S.; Tome, Augusto C.; Ferreira, Vitor F.; Cavaleiro, Jose A.S. [Australian Journal of Chemistry, 2011, vol. 64, # 7, p. 939 - 944]
[36]Linhares, Margarida; Rebelo, Susana L.H.; Simões, Mário M.Q.; Silva, Artur M.S.; Neves, M. Graça P.M.S.; Cavaleiro, José A.S.; Freire, Cristina [Applied Catalysis A: General, 2014, vol. 470, p. 427 - 433]
[37]Lipińska, Monika E.; Novais, João P.; Rebelo, Susana L.H.; Bachiller-Baeza, Belén; Rodríguez-Ramos, Inmaculada; Guerrero-Ruiz, Antonio; Freire, Cristina [Polyhedron, 2014, vol. 81, p. 475 - 484]
[38]Mesquita, Mariana Q.; Menezes, José C.J.M.D.S.; Pires, Sónia M.G.; Neves, Maria G.P.M.S.; Simões, Mário M.Q.; Tomé, Augusto C.; Cavaleiro, José A.S.; Cunha, Ângela; Daniel-Da-Silva, Ana L.; Almeida, Adelaide; Faustino, M. Amparo F. [Dyes and Pigments, 2014, vol. 110, p. 123 - 133]
[39]Golf, Hartwig R. A.; Oltmanns, Anna M.; Trieu, Duc H.; Reissig, Hans-Ulrich; Wiehe, Arno [European Journal of Organic Chemistry, 2015, vol. 2015, # 19, p. 4224 - 4237]
[40]Rebelo, Susana L. H.; Silva, Andre M. N.; Medforth, Craig J.; Freire, Cristina [Molecules, 2016, vol. 21, # 4]
[41]Castro, Kelly A.D.F.; Moura, Nuno M.M.; Fernandes, Ana; Faustino, Maria A.F.; Simões, Mário M.Q.; Cavaleiro, José A.S.; Nakagaki, Shirley; Almeida, Adelaide; Cunha, Ângela; Silvestre, Armando J.D.; Freire, Carmem S.R.; Pinto, Ricardo J.B.; Neves, Maria da Graça P.M.S. [Dyes and Pigments, 2017, vol. 137, p. 265 - 276] Castro, Kelly A.D.F.; Rodrigues, João M.M.; Faustino, M. Amparo F.; Tomé, João P.C.; Cavaleiro, José A.S.; Neves, Maria da Graça P.M.S.; Simões, Mário M.Q. [Journal of Organometallic Chemistry, 2021, vol. 938]
[42]Shen, Hai-Min; Wang, Xiong; Ning, Lei; Guo, A-Bing; Deng, Jin-Hui; She, Yuan-Bin [Applied Catalysis A: General, 2021, vol. 609]
[43]Zarrabi, Niloofar; Holzer, Noah; Bayard, Brandon J.; Seetharaman, Sairaman; Boe, Benjamin G.; D'Souza, Francis; Poddutoori, Prashanth K. [Journal of Porphyrins and Phthalocyanines, 2021, vol. 25, # 5-6, p. 456 - 468]
[44]Mesquita, Mariana Q.; Ferreira, Ana Rita; Neves, Maria da Graça P.M.S.; Ribeiro, Daniela; Fardilha, Margarida; Faustino, Maria A.F. [Journal of Photochemistry and Photobiology B: Biology, 2021, vol. 223]
[45]Elberskirch, Linda; Le Harzic, Ronan; Scheglmann, Dietrich; Wieland, Gerhard; Wiehe, Arno; Mathieu-Gaedke, Maria; Golf, Hartwig R.A.; von Briesen, Hagen; Wagner, Sylvia [European Journal of Pharmaceutical Sciences, 2022, vol. 168]
  • 2
  • 5,10,15,20-Tetrakis-pentafluorophenyl-porphyrinogene [ No CAS ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
With chloranil In chloroform at 61℃; for 1h; Yield given;
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 0.0833333h; Inert atmosphere; 2.1 General procedure for the synthesis of A3-corrole (3a-f) General procedure: For the synthesis of corrole, a round-bottom flask with N2saturated dichloromethane (10 mL) was used in which substituted benzaldehydes (1 mmol) and freshly distilledpyrrole (2 mmol) were added and stirred at room temperature.To this reaction mixture, instead of acid, iodine wasadded (as a catalytic amount) and the color change of thereaction mixture was observed. Further, the round-bottomflask was covered with foil paper and continued stirring for5-10 min. Progress of the reaction was monitored with thehelp of thin layer chromatography (TLC) (i.e., if no reactantremains). Following which, DDQ (1 mmol) was added andthe stirring was continued for another 5 min. The product(corrole) was separated by basic alumina column chromatographywith hexane/chloroform solution. The compoundwas solid in nature with purple color and corroleswere obtained in high yield with 1:2 molar ratio in theprocess.
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 0.5h;
  • 3
  • [ 135-48-8 ]
  • [ 25440-14-6 ]
  • C66H24F20N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% In various solvent(s) at 200℃; microwave irradiation;
60% In various solvent(s) at 200℃;
  • 4
  • [ 167482-91-9 ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
15 % Spectr. Stage #1: 5-(pentafluorophenyl)dipyrromethane With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 4h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane
Stage #1: 5-(pentafluorophenyl)dipyrromethane With boron trifluoride diethyl etherate In dichloromethane for 0.666667h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 1h; Inert atmosphere; 2.2. Synthesis of trans-porphyrins using BF3.OEt2 as catalyst The precursor, 5-(pentafluorophenyl)dipyrromethane was prepared using reported literature method [14]. All the free base porphyrins were synthesized according to Lindsey method using BF3.OEt2 as the catalyst[15]. 5-(Pentafluorophenyl)dipyrromethane (0.64 mmol) and appropriate aryl aldehyde (0.64 mmol) were added to 300 mL of CH2Cl2 in around bottomed flask and purged with N2 for few minutes. To that,BF3OEt2 (0.25 mL, 2.5 M) was added and stirred for 40 min. The oxidizing agent DDQ (1.28 mmol) was then added and again stirred for 1 h.The solvent was evaporated and subjected to silica column chromatography in hexane/chloroform mixture. All the reactions resulted in the formation of three products, among them first fraction was found to be 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, H2T(PFP)P (Scheme1). The yield of trans-porphyrins (1a-6a) is found to be 11-19% whereas for the tris(pentafluorophenyl)-mono-(aryl) porphyrins (1b-6b) it is of 6-14%.
  • 5
  • [ 135-48-8 ]
  • [ 25440-14-6 ]
  • C88H38F20N4 [ No CAS ]
  • C88H38F20N4 [ No CAS ]
  • C66H24F20N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% In various solvent(s) at 200℃; for 0.333333h; microwave irradiation;
  • 6
  • 5,10,15,20-tetraphenyl[1,2,3]triazolo[4,5-b]porphyrin [ No CAS ]
  • [ 25440-14-6 ]
  • C88H38F19N11 [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 4h;
  • 7
  • 5,10,15,20-tetrakis(pentafluorophenyl)[1,2,3]triazolo[4,5-b]porphyrin [ No CAS ]
  • [ 25440-14-6 ]
  • C88H18F39N11 [ No CAS ]
YieldReaction ConditionsOperation in experiment
35% With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 3h;
  • 8
  • [ 77-08-7 ]
  • [ 25440-14-6 ]
  • polymer; monomer(s): meso-tetrakis(pentafluorophenyl)porphyrin; 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In 1-methyl-pyrrolidin-2-one at 200℃; for 6h;
  • 9
  • [ 872-85-5 ]
  • [ 109-97-7 ]
  • [ 653-37-2 ]
  • meso-5-(pentafluorophenyl)-10,15,20-tris(4-pyridyl)porphyrin [ No CAS ]
  • 5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin [ No CAS ]
  • 5,10,15-tris(2,3,4,5,6-pentafluorophenyl)-20-(4-pyridyl)porphyrin [ No CAS ]
  • [ 25440-14-6 ]
  • [ 16834-13-2 ]
  • (5,15-di(pyridin-4-yl)-10,20-bis(pentafluorophenyl))porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
9.4%; 1.1% 1a) Preparation of the Intermediate Compounds-Condensation Step A mixture of 4.3 mL (45 mmol, 3 eq.) of 4-pyridinecarboxaldehyde, 2.06 mL (16.5 mmol, 1 eq.) of pentafluorobenzaldehyde, and 4.15 mL (60 mmol, 4 eq.) pyrrole was dissolved in 300 mL of acetic acid, and the mixture was heated to reflux for 2 h After cooling to room temperature, the solvent was evaporated to dryness by vacuum and the oily residue was washed by hot water, neutralized by aqueous ammonia (25%), and washed again with hot water. The purple solids obtained by this procedure were filtered and dried. The dry solid material was treated with three portions of 50 mL of dichloromethane, each followed by filtration. To the combined organic phases, 10 g of silica were added, and the solvent was evaporated to dryness. 1b) Chromatographic Separation Separation and purification of the components obtained in step 1a was achieved by column chromatography, in which the polarity of the eluents was gradually increased from dichloromethane to mixtures of dichloromethane and 2-10% ethanol. The order of elution (the Rf values are for silica with 2% ETOH in CH2Cl2) and the chemical yields were as follows: [5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (1a=P2, tra, Rf=0.95). 5,10,15-tris(2,3,4,5,6-pentafluorophenyl)-20-(4-pyrdyl)porphyrin (1b, 1.1%, Rf=0.66). 5,15-bis(2,3,4,5,6-pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin (1c, Rf=0.60)*. 5,10-bis(2,3,4,5,6-pentafluorophenyl)-15,20-bis(4pyridyl)porphyrin (1d, Rf=0.54)*. 5-(2,3,4,5,6-pentafluorophenyl)-10,15,20-tris(4-pyridyl)porphyrin (1e, 9.4%, Rf=0.45). 5,10,15,20-tetrakis(4-pyridyl)porphyrin (1f, traces, Rf=0.18). * The combined yield of compounds 1c and 1d was 13.4%. Their separation required an additional column in which the eluent was 2% ethanol in dichloromethane. Spectroscopic characteristics of the compounds (1a and 1f are known compounds): 1a, UV-vis (CH2Cl2): lambdamax (nm) 412, 506, 586; 1H NMR (CDCl3): delta8.91 (s, 8H), -2.93 (s, 2H); 19F NMR (CDCl3): delta-136.9 (dd, J1=22.8 Hz, J2=7.0 Hz, 8F), -151.6 (t, J=20.7 Hz 4F), -161.7 (dd, J1=22.4 Hz, J2=5.8 Hz, 8F). 1b, UV-vis (CH2Cl2): lambdamax (nm) 414, 506, 582; 1H NMR (CDCl3): delta9.06 (d, J=4.3 Hz, 2H), 8.89 (s, 6H), 8.16 (d, J=4.2 Hz, 2H), 8.15 (s, 2H), -2.92 (s, 2H); 19F NMR (CDCl3): delta137.0 (m, 6F), -151.8 (m (2 overlaying t), 3F), -161.8 (m, 6F); MS+ (e/z) 886.1 (MH+, 100%), MS- (e/z) 884.6 (M-, 40%), ([M-H]-, 60%). 1c, UV-vis (CH2Cl2): lambdamax (nm) 412, 508, 584; 1H NMR (CDCl3): delta9.06 (d, J=4.4 Hz, 4H), 8.89 (s, 4H), 8.85 (s, 4H), 8.15 (d, J1=4.5 Hz, 4H), -2.94 (s, 2H); 19F NMR (CDCl3): delta-137.2 (dd, J1=23.2 Hz, J2=7.2 Hz, 4F), -152.0 (t, J=20.9 Hz, 2F), -161.9 (J1=22.8 Hz, J2=7.3 Hz, 4F); MS+ (e/z) 797.4 (MH+, 100%), MS- (e/z) 794.9 ([M-H]-, 100%). 1d, UV-vis (CH2Cl2): lambdamax (nm) 414, 508, 582; 1HNMR (CDCl3): delta9.06 (d, J=5.8 Hz, 4H), 8.89 (d, J=6.6 Hz, 4H), 8.84 (m, 4H), 8.15 (dd, J1=4.3 Hz, J2=1.5 Hz, 4H), -2.90 (s, 2H); 19F NMR (CDCl3): delta-137.1 (dd, J1=23.4 Hz, J2=8.1 Hz, 4F), -152.0 (t, J=21.1 Hz, 2F), -161.9 (td, J1=22.8 Hz, J2=7.9 Hz, 4F); MS+ (e/z) 797.4 (MH+, 100%), MS- (e/z) 794.9 ([M-H]-, 100%). 1e, UV-vis (CH2Cl2): lambdamax (nm) 416, 510, 586; 1H NMR (CDCl3): delta9.05 (d, J=5.4 Hz, 6H), 8.90 (d, J=4.8 Hz, 2H), 8.84 (m (unresolved doublets), 6H), 8.14 (m (unresolved doublets), 6H), -2.92 (s, 2H); 19F NMR (CDCl3): delta-137.3 (dd, J1=22.8 Hz, J2=7.9 Hz, 2F), -152.1 (t, J=21.7 Hz, 1F), -162.0 (J1=23.0 Hz, J2=7.7 Hz, 2F); MS+ (e/z) 708.1 (MH+, 100%), MS- (e/z) 706.1 ([M-H]-, 100%). 1f, 1H NMR (CDCl3): lambda9.04 (d, J=5.5 HZ, 8H), 8.85 (s, 8H), 8.14 (d, J=5.5 Hz, 8H), -2.95 (s, 2H).
  • 10
  • [ 100-39-0 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis(pentafluorophenyl)-2-benzylchlorin [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 2,2'-azobis(isobutyronitrile); tri-n-butyl-tin hydride In toluene at 60℃; for 408h; 5 Example 5 H2TFPC'-SAcGlc 1g of H2TFPP prepared in the above was dissolved in 20 ml of toluene, and 9.76 mL of benzyl bromide, 24 mL of tributyltin hydride, and 1.7 g of azoisobutylonitrile were added under heating at 60°C for a period of 17 days. The target component was fractionated from the crude product by silica gel column chromatography with hexane as an eluding solution, and the target component was collected by gel permeation preparative chromatography. Recrystallization was also performed from chloroform and acetonitrile to give 35 mg of 10, 15, 20-tetrakis(pentafluorophenyl)-2-benzyl chlorin (abbr. H2TFPC') of the following structure. S-glucosylation was performed for H2TFPC' in the same manner of Example 1 to give S-glycosylated chlorin derivative (HTFPC'-SAcGlc) of the following structure. The spectrum of the resulting HTFPC'-SAcGlc was measured by ESI-MS (ionization mode ESI, spectrum recording interval: 1.0 sec, orifice voltage sweep: 150V). The spectrum obtained is shown in . The peak (2443.43072) which corresponds to 2444.13, theoretical average mass of the target compound was confirmed. The mass spectrum shown in and the simulated mass spectrum of HTFPC'-SAcGlc (ref. ) showed almost the same main peaks (2442.5, 2444.5, 2445.5, 2446.5), which confirmed that HTFPC'-SAcGlc was prepared. By removing acetyl protecting groups in the same manner of Example 1, the target chlorin derivative can be prepared.
  • 11
  • [ 25440-14-6 ]
  • palladium dichloride [ No CAS ]
  • [ 72076-09-6 ]
YieldReaction ConditionsOperation in experiment
70% In benzonitrile at 220℃; for 96h; Inert atmosphere; 2.1 (1) Preparation of PdTFPP (Introduction of metal) H2TFPP (1 g) prepared in Example 1, (1) and palladium chloride (0.4 g) were dissolved in benzonitrile (35 mL). After the atmosphere was substituted with nitrogen, the resulting solution was heated at reflux under nitrogen at 220°C for 96 hours. The resultant reaction mixture was cooled and then concentrated under reduced pressure. The resulting crude product was loaded onto an alumina column and eluted with chloroform for preparative isolation. Further isolation was performed by silica gel chromatography and the resulting product was concentrated under reduced pressure, followed by recrystallization from a mixture of dichloromethane and methanol to provide [5, 10, 15, 20-tetrakis(pentafluorophenyl)porphyrinato]palladium (II) (abbr. PdTFPP) (yield: 0.76 g; 70%).
Inert atmosphere;
  • 12
  • [ 109-04-6 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[(4-(pyridin-2-yl)-2,3,5,6-tetrafluoro-phenyl)]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
20% Stage #1: 2-bromo-pyridine With n-butyllithium In tetrahydrofuran at -78 - -70℃; Stage #2: tetrakis(pentafluorophenyl)porphyrin In tetrahydrofuran at -78℃; I.2.a 2a) Preparation of the precursor 5,10,15,20-tetrakis[(4-(2-pyridyl)-2,3,5,6-tetrafluoro-phenyl)]porphyrin 1 mL of an 1.6 M n-BuLi solution (1.6 mmol) was added to a stirred solution of 0.14 mL (1.5 mol) 2-bromopyridine in 8 mL of dry THF under an argon atmosphere at -78° C., at such a rate that the temperature of the reaction mixture did not exceed -70° C. After the addition was complete, the reaction mixture was stirred for 1 h at -78° C., resulting in a clear yellow solution. Next, a solution of 0.1 g (0.1 mmol) 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin in 5 mL of dry THF was added dropwise. The mixture was stirred for 3 h at -78° C., and then hydrolyzed with saturated aqueous bicarbonate solution. The layers were separated, the aqueous layer washed with ether, and the combined ether extracts were dried and evaporated to a solid residue. The product was purified by column chromatography on silica gel (2:1 EtOAc:Hexane) and recrystallized from EtOAc:EtOH to give 26-30 mg (20-25% yield) of the pure product as violet solids. 1H NMR (CDCl3): δ9.06 (s, 8H), 8.97 (d, J=3.9 Hz, 4H), 8.03 (t, J=7.7 Hz, 4H), 7.89 (d, J=7.5 Hz, 4H), 7.54 (t, J=6 Hz, 4H), -2.82 (s, 2H). 19F NMR (CDCl3): δ-137.57 (q, J=24.8 Hz, 8F), 144.11 (q, J=24.6 Hz, 8F). MS+ (e/z) 1211.4 (MH+, 100%), MS- (e/z) 1208.3 ([M-H]-, 100%).
  • 13
  • [ 109-97-7 ]
  • [ 653-37-2 ]
  • [ 158399-19-0 ]
  • 5-[2,7-di-tert-butyl-5-methoxycarbonyl-9,9-dimethylxanthen-4-yl]-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
1: 34% 2: 4% Stage #1: pyrrole; perfluorobenzaldehyde; 4-formyl-5-methoxycarbonyl-2,7-di-tert-butyl-9,9-dimethylxanthene With boron trifluoride diethyl etherate In chloroform for 1h; Darkness; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform for 1h;
1: 34% 2: 13% Stage #1: pyrrole; perfluorobenzaldehyde; 4-formyl-5-methoxycarbonyl-2,7-di-tert-butyl-9,9-dimethylxanthene With boron trifluoride diethyl etherate In chloroform for 1h; Stage #2: With triethylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform 2 5-[4-(2,7-Di-tert-butyl-5-methoxycarbonyl-9,9-dimethylxanthene)]-10,15,20-tris(pentafluorophenyl)porphyrin (HPX1-CO2Me). Method A was followed. A solution of 5, pentafluorophenylbenzaldehyde (0.735 g, 3.75 mmol), and pyrrole in CHCl3 was treated with BF3.OEt2. After 1 h, a sample of DDQ was added to the solution. The reaction mixture was treated with triethylamine and aqueous work-up was performed. The crude product was chromatographed on two columns. First silica column: meso-Tetrapentafluorophenyl porphyrin F20-TPP was eluted, (hexanes/CH2Cl2 (5:1)→CH2Cl2) from the column as a first component, which upon concentration gave a purple solid (32 mg, 13%). The crystal structure of this compound is provided in FIG. 5. 1H NMR, ESI-MS, LD-MS, and absorption spectral data were consistent with that previously reported. Silica chromatography on a second column (hexanes/CH2Cl2 (10:1)) to afford a purple solid (102 mg, 34% based on aldehyde 5). Data for HPX1-CO2Me: 1H NMR (500 MHz, CDCl3) δ/ppm: -2.77 (s, 2H), 0.04 (s, 3H), 1.26 (s, 9H), 1.53 (s, 9H), 1.95 (s, 6H), 7.32 (d, J=2.5 Hz, 1H), 7.65 (d, J=2.5 Hz, 1H), 7.93 (d, J=2.5 Hz, 1H), 7.95 (d, J=2.5 Hz, 1H), 8.85-8.86 (m, 2H), 8.92 (s, 4H), 8.97-8.98 (m, 2H). Anal. Calcd. for (M+H)+, M=C63H41F15N4O3: 1187.3016. Found for LD-MS: 1187.25, ESI-MS: 1187.3012. λmax,abs/nm (THF)=414, 508, 540, 584. λmax,em(414 exc)/nm=643, 708
  • 14
  • [ 109-97-7 ]
  • [ 50-00-0 ]
  • [ 2251-50-5 ]
  • 5,10,15-tris(pentafluorophenyl)porphyrin [ No CAS ]
  • [ 25440-14-6 ]
  • 5,10,15-tris(pentafluorophenyl)corrole [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% With boron trifluoride diethyl etherate; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform 1 Corrole formation may be a minor side-product under Lindsey conditions. The synthesis of the A3 corrole tris(pentafluorophenyl)corrole (11) was undertaken as an exemplar; the synthetic strategy is shown in FIG. 2. Large scale (75 mmol) synthesis of 11 was performed by condensation of commercially available pyrrole, pentafluorobenzaldehyde and paraformaldehyde under Lindsey conditions. Thin layer chromatography (TLC) and Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) analysis of the crude reaction mixture revealed 11 as a major product. Trace amounts of porphyrins 12 and 13 were also observed as side products. The desired product 11 was isolated by flash column chromatography in 42% yield.
  • 15
  • [ 15243-33-1 ]
  • [ 25440-14-6 ]
  • [ 171899-61-9 ]
YieldReaction ConditionsOperation in experiment
86% In 1,2,4-Trichlorobenzene at 195 - 200℃; Inert atmosphere; Preparation of [RuII(TDCPP)CO], [RuII(TMP)CO] and [RuII(F20-TPP)CO] General procedure: 0.3 mmol Ru3(CO)12, 0.2 mmol base free porphyrin, and 25 mL 1,2,4-trichlorobenzene were mixed in 50 mL flask. After degassed in vacuum and protected with Ar, the mixture was heated at 195-200 °C (the temperature of oil bath) for 4-7 h. The reaction solution was diluted with 75 mL petroleum ether (PE) and was loaded on a neutral Al2O3 flash chromatographer column. Washed with PE and CH2Cl2, 1,2,4-trichlorobenzene and product were collected respectively.
  • 16
  • [ 34143-74-3 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[4-(2-perfluorooctylethylthio)-2,3,5,6-tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 1.5h;
67% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 8h; Inert atmosphere; 1 1. Synthesis of the Photocatalyst 1. Synthesis of the Photocatalyst Highly fluorinated photocatalyst, referred to herein as F8, was synthesised following Scheme 1. Specifically, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane-1-thiol (325 mg, 0.68 mmol) (Sigma Aldrich) was dissolved in 15 mL ethyl acetate (Sigma Aldrich)/dimethylformamide (DMF) (Sigma Aldrich) (2:1 v/v) with diethylamine (DEA) (0.1 mL, 0.97 mmol) (Sigma Aldrich) under nitrogen. 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPFPP) (57.5 mg, 0.06 mmol) dissolved in 5 mL DMF was added to this solution. The resulting solution was stirred under nitrogen at room temperature for 8 hours. The solution underwent centrifugation (8000×g) for 15 minutes. The solid was isolated by filtration, and re-dissolved in acetone and purified by silica gel chromatography using hexane/acetone (9:1 v/v). The yield of F8 was 112 mg (0.04 mmol, 67%). The obtained F8 was characterised by 1H and 19F-NMR. 1H-NMR (CDCl3 5% TFA) δ: -2.84 (broad s, 2H, pyrrole NH), 2.64 to 2.81 (m, 8H, 2′H), 3.50 (t, 8H, 1′H), 8.94 (s, 8H, pyrrole βH). 19F-NMR: (CDCl3 5% TFA) δ: -136.12 to -135.99 (m, 8F, Ar-o-F), -133.69 to -133.56 (m, 8F, Ar-m-F), -126.18 to -126.08 (m, 8F, 3′F), -123.14 (m, 8F, 4′F), -122.71 (m, 8F, 5′F), -121.68 to -121.61 (m, 24F, 6′-8′F), -113.86 to -113.75 (m, 8F, 9′F), -80.83 to 80.76 (m, 12F, 10′F).
  • 17
  • [ 25440-14-6 ]
  • [ 119998-79-7 ]
YieldReaction ConditionsOperation in experiment
80% With dichloro(2-picolinato)gold(III); Oxone; sodium acetate; silver trifluoromethanesulfonate In acetic acid at 120℃; for 12h; Inert atmosphere;
30% With [2,2]bipyridinyl; ruthenium trichloride; Oxone; sodium hydroxide In water; 1,2-dichloro-ethane Reflux; ONE-STEP SYNTHESIS OF MESO-TETRAKIS(PENTAFLUOROPHENYL)-2-OXA-3-OXOPORPHYRINTFPL BY RUCL3 / OXONE MEDIATED OXIDATION. GENERAL PROCEDURE. General procedure: Prepared according to a modified procedure reported in literature (Note 1) [9]. In a 750 mlround-bottom (or a two neck round-bottom) flask equipped with a stir bar and reflux condenser,TFPP (0.8 g, 0.8 mmol, 1 equiv.) and RuCl3 (85 mg, 0.4 mmol, 0.5 equiv.) were dissolved in 1,2-dichloroethane (ClCH2CH2Cl, 250 mL) (Note 2). A solution containing 2,2’-bipyridine (65 mg,0.4 mmol, 0.5 equiv.) in ClCH2CH2Cl (7 mL) and water (250 mL) were added. A condenser wasattached to one of the necks and the solution was heated to reflux (Figure S13). A mixture ofOxone (7.4 g, 12 mmol, 15 equiv.) and NaOH (480 mg, 12 mmol, 15 equiv.) in water (15 mL)was added periodically in five equal portions over the course of 5 h to the refluxing solution.After completion of the addition, the reaction mixture was refluxed overnight. The mixture wasallowed to cool to room temperature, quenched with a saturated aqueous solution of Na2S2O3(2.0 g in 5 mL of water). The reaction mixture was stirred, allowed to stand for 30 min, andtransferred to a 750 mL separatory funnel (Figure S14). The (bottom) organic layer wasseparated, and the aqueous layer was extracted twice using CH2Cl2 (2 × 150 mL). The combinedorganic fractions were washed with a saturated aqueous NaCl solution (2 × 150 mL). Theorganic layer was dried with anhydrous Na2SO4 (30 min) and the drying agent was removed bygravity filtering. The filtrate was reduced to dryness using rotary evaporation (in a 500 mLround-bottom flask). The residue was dissolved in CH2Cl2 (2-5ml), loaded as a solution onto apacked column (silica, 5 × 60 cm, with a fritted disk, eluent: CH2Cl2/hexanes = 2:1) andseparated to obtain the product TFPL as a purple solid upon solvent removal in 30% yield(240 mg, 0.24 mmol).
Multi-step reaction with 2 steps 1.1: osmium(VIII) oxide; pyridine / chloroform / 24 h / 20 °C 1.2: 48 h / 20 °C 2.1: cethyltrimethylammonium permanganate / dichloromethane / 3 h / 20 °C
  • 18
  • [ 34143-74-3 ]
  • [ 25440-14-6 ]
  • C84H26F84N4S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 8h; Inert atmosphere;
67% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 8h; Inert atmosphere; 1 1. Synthesis of the photocatalyst Specifically, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane-l-thiol (325 mg, 0.68 mmol) (Sigma Aldrich) was dissolved in 15 mL ethyl acetate (Sigma Aldrich)/ dimethylformamide (DMF) (Sigma Aldrich) (2: 1 v/v) with diethylamine (DEA) (0.1 mL, 0.97 mmol) (Sigma Aldrich) under nitrogen. 5,10,15,20- tetrakis(pentafluorophenyl)porphyrin (TPFPP) (57.5 mg, 0.06 mmol) dissolved in 5 mL DMF was added to this solution. The resulting solution was stirred under nitrogen at room temperature for 8 hours. The solution underwent centrifugation (8000 x g) for 15 minutes. The solid was isolated by filtration, and re-dissolved in acetone and purified by silica gel chromatography using hexane / acetone (9: 1 v/v). The yield of F8 was 112 mg (0.04 mmol, 67%). The obtained F8 was characterised by 1H and 19F-NMR. 1H-NMR (CDC13 5% TFA) δ: -2.84 (broad s, 2H, pyrrole NH), 2.64 to 2.81 (m, 8H, 2Ή), 3.50 (t, 8H, 1 Ή), 8.94 (s, 8H, pyrrole βΗ). 19F-NMR: (CDC13 5% TFA) δ: -136.12 to -135.99 (m, 8F, Ar-o-F), - 133.69 to -133.56 (m, 8F, Ar-m-F), -126.18 to -126.08 (m, 8F, 3'F), -123.14 (m, 8F, 4'F), - 122.71 (m, 8F, 5'F), -121.68 to -121.61 (m, 24F, 6'-8'F), -113.86 to -113.75 (m, 8F, 9'F), - 80.83 to 80.76 (m, 12F, 10'F).
  • 19
  • [ 36653-82-4 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-meso-tetrakis(2,3,5,6-tetrafluoro-4-(hexadecyloxy)phenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With potassium hydroxide In tetrahydrofuran at 70℃; for 4h; Inert atmosphere;
  • 20
  • [ 240131-10-6 ]
  • [ 557-34-6 ]
  • [ 25440-14-6 ]
  • C53H47B30F17N4S3Zn [ No CAS ]
YieldReaction ConditionsOperation in experiment
30% Stage #1: 1-mercaptomethyl-para-carborane; tetrakis(pentafluorophenyl)porphyrin With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 48h; Stage #2: zinc diacetate In methanol; dichloromethane at 20℃; for 24h; 1 To a solution of TPPF (19.52 mg, 0.02 mmol) in 2 ml of dry DMF was added anhydrous K2CO3 (16.6 mg, 0.12 mmol), mercaptomethyl-p-carborane (15.2 mg, 0.08 mmol). The reaction mixture was stirred at room temperature for 48 h. The resulting solution was diluted with ethyl acetate (50 mL) and washed with brine (2 * 50 mL). The organic layer was dried over anhydrous sodium sulfate, the solvents evaporated under reduced pressure and the resulting residue was dissolved in dichloromethane (10 mL). A saturated solution of Zn(OAc)2 in methanol (10 mL) was added and the resulting mixture stirred at room temperature for 24 h. The solvents were evaporated under reduced pressure and the resulting residue was purified by prep-TLC using chloroform/petroleum ether 1:1 to give 23.3 mg (30%) of desired zinc(II) porphyrin, mp >300 °C. UV-Vis (DMSO) λmax (ε/M-1 cm-1) 426 (444,400), 555 (43,800). 1H NMR (CDCl3, 400 MHz): δ 8.93 (s, 8H, β-H), 3.45 (s, 6H, -SCH2), 2.19-3.33 (m, 33H, BH, CH). MS (MALDI-TOF) m/z 1550.789 [M], calcd for ZnC53H47F17N4B30S3 = 1550.494.
  • 21
  • manganese(II) chloride tetrahydrate [ No CAS ]
  • [ 25440-14-6 ]
  • manganese(III)-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin chloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In N,N-dimethyl-formamide at 153℃;
In 1-methyl-pyrrolidin-2-one at 250℃; for 0.5h; Inert atmosphere; Irradiation; The porphyrin 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin(H2TF5PP) was prepared according to described procedures [16].For the microwave-assisted metallation of H2TF5PP about 100 mgof H2TF5PP were transferred to a microwave quartz cell and dissolvedin 5 mL of NMP. Then 10 molar equivalents of MnCl2·4H2O were added and the reaction mixture was deaerated by bubblingwith argon for 15 min. The vessel was closed and introduced into the reactor and the mixture was irradiated during 30 min at 250 Wand 200° C. After that time, the reaction was controlled by TLC and UV-vis and the procedure was repeated with addition of thesame amount of MnCl2·4H2O.
  • 22
  • [ 1266248-85-4 ]
  • [ 292164-60-4 ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
20% Stage #1: 4-methyl-N-((perfluorophenyl)methylene)benzenesulfonamide With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 50℃; Inert atmosphere; Stage #2: 5,10-bis(pentafluorophenyl)tripyrrane In dichloromethane at 50℃; Darkness; Stage #3: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 50℃; Synthesis of meso-PentafluorophenylSubstituted Expanded Porphyrins (4, 5, 6, 7, 8) from N-Sulfonyl Aldimine General procedure: 4-Methyl-N-((perfluorophenyl)methylene)benzenesulfonamide (0.062 g, 0.180mmol) and Cu(OTf)2 (0.0065 g, 0.018 mmol) were dissolved in CH2Cl2at room temperature and stirred for 30 minutes under nitrogen atmosphere. To this mixture was added meso-pentafluorophenyl substitutedtripyrrane (0.100 g, 0.180 mmol) in CH2Cl2 and themixture was stirred for 8 h in the dark. Then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) (0.082 g, 0.360 mmol) was added and the resulting mixture was stirred for 2h. Mixturewas eluted from a short column of silica gel to remove the tar. Solvent was removedunder reduced pressure and the residuewas purified by using column chromatography on silica gel(EtOAc:Hexane 1:50).
  • 23
  • [ 1266248-85-4 ]
  • [ 292164-60-4 ]
  • meso-heptakis(pentafluorophenyl) heptaphyrin(1.1.1.1.1.1.1) [ No CAS ]
  • [ 25440-14-6 ]
  • [ 864429-34-5 ]
YieldReaction ConditionsOperation in experiment
1: 8% 2: 10% 3: 14% Stage #1: 4-methyl-N-((perfluorophenyl)methylene)benzenesulfonamide With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 20℃; Inert atmosphere; Stage #2: 5,10-bis(pentafluorophenyl)tripyrrane In dichloromethane at 20℃; Darkness; Stage #3: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; Synthesis of meso-Pentafluorophenyl Substituted Expanded Porphyrins (4, 5, 6, 7, 8) from N-Sulfonyl Aldimine General procedure: 4-Methyl-N-((perfluorophenyl)methylene)benzenesulfonamide (0.062 g, 0.180mmol) and Cu(OTf)2 (0.0065 g, 0.018 mmol) were dissolved in CH2Cl2at room temperature and stirred for 30 minutes under nitrogen atmosphere. To this mixture was added meso-pentafluorophenyl substitutedtripyrrane (0.100 g, 0.180 mmol) in CH2Cl2 and themixture was stirred for 8 h in the dark. Then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) (0.082 g, 0.360 mmol) was added and the resulting mixture was stirred for 2h. Mixturewas eluted from a short column of silica gel to remove the tar. Solvent was removedunder reduced pressure and the residuewas purified by using column chromatography on silica gel(EtOAc:Hexane 1:50).
  • 24
  • [ 1266248-85-4 ]
  • [ 292164-60-4 ]
  • [ 25440-14-6 ]
  • [ 864429-34-5 ]
  • meso-octakis(pentafluorophenyl)octaphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 12% 2: 22% 3: 7% Stage #1: 4-methyl-N-((perfluorophenyl)methylene)benzenesulfonamide With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 20℃; Inert atmosphere; Stage #2: 5,10-bis(pentafluorophenyl)tripyrrane In dichloromethane at 20℃; Darkness; Stage #3: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; Synthesis of meso-Pentafluorophenyl Substituted Expanded Porphyrins (4, 5, 6, 7, 8) from N-Sulfonyl Aldimine General procedure: 4-Methyl-N-((perfluorophenyl)methylene)benzenesulfonamide (0.062 g, 0.180mmol) and Cu(OTf)2 (0.0065 g, 0.018 mmol) were dissolved in CH2Cl2at room temperature and stirred for 30 minutes under nitrogen atmosphere. To this mixture was added meso-pentafluorophenyl substitutedtripyrrane (0.100 g, 0.180 mmol) in CH2Cl2 and themixture was stirred for 8 h in the dark. Then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) (0.082 g, 0.360 mmol) was added and the resulting mixture was stirred for 2h. Mixturewas eluted from a short column of silica gel to remove the tar. Solvent was removedunder reduced pressure and the residuewas purified by using column chromatography on silica gel(EtOAc:Hexane 1:50).
  • 25
  • [ 1266248-85-4 ]
  • [ 292164-60-4 ]
  • C99H22F45N9 [ No CAS ]
  • [ 25440-14-6 ]
  • [ 864429-34-5 ]
YieldReaction ConditionsOperation in experiment
1: 11% 2: 25% 3: 7% Stage #1: 4-methyl-N-((perfluorophenyl)methylene)benzenesulfonamide With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 20℃; Inert atmosphere; Stage #2: 5,10-bis(pentafluorophenyl)tripyrrane In dichloromethane at 20℃; Darkness; Stage #3: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; Synthesis of meso-Pentafluorophenyl Substituted Expanded Porphyrins (4, 5, 6, 7, 8) from N-Sulfonyl Aldimine General procedure: 4-Methyl-N-((perfluorophenyl)methylene)benzenesulfonamide (0.062 g, 0.180mmol) and Cu(OTf)2 (0.0065 g, 0.018 mmol) were dissolved in CH2Cl2at room temperature and stirred for 30 minutes under nitrogen atmosphere. To this mixture was added meso-pentafluorophenyl substitutedtripyrrane (0.100 g, 0.180 mmol) in CH2Cl2 and themixture was stirred for 8 h in the dark. Then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) (0.082 g, 0.360 mmol) was added and the resulting mixture was stirred for 2h. Mixturewas eluted from a short column of silica gel to remove the tar. Solvent was removedunder reduced pressure and the residuewas purified by using column chromatography on silica gel(EtOAc:Hexane 1:50).
  • 26
  • [ 25440-14-6 ]
  • [ 445487-66-1 ]
YieldReaction ConditionsOperation in experiment
96% With nickel chloride pentahydrate In dimethyl sulfoxide at 154℃; for 3h; Synthesis of the porphyrin 4 100 mg (0.103 mmol) of meso-tetrakis(pentafluorophenyl)porphyrin (3)was dissolved in 40 mL of DMSO. 245 mg (1.03 mmol) of NiCl2.6H2O was added andthe reaction was stirred and heated at 154°C for 3h. The reaction was quenched with asaturated solution of NaHCO3 (20 mL) and extracted with EtOAc (3x30 mL). Theorganic phase was washed with H2O, dried over Na2SO4 and concentrated underreduced pressure. After crystallization from pentane, compound 4 was obtained in 96%yield (101.6 mg, 98,5μmol).1H NMR: (CDCl3, 400.15 MHz) δ (ppm): 8.78 (s, 8H).19F NMR: (CDCl3, 376.52 MHz) δ (ppm): -159.7 (dt, 8F, J = 6.1 Hz, J = 22.5 Hz, J =22.5 Hz), -149.76 (t, 4F, J = 21.0 Hz), -135.1 (dd, 8F, J1 = 23.0 Hz, J2 = 7.69 Hz),
  • 27
  • 2,3,4,5-tetra-O-acetyl-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • 5-[4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-2,3,5,6-tetrafluorophenyl]-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
24.9% With potassium carbonate In dimethyl sulfoxide at 50℃; for 8h; Syntheses of the Glycoconjugated Porphyrins; H21OAcGlc, cis-H22OAcGlc, trans-H22OAcGlc, H23OAcGlc, and H24OAcGlc General procedure: TFPP (208 mg, 214mol), AcGlcOH (226 mg, 650 mol), and K2CO3 (125 mg,906 mol) were dissolved in dimethyl sulfoxide (DMSO) (60 mL) and shaken for 8 h at 50 °C. The solution was diluted with ethyl acetate (100 mL) and washed with cold 1M HCl (aq) (100mL x 1) and brine (100mL x 3). The solution was dried over Na2SO4, and the solvent was removed under reduced pressure. The crude product was initially purified by column chromatography (silica gel, gradient from CH2Cl2 to CH2Cl2/ethyl acetate= 9/16/4, v/v). For cis-H22OAcGlc, and trans-cis-H22OAcGlc, further purification was performed by preparative HPLC (silicagel, CH2Cl2/ethyl acetate = 8/2, v/v) to separate each other. Finally, all compounds were purified by preparative GPC to H21OAcGlc (14.4 mg, 5.2%), cis-H22OAcGlc (39.3 mg,11.3%), trans-H22OAcGlc(26.4 mg, 7.6%), , H23OAcGlc (67.3 mg,16.1%), and , H24OAcGlc (18.6 mg, 3.8%) as purple solids.
  • 28
  • 2,3,4,5-tetra-O-acetyl-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • 5,10-bis[4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-2,3,5,6-tetrafluorophenyl]-15,20-bis(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
11.3% With potassium carbonate In dimethyl sulfoxide at 50℃; for 8h; Syntheses of the Glycoconjugated Porphyrins; H21OAcGlc, cis-H22OAcGlc, trans-H22OAcGlc, H23OAcGlc, and H24OAcGlc General procedure: TFPP (208 mg, 214mol), AcGlcOH (226 mg, 650 mol), and K2CO3 (125 mg,906 mol) were dissolved in dimethyl sulfoxide (DMSO) (60 mL) and shaken for 8 h at 50 °C. The solution was diluted with ethyl acetate (100 mL) and washed with cold 1M HCl (aq) (100mL x 1) and brine (100mL x 3). The solution was dried over Na2SO4, and the solvent was removed under reduced pressure. The crude product was initially purified by column chromatography (silica gel, gradient from CH2Cl2 to CH2Cl2/ethyl acetate= 9/16/4, v/v). For cis-H22OAcGlc, and trans-cis-H22OAcGlc, further purification was performed by preparative HPLC (silicagel, CH2Cl2/ethyl acetate = 8/2, v/v) to separate each other. Finally, all compounds were purified by preparative GPC to H21OAcGlc (14.4 mg, 5.2%), cis-H22OAcGlc (39.3 mg,11.3%), trans-H22OAcGlc(26.4 mg, 7.6%), , H23OAcGlc (67.3 mg,16.1%), and , H24OAcGlc (18.6 mg, 3.8%) as purple solids.
  • 29
  • 2,3,4,5-tetra-O-acetyl-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • 5,15-bis[4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-2,3,5,6-tetrafluorophenyl]-10,20-bis(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
7.6% With potassium carbonate In dimethyl sulfoxide at 50℃; for 8h; Syntheses of the Glycoconjugated Porphyrins; H21OAcGlc, cis-H22OAcGlc, trans-H22OAcGlc, H23OAcGlc, and H24OAcGlc General procedure: TFPP (208 mg, 214mol), AcGlcOH (226 mg, 650 mol), and K2CO3 (125 mg,906 mol) were dissolved in dimethyl sulfoxide (DMSO) (60 mL) and shaken for 8 h at 50 °C. The solution was diluted with ethyl acetate (100 mL) and washed with cold 1M HCl (aq) (100mL x 1) and brine (100mL x 3). The solution was dried over Na2SO4, and the solvent was removed under reduced pressure. The crude product was initially purified by column chromatography (silica gel, gradient from CH2Cl2 to CH2Cl2/ethyl acetate= 9/16/4, v/v). For cis-H22OAcGlc, and trans-cis-H22OAcGlc, further purification was performed by preparative HPLC (silicagel, CH2Cl2/ethyl acetate = 8/2, v/v) to separate each other. Finally, all compounds were purified by preparative GPC to H21OAcGlc (14.4 mg, 5.2%), cis-H22OAcGlc (39.3 mg,11.3%), trans-H22OAcGlc(26.4 mg, 7.6%), , H23OAcGlc (67.3 mg,16.1%), and , H24OAcGlc (18.6 mg, 3.8%) as purple solids.
  • 30
  • 2,3,4,5-tetra-O-acetyl-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • 5,10,15-tris[4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-2,3,5,6-tetrafluorophenyl]-20-pentafluorophenylporphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
16.1% With potassium carbonate In dimethyl sulfoxide at 50℃; for 8h; Syntheses of the Glycoconjugated Porphyrins; H21OAcGlc, cis-H22OAcGlc, trans-H22OAcGlc, H23OAcGlc, and H24OAcGlc General procedure: TFPP (208 mg, 214mol), AcGlcOH (226 mg, 650 mol), and K2CO3 (125 mg,906 mol) were dissolved in dimethyl sulfoxide (DMSO) (60 mL) and shaken for 8 h at 50 °C. The solution was diluted with ethyl acetate (100 mL) and washed with cold 1M HCl (aq) (100mL x 1) and brine (100mL x 3). The solution was dried over Na2SO4, and the solvent was removed under reduced pressure. The crude product was initially purified by column chromatography (silica gel, gradient from CH2Cl2 to CH2Cl2/ethyl acetate= 9/16/4, v/v). For cis-H22OAcGlc, and trans-cis-H22OAcGlc, further purification was performed by preparative HPLC (silicagel, CH2Cl2/ethyl acetate = 8/2, v/v) to separate each other. Finally, all compounds were purified by preparative GPC to H21OAcGlc (14.4 mg, 5.2%), cis-H22OAcGlc (39.3 mg,11.3%), trans-H22OAcGlc(26.4 mg, 7.6%), , H23OAcGlc (67.3 mg,16.1%), and , H24OAcGlc (18.6 mg, 3.8%) as purple solids.
  • 31
  • 2,3,4,5-tetra-O-acetyl-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-2,3,5,6-tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
16.1% With potassium carbonate In dimethyl sulfoxide at 50℃; for 8h; Syntheses of the Glycoconjugated Porphyrins; H21OAcGlc, cis-H22OAcGlc, trans-H22OAcGlc, H23OAcGlc, and H24OAcGlc General procedure: TFPP (208 mg, 214mol), AcGlcOH (226 mg, 650 mol), and K2CO3 (125 mg,906 mol) were dissolved in dimethyl sulfoxide (DMSO) (60 mL) and shaken for 8 h at 50 °C. The solution was diluted with ethyl acetate (100 mL) and washed with cold 1M HCl (aq) (100mL x 1) and brine (100mL x 3). The solution was dried over Na2SO4, and the solvent was removed under reduced pressure. The crude product was initially purified by column chromatography (silica gel, gradient from CH2Cl2 to CH2Cl2/ethyl acetate= 9/16/4, v/v). For cis-H22OAcGlc, and trans-cis-H22OAcGlc, further purification was performed by preparative HPLC (silicagel, CH2Cl2/ethyl acetate = 8/2, v/v) to separate each other. Finally, all compounds were purified by preparative GPC to H21OAcGlc (14.4 mg, 5.2%), cis-H22OAcGlc (39.3 mg,11.3%), trans-H22OAcGlc(26.4 mg, 7.6%), , H23OAcGlc (67.3 mg,16.1%), and , H24OAcGlc (18.6 mg, 3.8%) as purple solids.
  • 32
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis(pentafluorophenyl)chlorin [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With pyridine; potassium carbonate; toluene-4-sulfonic acid hydrazide at 105℃; Inert atmosphere; 1.2 The tetrakis(pentafluorophenyl)porphyrin (500 mg, 0.51 mmol) obtained in the step (1) and anhydrous potassium carbonate (380 mg, 2.75 mmol) were dissolved in anhydrous pyridine under nitrogen. Then p-toluenesulfonylhydrazide (475 mg, 2.55 mmol) was added and refluxed at 105 ° C to avoid completereaction. After the end of the reaction, it was detected that the absorption peak reached a maximum at 650 nm.Then, the reaction system was cooled to room temperature, and refluxed with ethyl acetate/water (2:1, 300 mL)for 1 hour. After the solution was cooled, the organic phase was washed successively with 6 mol/L hydrochloricacid, water, and saturated sodium hydrogen carbonate solution. The extract was dried over anhydrous sodiumsulfate and the solvent was evaporated. The obtained crude solid was subjected to silica gel columnchromatography, using dichloromethane/hexane (1:3, v/v) as eluent. After drying under vacuum, Compound 1,which is a near-infrared light absorbing photosensitizer 1 of the present invention, was obtained in a yield of 65%.
With palladium 10% on activated carbon; hydrogen In ethanol at 20 - 25℃; for 48h; Darkness; General procedure for hydrogenation of TPPF20: 20 mg of TPPF20 and 10 mg of Pd/C (10%) were suspended in 7 mL of the appropriate solvent and 0.7 mL of NEt3, when was the case. Hydrogen was bubbled directly into the stirred suspension at room temperature (20-25 °C) and protected from light. At the end ofthe reaction the catalyst was filtered off and washed with chloroform, followed byevaporation of the solvents at a low temperature (<60 °C). The crude product was fractionated by preparative TLC on silica-gel plates using a mixture of petroleum ether/chloroform 4:1 as the eluent. TPCF20: 1H-NMR = -1.53 (s, 2H, NH), 4.31 (s, 4H, CH2), 8.34 (d, J = 5.0, 2H, H-), 8.45(s, 2H, H-), 8.67 (d, J = 5.0, 2H, H-), 19F-NMR = -185.05 and -184.15 (2dt, J = 19.7and 5.6, 8F, F-meta), -175.58 and -175.35 (2t, J = 19.7, 4F, F-para), -161,41 and -160.47(2dd, J = 8.4 and 22.5, 8F, F-ortho), HRMS (ESI) m/z calcd. for C44H13F20N4 [M+H]+:977.0821, found: 977.0812, UV-vis(CHCl3) max/nm (log ) 406 (5.09), 505 (4.01), 656(4.59).TPIF20: 1H-NMR = 3.43 (s, 8H, CH2), 4.82 (br s, 2H, NH), 6.99 (d, J = 4.5, 2H, H-), 7.46(d, J = 4.5, 2H, H-), 19F-NMR = -185.17 to -185.03 (m, 2F, F-meta), -184.59 to -184.41(m, 4F, F-meta), -183.45 to -183.29 (m, 2F, F-meta), -175.66 (t, J = 19.8, 2F, F-para), -176.18 (t, J = 19.8, 1F, F-para), -175.75 (t, J = 19.8, 1F, F-para), -162.41 (dd, J = 8.5 and25.4, 2F, F-ortho), -162.04 (dd, J = 8.5 and 22.6, 4F, F-ortho), -161.66 (dd, J = 5.6 and22.6, 2F, F-ortho), HRMS (ESI) m/z calcd. for C44H15F20N4 [M+H]+: 979.0977, found:979.0967, UV-vis(CHCl3) max/nm (log ) 403 (4.56), 509 (3.70), 547 (3.84), 589 (4.07).
  • 33
  • [ 25440-14-6 ]
  • C44H14F20N4 [ No CAS ]
  • 5,10,15,20-tetrakis(pentafluorophenyl)chlorin [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium 10% on activated carbon; hydrogen; triethylamine In ethanol; N,N-dimethyl-formamide at 20 - 25℃; for 16h; Darkness; General procedure for hydrogenation of TPPF20: 20 mg of TPPF20 and 10 mg of Pd/C (10%) were suspended in 7 mL of the appropriate solvent and 0.7 mL of NEt3, when was the case. Hydrogen was bubbled directly into the stirred suspension at room temperature (20-25 °C) and protected from light. At the end ofthe reaction the catalyst was filtered off and washed with chloroform, followed byevaporation of the solvents at a low temperature (<60 °C). The crude product was fractionated by preparative TLC on silica-gel plates using a mixture of petroleum ether/chloroform 4:1 as the eluent. TPCF20: 1H-NMR = -1.53 (s, 2H, NH), 4.31 (s, 4H, CH2), 8.34 (d, J = 5.0, 2H, H-), 8.45(s, 2H, H-), 8.67 (d, J = 5.0, 2H, H-), 19F-NMR = -185.05 and -184.15 (2dt, J = 19.7and 5.6, 8F, F-meta), -175.58 and -175.35 (2t, J = 19.7, 4F, F-para), -161,41 and -160.47(2dd, J = 8.4 and 22.5, 8F, F-ortho), HRMS (ESI) m/z calcd. for C44H13F20N4 [M+H]+:977.0821, found: 977.0812, UV-vis(CHCl3) max/nm (log ) 406 (5.09), 505 (4.01), 656(4.59).TPIF20: 1H-NMR = 3.43 (s, 8H, CH2), 4.82 (br s, 2H, NH), 6.99 (d, J = 4.5, 2H, H-), 7.46(d, J = 4.5, 2H, H-), 19F-NMR = -185.17 to -185.03 (m, 2F, F-meta), -184.59 to -184.41(m, 4F, F-meta), -183.45 to -183.29 (m, 2F, F-meta), -175.66 (t, J = 19.8, 2F, F-para), -176.18 (t, J = 19.8, 1F, F-para), -175.75 (t, J = 19.8, 1F, F-para), -162.41 (dd, J = 8.5 and25.4, 2F, F-ortho), -162.04 (dd, J = 8.5 and 22.6, 4F, F-ortho), -161.66 (dd, J = 5.6 and22.6, 2F, F-ortho), HRMS (ESI) m/z calcd. for C44H15F20N4 [M+H]+: 979.0977, found:979.0967, UV-vis(CHCl3) max/nm (log ) 403 (4.56), 509 (3.70), 547 (3.84), 589 (4.07).
With palladium 10% on activated carbon; hydrogen In ethanol; N,N-dimethyl-formamide at 20 - 25℃; for 16h; Darkness; General procedure for hydrogenation of TPPF20: 20 mg of TPPF20 and 10 mg of Pd/C (10%) were suspended in 7 mL of the appropriate solvent and 0.7 mL of NEt3, when was the case. Hydrogen was bubbled directly into the stirred suspension at room temperature (20-25 °C) and protected from light. At the end ofthe reaction the catalyst was filtered off and washed with chloroform, followed byevaporation of the solvents at a low temperature (<60 °C). The crude product was fractionated by preparative TLC on silica-gel plates using a mixture of petroleum ether/chloroform 4:1 as the eluent. TPCF20: 1H-NMR = -1.53 (s, 2H, NH), 4.31 (s, 4H, CH2), 8.34 (d, J = 5.0, 2H, H-), 8.45(s, 2H, H-), 8.67 (d, J = 5.0, 2H, H-), 19F-NMR = -185.05 and -184.15 (2dt, J = 19.7and 5.6, 8F, F-meta), -175.58 and -175.35 (2t, J = 19.7, 4F, F-para), -161,41 and -160.47(2dd, J = 8.4 and 22.5, 8F, F-ortho), HRMS (ESI) m/z calcd. for C44H13F20N4 [M+H]+:977.0821, found: 977.0812, UV-vis(CHCl3) max/nm (log ) 406 (5.09), 505 (4.01), 656(4.59).TPIF20: 1H-NMR = 3.43 (s, 8H, CH2), 4.82 (br s, 2H, NH), 6.99 (d, J = 4.5, 2H, H-), 7.46(d, J = 4.5, 2H, H-), 19F-NMR = -185.17 to -185.03 (m, 2F, F-meta), -184.59 to -184.41(m, 4F, F-meta), -183.45 to -183.29 (m, 2F, F-meta), -175.66 (t, J = 19.8, 2F, F-para), -176.18 (t, J = 19.8, 1F, F-para), -175.75 (t, J = 19.8, 1F, F-para), -162.41 (dd, J = 8.5 and25.4, 2F, F-ortho), -162.04 (dd, J = 8.5 and 22.6, 4F, F-ortho), -161.66 (dd, J = 5.6 and22.6, 2F, F-ortho), HRMS (ESI) m/z calcd. for C44H15F20N4 [M+H]+: 979.0977, found:979.0967, UV-vis(CHCl3) max/nm (log ) 403 (4.56), 509 (3.70), 547 (3.84), 589 (4.07).
  • 34
  • C16H21N2O3P [ No CAS ]
  • [ 25440-14-6 ]
  • 5-(4-[2-(dibenzyloxyphosphorylamino)ethyl]amino}-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
20% In 1-methyl-pyrrolidin-2-one at 200℃; for 0.133333h; Microwave irradiation; General procedure for monosubstituted TPPF20 phosphoramidates 1a-c by microwave irradiation: General procedure: In a small vial 0.04 mmol (39.0 mg) of 5,10,15,20-tetrakispentafluorophenylporphyrin (TPPF20) and 0.10 mmol of the aminoalkyldibenzylphosphoramidate derivatives (32.0 mgfor n = 2; 34.8 mg for n = 4; 37.6 mg for n = 6) were dissolved in N-methyl-2-pyrrolidinone(NMP, 2.0 mL). The closed vial was irradiated in a microwave oven (Mileston, Microsynth,800 W, 1 bar, 200 °C,) for 2 min intervals, until no starting material was visualized by TLC(usually 8 min). The mixture was diluted with chloroform, washed with aqueous KHCO3solution (3 x 5 mL) and dried over Na2SO4. The solvent was evaporated under reduced pressure. The crude product was purified by silica-gel column chromatography using ethylacetate/petroleum ether 70% as the eluent. 5-(4-[2-(Dibenzyloxyphosphorylamino)ethyl]amino}-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (1a): Dark brown solid. Isolated yield 20%. 1H-NMR = -2.91 (s, 2H, NH), 3.23-3.39 (m, 3H, CH2NHP), 3.69-3.73 (m, 2H, CH2NHPh), 4.80 (br s,1H, CH2NHPh), 5.16 (d, J = 8.2, 4H, OCH2Ph), 7.35-7.47 (m, 10H, OCH2Ph), 8.85-9.01(m, 8H, H-). 19F-NMR = -185.10 to - 184.88 (m, 6F, F-meta), -183.86 (d, J = 16.9, 2F, Fmeta),-175.10 to -174.91 (m, 3F, F-para), -163.95 (dd, J = 5.6 and 16.9, 2F, F-ortho), -160.00 (dd, J = 7.1 and 22.5, 6F, F-ortho), 31P-NMR = 10.29, HRMS (ESI) m/z calcd. for C60H31F19N6O3P [M+H]+: 1275.1892, found: 1275.1886, UV-vis(CHCl3) max/nm (log )408 (5.06), 506 (4.01), 584 (3.52).
  • 35
  • C18H25N2O3P [ No CAS ]
  • [ 25440-14-6 ]
  • 5-(4-[2-(dibenzyloxyphosphorylamino)butyl]amino}-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% In 1-methyl-pyrrolidin-2-one at 200℃; for 0.133333h; Microwave irradiation; General procedure for monosubstituted TPPF20 phosphoramidates 1a-c by microwave irradiation: General procedure: In a small vial 0.04 mmol (39.0 mg) of 5,10,15,20-tetrakispentafluorophenylporphyrin (TPPF20) and 0.10 mmol of the aminoalkyldibenzylphosphoramidate derivatives (32.0 mgfor n = 2; 34.8 mg for n = 4; 37.6 mg for n = 6) were dissolved in N-methyl-2-pyrrolidinone(NMP, 2.0 mL). The closed vial was irradiated in a microwave oven (Mileston, Microsynth,800 W, 1 bar, 200 °C,) for 2 min intervals, until no starting material was visualized by TLC(usually 8 min). The mixture was diluted with chloroform, washed with aqueous KHCO3solution (3 x 5 mL) and dried over Na2SO4. The solvent was evaporated under reduced pressure. The crude product was purified by silica-gel column chromatography using ethylacetate/petroleum ether 70% as the eluent.
  • 36
  • C20H29N2O3P [ No CAS ]
  • [ 25440-14-6 ]
  • 5-(4-[6-(dibenzyloxyphosphorylamino)hexyl]amino}-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
24% In 1-methyl-pyrrolidin-2-one at 200℃; for 0.133333h; Microwave irradiation; General procedure for monosubstituted TPPF20 phosphoramidates 1a-c by microwave irradiation: General procedure: In a small vial 0.04 mmol (39.0 mg) of 5,10,15,20-tetrakispentafluorophenylporphyrin (TPPF20) and 0.10 mmol of the aminoalkyldibenzylphosphoramidate derivatives (32.0 mgfor n = 2; 34.8 mg for n = 4; 37.6 mg for n = 6) were dissolved in N-methyl-2-pyrrolidinone(NMP, 2.0 mL). The closed vial was irradiated in a microwave oven (Mileston, Microsynth,800 W, 1 bar, 200 °C,) for 2 min intervals, until no starting material was visualized by TLC(usually 8 min). The mixture was diluted with chloroform, washed with aqueous KHCO3solution (3 x 5 mL) and dried over Na2SO4. The solvent was evaporated under reduced pressure. The crude product was purified by silica-gel column chromatography using ethylacetate/petroleum ether 70% as the eluent.
  • 37
  • iron(II) chloride monohydrate [ No CAS ]
  • [ 25440-14-6 ]
  • [ 81245-20-7 ]
YieldReaction ConditionsOperation in experiment
With pyridine In N,N-dimethyl-formamide for 2h; Inert atmosphere; Reflux; 2 2.2 Synthesis of μ-O(FeTPFPP)2 The dimeric porphyrin was synthesized adding pyridine (0.42 mL, 5.20 mmol) and FeCl2·H2O (0.21 g, 0.16 mmol) to a DMF solution of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) (100 mg, 0.10 mmol) under argon atmosphere. The resulting mixture was refluxed and after one hour, more pyridine (0.42 mL, 5.2 mmol) and FeCl2·H2O (0.21 g, 0.16 mmol) were added to the reaction mixture, and the reflux continued for another hour. The mixture was allowed to cool to room temperature and left in contact with air for 18 h. Then, the solvents of the reaction mixture were evaporated to dryness. The resulting residue was poured into water and extracted three times with dichloromethane. The dichloromethane extract was dried with anhydrous Na2SO4 and it was evaporated to dryness to give a solid residue. Then, the residue was recrystallized from dichloromethane/n-hexane.
  • 38
  • [ 4556-23-4 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(4-pyridylsulfanyl)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In N,N-dimethyl-formamide at 40℃;
44% With diethylamine In N,N-dimethyl-formamide for 4h; Inert atmosphere; 5,10,15,20-Tetrakis[2,3,5,6-tetrafluoro-4-(N-methylpyridinium-4-ylsulfanyl)phenyl] porphyrin tetra-iodide (porphyrin 11) Porphyrin 11 was prepared exactly as described by Gomes et al (2011). This synthesis was generally based on the nucleophilic displaycement of the four p-fluorine atoms of 5,10,15,20-tetraquis(pentafluorophenyl)porphyrin (TPPPF) with 4-mercatopyridine. Intermediate 5,10,15,20-tetraquis[2,3,5,6-tetrafluor-4-(4-pyridylsulfanyl)phenyl]porfirina (TPPPF-SPyr) was then submitted to pyridine nitrogen cationization to give porphyrin 11. Detailed procedure to synthesize porphyrin 11 was as follows: Firstly, TPPPF was prepared by adding pentafluorbenzaldehyde (4 mL, 32 mmol) on a refluxing mixture of glacial acetic acid (200 mL) and nitrobenzene (150 mL). Pyrrole (2,5 mL, 36 mmol) was then added dropwise for 15 min and the resulting mixture was kept under reflux for one hour. Reaction mixture was then cooled to room temperature and the acetic acid and nitrobenzene were disttilled with reduced pressure. Residue was resuspended in chloroform and applied to a silica gel column with chloroform: petroleum ether (1:1) as eluent. Porphyrin fraction was concentrated and recrystalized from dichloromethane/petroleum ether (8% yield). Secondly, TPPPF-SPyr was then prepared from TPPPF (100.0 mg; 0.1 mmol) in dry DMF (5 mL) by adding 47 mg of 4-mercatopyridine (4.1 equivalents) and 1 mL of diethylamine. The resulting mixture was stirred under room temperature for 4 h, under argon, in an ice bath. Reaction mixture was then vacuum dried and the residue was chromatographed by preparative TLC, first eluted with petroleum ether followed by dichloromethane (for DMF removal), with fractioning being performed with dichloromethane: methanol (98:2). The fraction containing TPPPF-SPyr was crystallyzed from n-hexane and dichloromethane with 44% yield. 5,10,15,20-Tetrakis[2,3,5,6-tetrafluoro-4-(N-methylpyridinium-4-ylsulfanyl)phenyl] (porphyrin 11) was finally synthesized from a suspension of TPPPF-SPyr (75.0 mg, 56 mmol) in DMF (15 mL) added by 3 mL (48 mmol) of methyl iodide. The resulting mixture was kept under stirring from 24 h at 40 oC. Reaction mixture was then cooled to room temperature and the product (porphyrin 11) was precipitated with added diethyl ether, and then washed with cold diethyl ether (68 mg, 64%). 1H-NMR (DMSOd6) 9.66 (s, 8H, pyrrole); 8.97 (d, 8H, m-Ar); 8.48 (d, 8H, o-Ar); 4.38 (12H, CH3); -3.06 (s, 2H, NH). NMR spectral data of porphyrin 11 is in accordance with the following reference: Gomes, M. C.; Barreira, S. M. W.; Faustino, M. A. F.; Fernandes, R; Neves, M. G.; Tom, A. C.; Gomes, N. C. M.; Almeida, A.; Cavaleiro, J. A. S.; Cunha, A.; Tom, J. P. C. Photochem. Photobiol. Sci. 2011, 10, 1735-1743.
  • 39
  • [ 626-64-2 ]
  • [ 25440-14-6 ]
  • C64H26F16N8O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
14% With potassium carbonate In N,N-dimethyl-formamide at 40℃; for 1h; Inert atmosphere; Synthesis of porphyrin 3a to a solution of porphyrin 1 (TPPF20) (105 mg,0.1 mmol) in DMF (6.25 mL) 4-hydroxypyridine (40.2 mg, 0.4 mmol, 4.0 equiv)and anhydrous potassium carbonate (250 mg, 1.81 mmol, 18 equiv) wereadded. The mixture was kept under nitrogen atmosphere for one hour at 40 Cand the reaction monitored by TLC. After that time the starting compound 1was completely consumed and the reaction mixture showed five differentcompounds. Then the mixture was filtered from any solid and the filtrate wastreated with toluene upon which a precipitate was formed. This solid wasfiltered and submitted to column chromatography using dichloromethane/methanol as eluent applying a gradient of 95/5 to 85/15. The desired productwas obtained from the most polar fraction. After re-crystallization fromdichloromethane/petroleum ether 18 mg (yield 14%) of 3a was obtained. 1HNMR (DMSO-d6): d 3.03 (s, 2H, NH), 6.54 (d, J = 7.8 Hz, 8H, H-30,50 ), 8.18 (d,J = 7.8 Hz, 8H, H-20,60), 9.44 (s, 8H, b-pyrrolic). 19F NMR (DMSO-d6): d 172.64(dd, J = 25.3 and 10.0 Hz, 8F, Ar-m-F), 162.31 (dd, J = 25.3 and 10.0 Hz, 8F,Ar-o-F). 13C NMR (DMSO-d6): d 103.7 (s, 4C, C-meso), 118.5 (s, 8C, C-30 ), 119.5(t, J = 19.5 Hz, 4C, C-p-Ph), 122.9 (t, J = 14.2 Hz, 4C, C-N), 132.0-132.5 (m, 8H,b-pyrrolic), 141.2 (s, 8C, C-20 ), 141.4-147.2 (m, C-macrocycle), 177.4 (s, 4C,C-40 ). ESI-HRMS (m/z): calcd. for (M+H)+ 1275.1894, found 1275.1921.
  • 40
  • [ 25440-14-6 ]
  • nickel(II) acetylacetonate [ No CAS ]
  • [ 445487-66-1 ]
YieldReaction ConditionsOperation in experiment
97% In toluene for 96h; Reflux;
94% In toluene at 110℃; for 120h;
  • 41
  • [ 109-97-7 ]
  • [ 653-37-2 ]
  • [ 25440-14-6 ]
  • [ 864429-34-5 ]
  • meso-pentakis(pentafluorophenyl) N-fused [22]pentaphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 25% 2: 15% 3: 10% With sulfonated graphene In 1,2-dichloro-benzene at 20℃; for 2h; Inert atmosphere; 2.2 Reaction of pyrrole with aryl aldehydes inpresence of different carbocatalyst General procedure: 2.2a Method A: Reaction of pyrrole with aryl aldehyde:A mixture of pyrrole (276 μL, 4 mmol) and aldehyde (4 mmol) and sulfonated graphene 4 (170 mg)in o-DCB (60 mL) was stirred at room temperatureunder inert atmosphere for 2 h followed by addition ofDDQ with further stirring for 2 h. Progress of reactionwas monitored by TLC. After completion of reaction,catalyst was filtered and rinsed with chloroform followedby ethanol. DDQ (10 g) was then added in thereaction mixture with further stirring for 2 h. Reactionmixture was passed through a short alumina plug andthen chromatographed on silica gel 60-120 mesh (9:1hexane: ethyl acetate) to obtain mixture of desired productsleaving behind the polymeric materials. Repeatedchromatography of the mixture was done on silica gelusing hexane and chloroform (4:6) as eluent to obtainpurple (Rf = 0.8), blue (Rf = 0.6), violet (Rf = 0.5),red (Rf = 0.3) and dark green fraction (Rf = 0.1)solid. Mixture of hexaphyrins was further separated bypreparative TLC.
1: 20% 2: 14% 3: 8% With sulfonated graphene In dichloromethane at 20℃; for 2h; Inert atmosphere; 2.2 Reaction of pyrrole with aryl aldehydes inpresence of different carbocatalyst General procedure: 2.2a Method A: Reaction of pyrrole with aryl aldehyde:A mixture of pyrrole (276 μL, 4 mmol) and aldehyde (4 mmol) and sulfonated graphene 4 (170 mg)in o-DCB (60 mL) was stirred at room temperatureunder inert atmosphere for 2 h followed by addition ofDDQ with further stirring for 2 h. Progress of reactionwas monitored by TLC. After completion of reaction,catalyst was filtered and rinsed with chloroform followedby ethanol. DDQ (10 g) was then added in thereaction mixture with further stirring for 2 h. Reactionmixture was passed through a short alumina plug andthen chromatographed on silica gel 60-120 mesh (9:1hexane: ethyl acetate) to obtain mixture of desired productsleaving behind the polymeric materials. Repeatedchromatography of the mixture was done on silica gelusing hexane and chloroform (4:6) as eluent to obtainpurple (Rf = 0.8), blue (Rf = 0.6), violet (Rf = 0.5),red (Rf = 0.3) and dark green fraction (Rf = 0.1)solid. Mixture of hexaphyrins was further separated bypreparative TLC.
1: 20% 2: 14% 3: 10% With methanesulfonic acid In dichloromethane at 20℃; for 2h; Inert atmosphere; 2.2 Reaction of pyrrole with aryl aldehydes inpresence of different carbocatalyst General procedure: 2.2a Method A: Reaction of pyrrole with aryl aldehyde:A mixture of pyrrole (276 μL, 4 mmol) and aldehyde (4 mmol) and sulfonated graphene 4 (170 mg)in o-DCB (60 mL) was stirred at room temperatureunder inert atmosphere for 2 h followed by addition ofDDQ with further stirring for 2 h. Progress of reactionwas monitored by TLC. After completion of reaction,catalyst was filtered and rinsed with chloroform followedby ethanol. DDQ (10 g) was then added in thereaction mixture with further stirring for 2 h. Reactionmixture was passed through a short alumina plug andthen chromatographed on silica gel 60-120 mesh (9:1hexane: ethyl acetate) to obtain mixture of desired productsleaving behind the polymeric materials. Repeatedchromatography of the mixture was done on silica gelusing hexane and chloroform (4:6) as eluent to obtainpurple (Rf = 0.8), blue (Rf = 0.6), violet (Rf = 0.5),red (Rf = 0.3) and dark green fraction (Rf = 0.1)solid. Mixture of hexaphyrins was further separated bypreparative TLC.
  • 42
  • [ 653-37-2 ]
  • [ 167482-91-9 ]
  • C88H20F40N8 [ No CAS ]
  • [ 25440-14-6 ]
  • [ 864429-34-5 ]
YieldReaction ConditionsOperation in experiment
1: 28% 2: 16% 3: 10% With sulfonated graphene In 1,2-dichloro-benzene at 20℃; for 2h; Inert atmosphere; 2.2b Method B: Reaction of dipyrromethane with arylaldehyde General procedure: A mixture of dipyrromethane (2mmol),aryl aldehyde (2 mmol) and sulfonated graphene 4 (170mg) in o-DCB (30 mL) was taken in a round bottomflask under inert atmosphere for 2 h. Progressof reaction was monitored by TLC. After completionof reaction, catalyst was filtered and rinsed withchloroform followed by ethanol. DDQ (10 g) wasthen added in the reaction mixture with further stirringfor 2 h. Reaction mixture was passed througha short alumina plug and then chromatographed onsilica gel 60-120 mesh (9:1 hexane:ethyl acetate) toobtain mixture of desired products leaving behindthe polymeric materials. Repeated chromatographyof the mixture was done on silica gel using hexaneand chloroform (4: 6) as eluent to obtainpurple, blue, violet and green coloured fractions.Mixture of hexaphyrins was further separated bypreparative TLC.
  • 43
  • [ 25440-14-6 ]
  • [ 67-63-0 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(2-propyloxy)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With potassium hydroxide In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; regioselective reaction;
  • 44
  • [ 110-63-4 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(4-hydroxy-n-butyloxy)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With potassium hydroxide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; regioselective reaction;
78% With potassium hydroxide In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; 4.1 4.1. Preparation of 5,10,15,20-tetrakis-[4-(4-hydroxybutyloxy)-2,3,5,6-tetrafluorophenyl]- porphyrin In a typical experiment, 5, 10, 15,20-tetrakis(pentafluorophenyl)-porphyrin (110 mg, 113 μπιο) was dissolved in dry THF under argon atmosphere, KOH (1.43 g, 23.8 mmol) and butane- 1,4-diol (2.0 ml, 22.64 mmol) were added and the reaction mixture stirred under room temperature for 18 hours. After aqueous workup, extraction with DCM and drying with Na2S04, the crude product was purified by column cromatography (DCM/MeOH = 9: 1) and recrystallized (DCM/hexane) to obtain a purple solid (110 mg, 78%). 5,10,15,20-Tetrakis-[4-(4-hydroxybutyloxy)-2,3,5,6-tetrafluorophenyl]-porphyrin ^-NMR (500 MHz, acetone-d6): δ = -2.89 (s, 2H, NH , 1.84-1.90 (m, 8H, H-3), 2.07-2.13 (m, 8H, H-2), 3.72-3.77 (m, 8H, H-4), 4.66 (t, J = 6.5 Hz, 8H, H-l), 9.30 (s, 8H, ^-HPyirol) ppm. 13C-NMR (126 MHz, acetone-d6): δ = 26.8 (C-2), 29.0 (C-3), 61.2 (C-4), 75.7 (C-l), 104.6 (ArF- CMESO), 113.4 (t, 2JC-F = 19.7 Hz, ArF-C,pso), 139.2 (ArF-Cpara), 141.56 (dd, L'2JC.F = 246.6, 15.1 Hz, ArF- CMAA) 146.98 (d, LJC-F = 244.2 Hz, ArF-Cort0) ppm. 19F-NMR (376 MHz, acetone-d6): δ = -141.97 (dd, J = 21.5, 7.4 Hz, 8F, Ar-Fort0), -159.52 (dd, J = 21.9, 7.5 Hz, 8F, Ar-FM) ppm. HRMS (ESI-TOF): m/z calc. for C6oH47Fi6N408 [M + H]+: 1255.3133; found: 1255.3123. UV/Vis (DCM), max / nm (lg ε / L · mol · cm-1): 413.5 (5.47), 507.5 (5.35), 585 (3.90), 655 (3.27)
  • 45
  • [ 4221-99-2 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis{2,3,5,6-tetrafluoro-4-[(S)-2-butyloxy]phenyl}porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With potassium hydroxide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; regioselective reaction;
  • 46
  • [ 307-30-2 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(1H,1H-perfluorooctyloxy)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With potassium hydroxide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; regioselective reaction;
  • 47
  • [ 26690-80-2 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis{2,3,5,6-tetrafluoro-4-[2-(N-butyloxycarbonylamino)ethyloxy]phenyl}porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With potassium hydroxide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; regioselective reaction;
  • 48
  • [ 107-19-7 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(2-propynyloxy)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With potassium hydroxide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; regioselective reaction;
With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.416667h; Inert atmosphere;
  • 49
  • [ 25440-14-6 ]
  • [ 107-18-6 ]
  • 5,10,15,20-tetrakis[4-(prop-2-enyloxy)-2,3,5,6-tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With potassium hydroxide In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; regioselective reaction;
  • 50
  • [ 25440-14-6 ]
  • [ 100-79-8 ]
  • 5,10,15,20-tetrakis[4-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxy)-2,3,5,6-tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.75h; Inert atmosphere; regioselective reaction;
With potassium hydroxide In dimethyl sulfoxide at 20℃; for 2h; Inert atmosphere; 1.1.2 1.1.2 Preparation of 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(2,3-dihydroxypropyloxy)-phenyl]- porphyrin In a typical experiment, tetrakis(pentafluorophenyl)porphyrin (215 mg, 0.22 mmol) was dissolved in dry DMSO (4.0 ml) under argon atmosphere, KOH (210 mg, 3.74 mmol) and solketal (1.0 ml, 8.06 mmol) were added and the reaction mixture stirred under room temperature for 2 hours. After aqueous workup, extraction with ethyl acetate and drying with Na2S04, the crude product was purified by column cromatography (DCM/ethyl acetate = 85: 15) and recrystallized (acetone/hexane) to obtain the protected precursor as a purple solid. The solid was afterwards dissolved in a mixture of THF (20 ml) and MeOH (30 ml), TFA (5 ml) and HC1 (25%, 4 ml) were added and the mixture stirred for 2 h at room temperature. After aqueous workup, extraction with ethyl acetate and drying with Na2S04, the crude product was purified by reversed phase column cromatography (MeOH/ethyl acetate = 85: 15) and recrystallized (acetone/hexane) to obtain the product as a purple solid (145 mg, 114.8 μπιο, 52%). 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(2,3-dihydroxypropyloxy)-phenyl]-porphyrin ^-NMR (500 MHz, acetone-d6): δ = -2.89 (s, 2H, NH), 3.79-3.87 (m, 8H, OCH2), 3.99 (t, J = 5.7 Hz, 4H, β-ΟΗ , 4.20-4.25 (m, 4H, OCH2C//), 4.39 (d, J = 5.3 Hz, 4H, γ-ΟΗ), 4.62 (dd, J = 10.2, 6.2 Hz, 4H, ArF-OCH2), 4.74 (dd, J = 10.1, 4.3 Hz, 4H, ArF-OCH2), 9.30 (s, 8H, ^-HPyirole) ppm. 13C-NMR (126 MHz, acetone-d6): δ = 62.9 (OCH2), 63.0 (OCH2), 71.2 (OCH2CH), 71.3 (OCH2CH), 76.7 (ArF-OCH2), 104.6 (ArF-Cmeso), 113.4 (ArF-C,pso), 139.5 (t, 2JC.F = 12.1 Hz, ArF-Cpara), 141.4 (dd, 2J = 246.6, 15.2 Hz, ArF-CM), 146.9 (d, lJc.F = 243.8 Hz, ArF-Cort0) ppm. 19F-NMR (376 MHz, acetone-d6): δ = -141.72 (dd, J = 23.0 Hz, 2F, Ar-Fort0), -158.53 (dd, J = 23.1 Hz, Ar-Fmela) ppm. HRMS (ESI-TOF): m/z calc. for [M + H]+: 1263.2309; found: 1263.2233. UV-VIS (DCM), Amax [log ε (L · mol-1 · cm-1)]: 413 (3.99), 508 (3.85), 584 (3.41) nm.
  • 51
  • [ 5466-06-8 ]
  • [ 25440-14-6 ]
  • C49H19F19N4O2S [ No CAS ]
  • C54H28F18N4O4S2 [ No CAS ]
  • C54H28F18N4O4S2 [ No CAS ]
  • C59H37F17N4O6S3 [ No CAS ]
  • C64H46F16N4O8S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 5% 2: 30% 3: 12% 4: 37% 5: 13% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Darkness; 4.2 Reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (5) with ethyl 3-mercaptopropionate (11) Reaction conditions adapted from the literature [38-40]. In a 50 mL round-bottom flask equipped with nitrogen line and a stir bar, TFPP 5 (200 mg, 0.205 mmol) was dissolved in DMF (4 mL), diethylamine (Et2NH, 100 μL), and ethyl acetate (8 mL). To this was added ethyl 3-mercaptopropionate (11) (170 mg, ~6 equiv). Under N2 and shielded from light with aluminum foil, the reaction mixture was stirred at ambient temperature. The disappearance of the starting material/appearance of the products was monitored by TLC. Once no further progress of the reaction was detectable (after ~1/2 h), the reaction mixture was reduced to dryness by rotary evaporation. The residue was taken up in CH2Cl2 (25 mL) and the organic phase was washed with distilled water (at least 3×100 mL). The organic layer was isolated, dried over Na2SO4, and reduced to dryness by rotary evaporation. A gentle stream of N2 was passed over the residue for several h to ensure that it was thoroughly dried before it was purified by flash chromatography (silica gel-50% CH2Cl2/hexanes). Following the low polarity starting material 5 (~6.0 mg, ~3% recovery), four major fractions were isolated. The second fraction of 6btrans and 6bcis were isolated together (and subsequently separated using preparative plate chromatography using silica-25% hexanes/CH2Cl2). Thus, the five major products 6a (5%) 6btrans (30%), 6bcis (12%), 6c (37%), and 6d (13%) were isolated as dark purple solids. 6a: Rf (silica-CH2Cl2/25% hexanes)=0.85; 1H NMR (400 MHz; CDCl3): δ 8.97 (s, 6H), 4.32 (q, J=7.1Hz, 2H), 3.56 (t, J=7.0Hz, 2H), 2.95 (t, J=7.0Hz, 2H), 1.40 (t, J=7.1Hz, 3H),-2.84 (s, 2H) ppm; 19F NMR (376 MHz; CDCl3): δ-133.5 (dd, J=25.2, 12.4Hz, 2F),-136.5 (dd, J=23.8, 8.1Hz, 6F),-136.8 (dd, J=25.2, 12.1Hz, 2F),-151.3 (t, J=20.8Hz, 3F), -161.4 (td, J=22.0, 6.9Hz, 6F) ppm; 13C NMR (100 MHz; CDCl3): δ 171.2, 104.7, 103.6, 61.2, 35.4, 29.9, 14.3ppm; UV-vis (CH2Cl2) λmax (log): 412 (5.82), 507 (4.53), 584 (3.69) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I) 641, 706 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN): calculated for C49H19F19N4O2S [M+H]+, 1089.0900, found 1089.1000. 6btrans: Rf (silica-CH2Cl2/25% hexanes)=0.48; 1H NMR (400 MHz; CDCl3): δ 9.00 (d, J=4.6Hz, 2H), 8.93 (d, J=4.6Hz, 2H), 4.31 (q, J=7.1Hz, 2H), 3.55 (t, J=7.0Hz, 2H), 2.94 (t, J=7.0Hz, 2H), 1.38 (t, J=7.1Hz, 3H),-2.86 (s, 1H) ppm; 19F NMR (376 MHz; CDCl3): δ-133.6 (dd, J=25.1, 12.4Hz, 2F),-136.5 (dd, J=23.5, 8.0Hz, 2F),-136.9 (dd, J=25.3, 12.3Hz, 2F),-151.4 (t, J=20.9Hz, 1F),-161.4 (td, J=22.0, 6.8Hz, 2F) ppm; 13C NMR (100 MHz; CDCl3): δ 171.2, 104.6, 103.5, 61.2, 35.4, 29.9, 14.3ppm; UV-vis (CH2Cl2) λmax (log): 413 (5.52), 507 (4.08), 585 (3.70), 595 (3.30) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 642, 706 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN): calculated for C54H28F18N4O4S2 [M+H]+, 1203.1334, found 1203.1394. 6bcis: Rf (silica-CH2Cl2/25% hexanes)=0.42; 1H NMR (400 MHz; CDCl3): δ 9.01 (s, 2H), 8.95 (s, 2H), 4.31 (q, J=7.1Hz, 2H), 3.55 (t, J=7.0Hz, 2H), 2.94 (t, J=7.0Hz, 2H), 1.39 (t, J=7.1Hz, 3H),-2.84 (s, 1H) ppm; 19F NMR (376 MHz; CDCl3): δ-133.6 (dd, J=25.4, 12.2Hz, 2F),-136.5 (d, J=15.6Hz, 2H),-136.8 (dd, J=25.4, 12.2Hz, 2H),-151.4 (t, J=20.8Hz, 1H),-161.4 (t, J=18.1Hz, 2H) ppm; 13C NMR (100 MHz; CDCl3): δ 171.2, 104.6, 103.5, 61.2, 35.4, 29.9, 14.2ppm; UV-vis (CH2Cl2) λmax, nm (log): 415 (5.88), 508 (4.59), 582 (3.84) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 643, 706 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN): calculated for C54H28F18N4O4S2 [M+H]+, 1203.1334, found 1203.1297. 6c: Rf (silica-CH2Cl2/25% hexanes)=0.4; 1H NMR (400 MHz; CDCl3): δ 9.05 (s, 6H), 8.98 (d, J=4.7Hz, 2H), 4.33 (q, J=7.1Hz, 6H), 3.57 (t, J=7.0Hz, 6H), 2.96 (t, J=7.0Hz, 6H), 1.40 (t, J=7.1Hz, 9H),-2.79 (s, 2H) ppm; 19F NMR (376 MHz; CDCl3): δ-133.6 (dd, J=25.0, 12.2Hz, 6F),-136.5 (dd, J=23.5, 7.8Hz, 2F),-136.8 (dd, J=25.3, 12.3Hz, 6F),-151.4 (t, J=20.9Hz, 1F),-161.4 (td, J=22.1, 6.8Hz, 2F); 13C NMR (100 MHz; CDCl3): δ 171.2, 148.2, 147.6, 145.6, 145.1, 120.7, 116.0, 104.6, 103.5, 61.2, 35.4, 29.9, 14.3ppm; UV-vis (CH2Cl2) λmax, nm (log): 414 (5.69), 507 (4.34), 584 (3.30) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 643, 707 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN): calculated for C59H37F17N4O6S3 [M+H]+, 1317.1682, found 1317.1649. 6d: Rf (silica-CH2Cl2/25% hexanes)=0.20; 1H NMR (400 MHz; CDCl3): δ 9.00 (s, 4H), 4.31 (q, J=7.1Hz, 4H), 4.20 (q, J=7.1Hz, 1H), 3.55 (t, J=7.0Hz, 4H), 2.94 (t, J=7.0Hz, 4H), 1.38 (t, J=7.1Hz, 6H), 1.30 (t, J=7.1Hz, 1H),-2.82 (s, 1H) ppm; 19F NMR (376 MHz; CDCl3): δ-133.6 (dd, J=25.3, 12.3Hz, 1F),-136.8 (dd, J=25.1, 12.2Hz, 1F) ppm; 13C NMR (100 MHz; CDCl3): δ 171.2, 104.5, 61.2, 35.4, 29.9, 14.3ppm; UV-vis (CH2Cl2) λmax, nm (log): 415 (5.87), 508 (4.59), 583 (3.84); fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 645, 707 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN): calculated for C64H46F16N4O8S4 [M+H]+, 1431.3100, found 1431.2182.
  • 52
  • [ 25440-14-6 ]
  • [ 107-96-0 ]
  • 5-(4-[[(2-carboxyethyl)thio]-2,3,5,6-tetrafluorophenyl])-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere; Darkness; 4.2 Reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (5) with ethyl 3-mercaptopropionate (11) General procedure: Reaction conditions adapted from the literature [38-40]. In a 50 mL round-bottom flask equipped with nitrogen line and a stir bar, TFPP 5 (200 mg, 0.205 mmol) was dissolved in DMF (4 mL), diethylamine (Et2NH, 100 μL), and ethyl acetate (8 mL). To this was added ethyl 3-mercaptopropionate (11) (170 mg, ~6 equiv). Under N2 and shielded from light with aluminum foil, the reaction mixture was stirred at ambient temperature. The disappearance of the starting material/appearance of the products was monitored by TLC. Once no further progress of the reaction was detectable (after ~1/2 h), the reaction mixture was reduced to dryness by rotary evaporation. The residue was taken up in CH2Cl2 (25 mL) and the organic phase was washed with distilled water (at least 3×100 mL). The organic layer was isolated, dried over Na2SO4, and reduced to dryness by rotary evaporation. A gentle stream of N2 was passed over the residue for several h to ensure that it was thoroughly dried before it was purified by flash chromatography (silica gel-50% CH2Cl2/hexanes). Following the low polarity starting material 5 (~6.0 mg, ~3% recovery), four major fractions were isolated. The second fraction of 6btrans and 6bcis were isolated together (and subsequently separated using preparative plate chromatography using silica-25% hexanes/CH2Cl2). Thus, the five major products 6a (5%) 6btrans (30%), 6bcis (12%), 6c (37%), and 6d (13%) were isolated as dark purple solids.
30% With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h;
  • 53
  • [ 25440-14-6 ]
  • [ 107-96-0 ]
  • 5,10,15,20-tetrakis[4-(2-carboxyethyl)thio-2,3,5,6-tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
82.4% With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 1h;
40% With diethylamine In ethyl acetate; N,N-dimethyl-formamide at 20℃; for 4h; Inert atmosphere; Darkness; 4.2 Reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (5) with ethyl 3-mercaptopropionate (11) General procedure: Reaction conditions adapted from the literature [38-40]. In a 50 mL round-bottom flask equipped with nitrogen line and a stir bar, TFPP 5 (200 mg, 0.205 mmol) was dissolved in DMF (4 mL), diethylamine (Et2NH, 100 μL), and ethyl acetate (8 mL). To this was added ethyl 3-mercaptopropionate (11) (170 mg, ~6 equiv). Under N2 and shielded from light with aluminum foil, the reaction mixture was stirred at ambient temperature. The disappearance of the starting material/appearance of the products was monitored by TLC. Once no further progress of the reaction was detectable (after ~1/2 h), the reaction mixture was reduced to dryness by rotary evaporation. The residue was taken up in CH2Cl2 (25 mL) and the organic phase was washed with distilled water (at least 3×100 mL). The organic layer was isolated, dried over Na2SO4, and reduced to dryness by rotary evaporation. A gentle stream of N2 was passed over the residue for several h to ensure that it was thoroughly dried before it was purified by flash chromatography (silica gel-50% CH2Cl2/hexanes). Following the low polarity starting material 5 (~6.0 mg, ~3% recovery), four major fractions were isolated. The second fraction of 6btrans and 6bcis were isolated together (and subsequently separated using preparative plate chromatography using silica-25% hexanes/CH2Cl2). Thus, the five major products 6a (5%) 6btrans (30%), 6bcis (12%), 6c (37%), and 6d (13%) were isolated as dark purple solids.
  • 54
  • [ 3943-89-3 ]
  • [ 25440-14-6 ]
  • C53H20F18N4O4 [ No CAS ]
  • C53H20F18N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 2h; Darkness; 4.5 Reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (5) with ethyl 3,4-dihydroxybenzoate (10) Reaction conditions adapted from the literature [43]. 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin 5 (200 mg, 0.205 mmol) was dissolved in a 50 mL round-bottom flask equipped with a stir bar, reflux condenser, and heating mantle in N-methylpyrrolidone (25 mL) and K2CO3 (80 mg) was added. Ethyl 3,4-dihydroxybenzoate (10) (225 mg, 6equiv) was added to the mixture. Shielded from light with aluminum foil, the reaction mixture was stirred and heated to 100 °C. Once no further progress of the reaction was detectable by TLC (after ~2 h), CH2Cl2 (50 mL) was added to the cooled reaction mixture. After transfer to a separatory funnel, the mixture was extensively washed with distilled water (3×100 mL each). The organic layer was isolated, dried (Na2SO4), and the solvent was removed by rotary evaporation. A gentle stream of N2 for several hours ensured that the crude material was thoroughly dried. The crude material was purified by flash chromatography (silica gel-50% CH2Cl2/hexanes). The first low polarity fraction was recovered starting material 5H2 (~10 mg, 5% recovery), followed by four major fractions with increasing polarity were isolated to provide, after the removal of the solvents, 8a (17 %), 8b (presumably as a mixture of the trans and cis-isomers, 36 %), 8c (21 %), and 8d (4 %) as dark purple solids. 8a as a 2:1 mixture of isomers varying in the position of the ester functionality on the catechol moiety: Rf (silica-CH2Cl2/25% hexanes)=0.89; 1H NMR (400 MHz, CDCl3): δ 9.15 (d, J=4.7Hz, 2H), 9.01 (s, 6H), 7.96 (d, J=2.0Hz, 1H), 7.91 (d, J=2.0Hz), 7.89 (dd, J=2.0Hz, 1H), 7.84 (d, J=1.9Hz), 7.28 (d, J=8.6Hz), 7.17 (d, J=8.4Hz, 1H), 4.48 (q, J=6.4Hz, 2H), 4.43 (dd, J=12.8, 5.6Hz), 1.49 (t, J=7.2Hz, 3H), 1.44 (t, J=7.1Hz, 1H),-2.80 (s, 2H) ppm; 19F NMR (376 MHz; CDCl3): δ-136.5 (s, 6F),-136.7 (s, 1F),-139.1 (d, J=23.4Hz, 1F),-139.5 (d, J=23.3Hz),-151.4 (s, 3F),-161.4 (s, 6F),-162.1 (dd, J=23.4, 10.3Hz, 1F) ppm; 13C NMR (100 MHz; CDCl3): δ 164.9, 147.8, 145.4, 144.2, 141.0, 140.0, 138.9, 136.4, 128.0, 127.4, 118.56, 118.53, 117.1, 115.7, 114.0, 105.0, 103.5, 61.5, 14.33, 14.28ppm; UV-vis (CH2Cl2) λmax (log): 415 (5.37), 505 (4.25), 585 (3.81) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 641, 708 nm (1:2); HR-MS (ESI+, 1% CH3CN/CH2Cl2), calculated for C53H18F18N4O4 [M+H]+, 1117.1119, found 1117.1121. 8b as a 2:1 mixture of isomers varying in the position of the ester functionality on the catechol moiety: Rf (silica-CH2Cl2/25% hexanes)=0.55; 1H NMR (400 MHz; CDCl3): δ 9.15 (s, 2H), 8.99 (s, 2H), 7.95 (s, 1H), 7.90 (s), 7.87 (d, 8.3Hz, 1H) 7.83 (s), 7.28 (s), 7.16 (d, J=8.4Hz, 1H), 4.42 (q, 7.1Hz) 4.45 (q, J=16.6, 7.9Hz, 2H), 1.49 (t, J=7.2Hz, 3H), 1.44 (t, J=7.1Hz, 1H),-2.80 (s, 1H) ppm; 19F NMR (376 MHz; CDCl3): δ-136.5 (s, 2F),-136.7 (s, 1F),-139.0 (dd, 37.4, 15.8Hz, 1F),-139.5 (dd, 37.1, 15.3Hz),-151.5 (t, 20.53Hz, 1F),-161.5 (s, 2F),-162.2 (td, 21.8, 10.7Hz, 1F) ppm; 13C NMR (100 MHz; CDCl3): δ 164.9, 144.2, 143.8, 140.5, 140.0, 128.2, 127.9, 127.4, 127.2, 118.5, 117.1, 104.8, 103.2, 61.5, 14.3ppm; UV-vis (CH2Cl2) λmax (log): 415 (5.10), 510 (3.91), 585 (3.45) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 643, 707 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN), calculated for C62H26F16N4O8 [M+H]+, 1259.1573, found 1259.1612. 8c as a 2:1 mixture of isomers varying in the position of the ester functionality on the catechol moiety: Rf (silica-CH2Cl2/25% hexanes)=0.32; 1H NMR (400 MHz; CDCl3): δ 9.17 (s, 6H), 9.01 (d, J=4.6Hz, 2H), 7.95 (s, 3H), 7.90 (s), 7.87 (d, 8.0Hz, 3H), 7.86 (s, 1H), 7.84 (s), 7.26 (d, 8.4Hz), 7.16 (d, J=8.4Hz, 3H), 4.47 (q, J=7.1Hz, 6H), 1.47 (q, J=6.5Hz, 9H), 1.43 (t, J=7.1Hz, 1H),-2.77 (s, 2H) ppm; 19F NMR (376 MHz; CDCl3): δ-136.4 (2F),-136.6 (3F),-139.0 (3F),-139.4,-151.7 (t, 20.6Hz, 1F),-161.6 (2F),-162.3 (3F); UV-vis (CH2Cl2) λmax (log): 415 (5.49), 510 (4.40), 585 (3.92) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 643, 707 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN), calculated for C71H34F14N4O12 [M+H]+, 1401.2028, found 1401.2019. 8d as a 2:1 mixture of isomers varying in the position of the ester functionality on the catechol moiety: Rf (silica-CH2Cl2/25% hexanes)=0.16; 1H NMR (400 MHz; CDCl3): δ 9.06 (s, 4H), 7.91 (s, 2H), 7.88 (s), 7.84 (d, J=8.4Hz, 2H), 7.79 (s, 1H), 7.25 (d, J=8.5Hz, 1H), 7.14 (d, J=8.4Hz, 2H), 4.45 (q, J=7.2Hz, 4H), 1.47 (t, J=7.1Hz, 6H), 1.42 (t, J=7.1Hz, 2H),-2.84 (s, 1H) ppm; 19F NMR (376 MHz; CDCl3): δ-136.7 (s, 1F),-139.0 (s, 1F),-139.4 (s),-162.4 (dt, J=20.4, 10.5Hz, 1F) ppm; UV-vis (CH2Cl2) λmax (log): 415 (5.31), 510 (4.13), 585 (3.63) nm; fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax (rel. I): 644, 707 nm (1:2); HR-MS (ESI+, 1% CH2Cl2/CH3CN), calculated for C80H42F12N4O15 [M+H]+, 1542.2404, found 1542.2407.
  • 55
  • [ 3943-89-3 ]
  • [ 25440-14-6 ]
  • C51H16F18N4O4 [ No CAS ]
  • C51H16F18N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: Ethyl protocatechuate; tetrakis(pentafluorophenyl)porphyrin With potassium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 2h; Darkness; Stage #2: With lithium hydroxide In tetrahydrofuran; water for 4h; Darkness; Reflux; 4.6 Saponification of 8a and 8d Ethyl ester 8a or 8d (10 mg) was dissolved in a 50 mL round-bottom flask equipped with a stir bar, LiOH (20 mg), THF (5.0 mL) and water (5.0 mL). The flask was connected to reflux condenser, shielded from light with aluminum foil, and stirred and heated to reflux. TLC monitored the disappearance of the starting material. Once no further progress of the reaction was detectable (after ~4h), an acidic buffer (10 % NaH2PO4 acidified by KHSO4 until pH 2.5) was added to the crude reaction mixture and the product was extracted with CH2Cl2. The organic layer was washed with brine, dried over Na2SO4, and removed by rotary evaporation. The crude material was purified via chromatography (silica gel-5% MeOH/CH2Cl2) to obtain 9a or 9d, respectively, each in ~90% yield (~9.0mg). 9a: Rf (silica-5% MeOH/CH2Cl2)=0.54; 1H NMR (400 MHz; CD3OD): δ 9.12 (s, 10H), 7.84 (s, 1H), 7.78 (s, 1H), 7.73 (s, 1H), 7.23 (d, J=8.5Hz), 7.10 (d, J=8.4Hz, 1H); 19F NMR (376 MHz; CD3OD+CDCl3): δ-138.9,-141.0,-142.0,-142.3,-154.3,-159.6,-164.0,-164.6; UV-vis (CH2Cl2) λmax, nm (log): 413 (5.10), 506 (3.95), 583 (3.48); fluorescence emission (λexcitation=λSoret) (CH2Cl2) λmax: 641, 707 nm (1:2); HR-MS (ESI+, 100% CH3CN): calculated for C51H14F18N4O4 [M+H]+, 1089.0728, found 1089.0832. 9d: Rf (silica-10% MeOH/CH2Cl2)=0.34; 1H NMR (400 MHz; CD3OD): δ 9.24 (s, 3H), 7.83 (s, 1H), 7.79 (d, J=8.3Hz, 1H), 7.72 (s), 7.26 (d, J=8.5Hz), 7.14 (d, J=8.3Hz, 1H); 19F NMR (376 MHz; CD3OD+CDCl3): δ-137.8,-140.6,-141.0,-163.6; UV-vis (CH3OH) λmax, nm (log): 412 (5.33), 505 (4.13), 581 (3.65); fluorescence emission (λexcitation=λSoret) (CH3OH) λmax: 643, 707 nm (1:2); HR-MS (ESI+, 100% CH3CN): calculated for C76H42F12N4O16 [M+H]+, 1431.1152, found 1431.1230.
  • 56
  • [ 1074-36-8 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis(4-carboxyphenylthio-2,3,5,6-tetrafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% The protons signal relative to N-H was not observed, due to their replacement by deuterium from deuterated methanol in porphyrins P2-P6. Finally, the fifth fraction was identified as porphyrin P6 (3.1% yield), m.p. > 300 C, 1H NMR: deltaH ppm (Acetone-d6) 9.46 (broad, 8H, H-beta), 8.14 (d, J = 8.4 Hz, 8H, S-C6H4-CO2H), 7.82 (d, J = 8.3 Hz, 8H, S-C6H4-CO2H), and -2.87 (s, 2H, NH). 19F NMR: deltaF ppm (Acetone-d6) -162.02 (dd, J = 11.9 and 24.7 Hz, 8F, F-meta), and -157.70 (dd, J = 11.9 and 24.7 Hz, 8F, F-ortho). UV-vis (Acetone) lambdamax, nm (log ?): 412 (5.14), 504 (4.07), 582 (3.57). HRMS (FAB+) m/z: calcd for C72H31F16N4O8S4 (M+H)+: 1511.0764; found: 1511.0752.
  • 57
  • manganese(II) chloride tetrahydrate [ No CAS ]
  • [ 25440-14-6 ]
  • Mn(5,10,15,20-tetrakis (pentafluorophenyl)porphyrin) manganese chloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium acetate In N,N-dimethyl-formamide at 80℃; for 2h; Inert atmosphere; Reflux; 2.2.3. Synthesis of porphyrins and metalloporphyrins The free base porphyrin [5,10,15,20-tetrakis (pentafluorophenyl)porphyrin] (H2TF20PP) was prepared according to an established procedure [16]. For the metallation of H2TF20PP[17], in a three-neck flask, 200 mg of H2TF20PP and 1 g ofCH3COONa were dissolved in 100 mL of DMF. Manganese chloride tetrahydrate (20 mmol) was added, and the mixture was refluxed at 80 °C under a nitrogen atmosphere for 2 h. After cooling the resulting solution to room temperature, the product was collected by centrifugation and washed with DMF and water, and the product was labeled as TF20PPMnCl.
  • 58
  • [ 142-71-2 ]
  • [ 25440-14-6 ]
  • [ 27882-93-5 ]
YieldReaction ConditionsOperation in experiment
96% In methanol; chloroform at 20℃; Metalloporphyrin. General procedure: A solution of freebase (100 mg) and Cu(OAc)2 (400 mg) in 30 mL CHCl3 and 10 mL MeOH was stirred at room temperature until the fluorescence was disappeared. Then the reaction mixture was concentrated in a vacuum, obtained solid was purified by flash column chromatography on silica gel. Recrystallization from DCM/n-hexane affords the metalloporphyrin complex.
In N,N-dimethyl-formamide at 120℃; for 3h;
With sodium acetate In N,N-dimethyl-formamide for 3h; Reflux; Inert atmosphere; (iii) Preparation of manganese, iron, and copper porphyrins (MPx): General procedure: Copper was also inserted into porphyrins P1 and P6, using copper(II) acetate, DMF as solvent, and reaction time of 3h, to give CuP1 and CuP6. After metal insertion, the solvents were removed under vacuum. The resulting solids were thoroughly washed with water, to remove excess metal salts. The complexes were purified by column chromatography using dichloromethane as eluent. The preparation of CuP2 was not performed in this stage, since the material amount (free base porphyrin) was insufficient.
  • 59
  • 1-mercapto-1-carba-closo-dodecaborate [ No CAS ]
  • [ 25440-14-6 ]
  • tetracesium {5,10,15,20-tetrakis[4-(1'-carba-closo-dodecaboran-1'-ylthio)tetrafluorophenyl]porphyrin} (4-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With sodium acetate In N,N-dimethyl-formamide at 40℃; for 30h; Inert atmosphere; General procedure: To a solution of porphyrin 1 or 8-10 (0.05 mmol) in anhydrous DMF (10 mL), carborane 11 (0.4 mmol) and anhydrous NaOAc (0.1 mmol) were added under argon. The reaction mixture was stirred for 30 h at 40 °C and the solvent was removed in vacuo. Purification of the residue by silica gel (L 40×60) column chromatography (successive elution with chloroform, chloroform-acetone (5 : 2), and chloroform-acetone (1 : 1)) afforded target compound.
  • 60
  • [ 64493-43-2 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[4-(o-carboran-9'-ylthio)tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
81.7% With sodium acetate In N,N-dimethyl-formamide at 40℃; for 30h; Inert atmosphere; Synthesis of boronated porphyrins 5-7 (general procedure) General procedure: To a solution of porphyrin 1 (0.05 mmol) in DMF (10 mL), the corresponding mercaptocarborane 2-4 (0.4 mmol) and anhydrous NaOAc (0.1 mmol) were added under argon. The reaction mixture was stirred for 30 h at 40 °C and poured in water. The mixture was extracted with ethyl acetate, the organic layer was separated, and the solvent was removed in vacuo. Purification of the residue by silica gel (L 40×60) column chromatography (successive elution with chloroform, chloroform-acetone (5 : 1), and chloroform-acetone (5 : 2)) afforded target compound.
  • 61
  • [ 64493-44-3 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[4-(m-carboran-9'-ylthio)tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
86.5% With sodium acetate In N,N-dimethyl-formamide at 40℃; for 30h; Inert atmosphere; Synthesis of boronated porphyrins 5-7 (general procedure) General procedure: To a solution of porphyrin 1 (0.05 mmol) in DMF (10 mL), the corresponding mercaptocarborane 2-4 (0.4 mmol) and anhydrous NaOAc (0.1 mmol) were added under argon. The reaction mixture was stirred for 30 h at 40 °C and poured in water. The mixture was extracted with ethyl acetate, the organic layer was separated, and the solvent was removed in vacuo. Purification of the residue by silica gel (L 40×60) column chromatography (successive elution with chloroform, chloroform-acetone (5 : 1), and chloroform-acetone (5 : 2)) afforded target compound.
  • 62
  • 7-isopropyl-1-mercapto-m-carborane [ No CAS ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetrakis[4-(7'-isopropyl-m-carboran-1'-ylthio)tetrafluorophenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
69.5% With sodium acetate In N,N-dimethyl-formamide at 40℃; for 30h; Inert atmosphere; Synthesis of boronated porphyrins 5-7 (general procedure) General procedure: To a solution of porphyrin 1 (0.05 mmol) in DMF (10 mL), the corresponding mercaptocarborane 2-4 (0.4 mmol) and anhydrous NaOAc (0.1 mmol) were added under argon. The reaction mixture was stirred for 30 h at 40 °C and poured in water. The mixture was extracted with ethyl acetate, the organic layer was separated, and the solvent was removed in vacuo. Purification of the residue by silica gel (L 40×60) column chromatography (successive elution with chloroform, chloroform-acetone (5 : 1), and chloroform-acetone (5 : 2)) afforded target compound.
  • 63
  • [ 51921-56-3 ]
  • [ 25440-14-6 ]
  • [ 109781-47-7 ]
YieldReaction ConditionsOperation in experiment
78% With sodium proprionate In chlorobenzene for 27h; Reflux; Synthesis of [5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinato]platinum(II) (1g(Pt)). A mixture of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (1g(2H)) (39.0mg, 0.040 mmol), PtCl2(PhCN)2 (2d) (37.8 mg, 0.080mmol), and sodium propionate (19.2 mg, 0.20mmol) in chlorobenzene (1 mL) was refluxed for 23.5 h under atmospheric conditions. PtCl2(PhCN)2 (2d) (9.4 mg, 0.020 mmol) was added to the resultant solution, and the mixture was further refluxed for 2 h. Again, PtCl2(PhCN)2 (2d) (9.4 mg, 0.020 mmol) was added to the resultant solution, and the mixture was further refluxed for 1.5 h. The reaction mixture was directly poured on top of a silica gel column, and then eluted with toluene. After the removal of solvent under reduced pressure, acetonitrile (10 mL) and concentrated HCl (3 drops) was added to the crude product. The resultant suspension was stirred at 60 °C for 15 min, and then cooled to room temperature. The precipitate was collected by filtration, washed with acetonitrile, and dried under vacuum to give 1g(Pt) as reddish purple powder (36.5 mg, 0.031mmol, 78%). Spectral data were consistent with thepreviously reported one.S12 1HNMR(500MHz, CDCl3) δ (ppm)= 8.82 (s + d, J4(195Pt-H) = 9.8 Hz, 8H, PorHβ).
  • 64
  • [ 3144-09-0 ]
  • [ 25440-14-6 ]
  • 5-[(2',3',5',6'-tetrafluoro-4'-methanesulfamoyl)phenyl]-10,15,20-tri-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
19% With caesium carbonate In 1,4-dioxane at 100℃; 4.4 Synthesis of meso-sulfonamide perfluorophenylporphyrins using Method A General procedure: In a round bottom flask containing 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (100 mg; 1.02×10-4mol) (1) and the desired sulfonamide (2a-c) (porphyrin/sulfonamide 1:6 mol) was dissolved in dioxane (20 ml) and cesium carbonate (6.15×10-4mol) was added. The reaction mixture was stirred at 100°C along 2-4 days until no further evolution reaction by TLC. The crude was washed with a saturated solution of sodium bicarbonate (6×) and then with water (6×) and dried over anhydrous Na2SO4. The solvent was evaporated in a rotary evaporator and the resulting solid dissolved in dichloromethane and purified by silica gel column chromatography using hexane/ethyl acetate (2:1) as eluent, followed by preparative silica gel thin layer chromatography (PrepTLC).
  • 65
  • [ 3144-09-0 ]
  • [ 25440-14-6 ]
  • 5,10,15,20-tetra-[(2',3',5',6'-tetrafluoro-4'-methanesulfamoyl)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With caesium carbonate In 1,4-dioxane at 100℃; for 48h; 4.5 Synthesis of meso-sulfonamide perfluorophenylporphyrins using Method B General procedure: In a round bottom flask, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (30 mg; 3.07×10-5mol) (1) and methanesulfonamide (porphyrin/sulfonamide 1:18 mol equivalents) (2a) were dissolved in dioxane (2 ml) and cesium carbonate (3.69×10-4mol) was added. The reaction mixture was stirred at 100°C for 2 days until complete consumption of starting material was observed by TLC. The crude was washed with acetone and the resulting precipitate was purified using the Amicon device (10 kDa membranes).
  • 66
  • [ 70-55-3 ]
  • [ 25440-14-6 ]
  • C58H26F18N6O4S2 [ No CAS ]
  • 5,15-[(2',3',5',6'-tetrafluoro-4'-p-toluenesulfamoyl)phenyl]-10,20-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
  • 5-[(2',3',5',6'-tetrafluoro-4'-p-toluenesulfamoyl)phenyl]-10,15,20-tri-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
4.5% With caesium carbonate In 1,4-dioxane at 100℃; 4.4 Synthesis of meso-sulfonamide perfluorophenylporphyrins using Method A General procedure: In a round bottom flask containing 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (100 mg; 1.02×10-4mol) (1) and the desired sulfonamide (2a-c) (porphyrin/sulfonamide 1:6 mol) was dissolved in dioxane (20 ml) and cesium carbonate (6.15×10-4mol) was added. The reaction mixture was stirred at 100°C along 2-4 days until no further evolution reaction by TLC. The crude was washed with a saturated solution of sodium bicarbonate (6×) and then with water (6×) and dried over anhydrous Na2SO4. The solvent was evaporated in a rotary evaporator and the resulting solid dissolved in dichloromethane and purified by silica gel column chromatography using hexane/ethyl acetate (2:1) as eluent, followed by preparative silica gel thin layer chromatography (PrepTLC).
  • 67
  • [ 25440-14-6 ]
  • [ 640-61-9 ]
  • 5,10-[(2',3',5',6'-tetrafluoro-4'-N-methyl-p-toluenesulfamoyl)phenyl]-15,20-dis-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
  • 5,15-[(2',3',5',6'-tetrafluoro-4'-N-methylptoluenesulfamoyl)phenyl]-10,20-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
  • 5,10,15-tri-[(2',3',5',6'-tetrafluoro-4'-N-methyl-p-toluenesulfamoyl)phenyl]-20-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
  • 5-[(2',3',5',6'-tetrafluoro-4'-N-methyl-p-toluenesulfamoyl)phenyl]-10,15,20-tri-[(2',3',4',5',6'-pentafluoro)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 3.1% 2: 0.6% With caesium carbonate In 1,4-dioxane at 100℃; 4.4 Synthesis of meso-sulfonamide perfluorophenylporphyrins using Method A General procedure: In a round bottom flask containing 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (100 mg; 1.02×10-4mol) (1) and the desired sulfonamide (2a-c) (porphyrin/sulfonamide 1:6 mol) was dissolved in dioxane (20 ml) and cesium carbonate (6.15×10-4mol) was added. The reaction mixture was stirred at 100°C along 2-4 days until no further evolution reaction by TLC. The crude was washed with a saturated solution of sodium bicarbonate (6×) and then with water (6×) and dried over anhydrous Na2SO4. The solvent was evaporated in a rotary evaporator and the resulting solid dissolved in dichloromethane and purified by silica gel column chromatography using hexane/ethyl acetate (2:1) as eluent, followed by preparative silica gel thin layer chromatography (PrepTLC).
  • 68
  • cobalt(II) chloride hexahydrate [ No CAS ]
  • [ 25440-14-6 ]
  • [ 52242-06-5 ]
YieldReaction ConditionsOperation in experiment
90% With sodium acetate; acetic acid for 1h; Reflux; Synthesis of the Catalyst CoP2 Perfluorinated tetraphenylporphyrin TPPH2F20 (0.5 mmol, 480 mg) was refluxed in acetic acid (300 mL) with an excess of CoCl2*6H2O (2.6 mmol, 620 mg) and sodium acetate (15 mmol, 1.24 g) for 1 h. The mixture was allowed to cool down and the solvent was evaporated until most solids precipitated out. The red solids thus obtained were washed with water, aqueous sodium bicarbonate and finally with a minimum amount of cold methanol. The solid was then dried in-vacuo to give CoP2 (90% yield). UV-vis spectrum (THF), λmax/nm: 408, 520, 558.
With sodium acetate; acetic acid for 1h; Reflux;
  • 69
  • [ 25440-14-6 ]
  • [ 534-03-2 ]
  • 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(1,3-dihydroxyprop-2-ylamino)phenyl]porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% In dimethyl sulfoxide at 100℃; for 4h; Inert atmosphere; General procedure for the functionalization of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with amines: General procedure: First, the porphyrin wasdissolved in dry DMSO in a three-necked round bottom flask equippedwith argon gas inlet and magnetic stirrer. Then, the respective aminewas added, and the reaction was stirred for 4 h at 100 C. Afterextraction with ethyl acetate and aqueous workup, the organic phasewas dried with sodium sulfate, filtered and the solvent evaporated. Thecrude product was purified by column chromatography (silica gel,DCM/MeOH, 85:15 - 8:2). The product fraction was evaporated todryness, treated with dichloromethane and suction filtered.
54% In dimethyl sulfoxide at 100℃; for 4h; 1.4 1.4. Preparation of 5,10,15,20-tetrakis-[2,3,5,6-tetrafluoro-4-(l,3-dihydroxyprop-2-ylamino)- phenyl] -porphyrin In a typical experiment, tetrakis(pentafluorophenyl)porphyrin (107 mg, 0.109 mmol) was dissolved in a two-necked round bottom flask with dry DMSO (2.0 ml), 2-Amino-l,3-dihydroxy- propane (260 mg, 2.85 mmol) was added and the reaction mixture stirred at 100 °C for 4 hours. After aqueous workup, extraction with ethyl acetate and drying with Na2S04, the crude product was purified by reversed phase column cromatography (MeOH/H20 = 85: 15) and recrystallized (MeOH/H20) to obtain a purple solid (77.0 mg, 59.8 μτηο, 54%). 5,10,15,20-tetrakis-[2,3,5,6-tetrafluoro-4-(l,3-dihydroxyprop-2-ylamino)-phenyl]- porphyrin ^-NMR (500 MHz, acetone-d6): δ = -2.82 (s, 2H, NH), 3.94-4.08 (m, 16H, OCH2), 4.17 (dp, J = 9.9, 5.1 Hz, 4H, NHCtf), 4.25 (t, J = 5.5 Hz, 8H, OH), 5.30 (dt, 3J„.„ = 9.8, %.F = 3.0 Hz, 4H, NH), 9.25 (s, 8H, y?-HpylTOie) ppm. 13C-NMR (126 MHz, acetone-d6): δ = 58.8 (NH-CH), 62.7 (OCH2), 62.8 (OCH2), 106.0 (ArF-Cmeso), 107.2 (t, 2JC-F = 20.1 Hz, ArF-C,pso), 130.5 (t, J = 11.5 Hz, ArF-Cpara), 132.7 0-CPyirole), 138.3 (dd, L'2JC. F = 238.8, 16.0 Hz, ArF-CM), 147.8 (d, LJC.F = 238.8 Hz, ArF-Cort0) ppm. 19F-NMR (376 MHz, acetone-d6): δ = -143.38 (d, J = 16.1 Hz, 4F, Ar-Fort0), -161.29 (d, J = 19.3 Hz, 4F, Ar-Fmem) ppm. HRMS (ESI-TOF): m/z calc. for [M + H]+: 1259.2948; found: 1259.3045. UV-VIS (DCM), Amax [log ε (L · mol · cm-1)]: 417 (5.42), 509 (4.38), 544 (3.82), 586 (3.88), 648 (3.07) nm.
  • 70
  • [ 25440-14-6 ]
  • [ 60-24-2 ]
  • 5-(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin [ No CAS ]
  • 5,15-bis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin [ No CAS ]
  • 5,10-bis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin [ No CAS ]
  • 5,10,15-tris(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-20-pentafluorophenylporphyrin [ No CAS ]
  • 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 43% 2: 27% 3: 15% 4: 10% 5: 6% With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 20h; 2.3. General Synthesis of TFPPs Bearing 2-Hydroxyethylthio Groups A typical procedure was as follows: TFPP (687 mg, 705 μmol) anddry N,N-dimethylformamide (DMF, 70 mL) were placed into a 100 mLflask and sealed with a rubber septum. 2-Hydroxyethanethiol (148 μL,2.13 mmol) and diisopropylethylamine (400 μL) were added to the solution.The mixture was stirred at ambient temperature for 20 h in thedark. The reaction mixture was poured into water (70 mL) and extractedwith chloroform (20 mL × 3). The combined organics were washedwith water and brine. After drying over anhydrous sodium sulfate, thesolvent was evaporated under reduced pressure. The residue was purifiedby silica gel column chromatography using chloroform containingmethanol (from 0 to 3 vol%) as an eluent to give 1ME (44.9 mg,43.5 μmol), trans-2ME (77.2 mg, 70.8 μmol), cis-2ME (122 mg,112 μmol), 3ME (363 mg, 316 μmol) and 4ME (237 mg, 196 μmol). 2.3.1. 5-(4-(2-Hydroxyethylthio)-2,3,5,6-Tetrafluorophenyl)-10,15,20-Tris(Pentafluorophenyl)Porphyrin (1ME)Purity(HPLC): N99%. TLC (silica gel, CHCl3/CH3OH = 9/1, v/v): Rf =0.59. ESI-TOF HRMS: m/z for C46H15N4F19OSNa ([M + Na]+) calcd1055.05609; found 1055.05619 (error 0.10 mmu, 0.10 ppm). 1H NMR(acetone-d6, 500 MHz, acetone-d5H = 2.04 ppm): δ (ppm) = 9.37 (s,8H, β-pyrroleH), 4.24 (t, 3J = 5.65 Hz, 1H, -OH), 4.01 (q, 3J = 6.10 Hz,2H, -CH2OH), 3.43 (t, 3J = 6.33 Hz, 2H, -SCH2-), -2.91 (s, 2H, NH).19F NMR (acetone-d6, 470.34 MHz, CF3CO2H = -76.55 ppm): δ(ppm) = -135.46 (dd, 3JF-F = 24.8 Hz, 5JF-F = 11.4 Hz, 2F, 5-(2,6- or3,5-PhF)), -139.61 (dd, 3JF-F = 22.9 Hz, 5JF-F = 7.63 Hz, 6F, 10,15,20-(2,6-PhF)), -139.99 (dd, 3JF-F=25.3 Hz, 5JF-F=11.9 Hz, 2F, 5-(3,5- or2,6-PhF)), -155.15 (t, 3JF-F = 20.5 Hz, 2F, 10,20-(4-PhF)), -155.17 (t,3JF-F = 20.5 Hz, 1F, 15-(4-PhF)), -164.21 (dt, 3JF-F = 21.5 Hz (t), 5JFF= 6.36 Hz (d), 6F, 10,15,20-(3,5-PhF)). UV-vis (c = 2 μM, DMSO,path length = 1 cm, 25 °C): λ/nm (ε × 10-3/M-1 cm-1) = 412.0(299), 505.5 (21.3), 536 (2.51), 579.5 (6.88).2.3.2. 5,15-Bis(4-(2-Hydroxyethylthio)-2,3,5,6-Tetrafluorophenyl)-10,20-Bis(Pentafluorophenyl)Porphyrin (Trans-2ME)Purity(HPLC): N99%. TLC (silica gel): Rf=0.55 (CHCl3/CH3OH=9/1,v/v) and Rf=0.36 (CHCl3/CH3OH=100/5, v/v). ESI-TOF HRMS:m/z forC48H20N4F18O2S2Na ([M+Na]+) calcd 1113.06379; found 1113.06322(error -0.58 mmu, -0.52 ppm). 1H NMR (acetone-d6, 500 MHz, acetone-d5H = 2.04 ppm): δ (ppm) = 9.36 (s, 8H, β-pyrroleH), 4.24 (t,3J = 5.65 Hz, 2H, -OH), 4.01 (q, 3J = 6.08 Hz, 4H, -CH2OH), 3.43 (t,3J = 6.33 Hz, 4H, -SCH2-), -2.90 (s, 2H, NH). 1H NMR (C6D6,500 MHz, C6HD5 = 7.15 ppm): δ (ppm) = 8.80 (d, 3J = 4.70 Hz, 4H,β-pyrroleH), 8.63 (d, 3J = 4.70 Hz, 4H, β-pyrroleH), 3.47 (t, 3J =5.15 Hz, 4H, -CH2OH), 2.83 (t, 3J = 5.85 Hz, 4H, -SCH2-), 1.17 (s, 2H,-OH), -3.25 (s, 2H, NH). 19F NMR (acetone-d6, 470.34 MHz,CF3CO2H =-76.55 ppm): δ (ppm) = -135.47 (dd, 3JF-F = 25.3 Hz,5JF-F = 11.9 Hz, 4F, 5,15-(2,6- or 3,5-PhF)), -139.61 (dd, 3JF-F =23.8 Hz, 5JF-F = 7.63 Hz, 4F, 10,20-(2,6-PhF)), -139.98 (dd, 3JFF= 24.8 Hz, 5JF-F = 11.4 Hz, 4F, 5,15-(3,5- or 2,6-PhF)), -155.15(t, 3JF-F = 20.5 Hz, 2F, 10,20-(4-PhF)), -164.21 (dt, 3JF-F = 21.5 Hz(t), 5JF-F = 6.04 Hz (d), 4F, 10,20-(3,5-PhF)). UV-vis (c = 2 μM, DMSO,path length = 1 cm, 25 °C): λ/nm (ε × 10-3/M-1 cm-1) = 413.5 (320),506.0 (22.6), 538 (2.88), 580.0 (7.35).2.3.3. 5,10-Bis(4-(2-Hydroxyethylthio)-2,3,5,6-Tetrafluorophenyl)-15,20-Bis(Pentafluorophenyl)Porphyrin (Cis-2ME)Purity(HPLC): N99%. TLC (silica gel): Rf=0.55 (CHCl3/CH3OH=9/1,v/v) and Rf=0.26 (CHCl3/CH3OH=100/5, v/v). ESI-TOF HRMS:m/z forC48H20N4F18O2S2Na ([M+Na]+) calcd 1113.06379; found 1113.06339(error -0.41 mmu, -0.36 ppm). 1H NMR (acetone-d6, 500 MHz, acetone-d5H = 2.04 ppm): δ (ppm) = 9.50-9.21 (br, 8H, β-pyrroleH),4.00 (t, 3J = 6.35 Hz, 4H, -CH2OH), 3.43 (t, 3J=6.33 Hz, 4H, -SCH2-).1H NMR (C6D6, 500 MHz, C6HD5 = 7.15 ppm): δ (ppm) = 8.80(d, 3J = 4.70 Hz, 2H, β-pyrroleH), 8.72 (s, 2H, β-pyrroleH), 8.69 (s, 2H,β-pyrroleH), 8.63 (d, 3J = 4.75 Hz, 2H, β-pyrroleH), 3.48 (q, 3J =5.68 Hz, 4H, -CH2OH), 2.83 (t, 3J = 5.85 Hz, 4H, -SCH2-), 1.18 (t,3J = 5.65 Hz, 2H, -OH), -3.25 (s, 2H, NH). 19F NMR (acetone-d6,470.34 MHz, CF3CO2H = -76.55 ppm): δ (ppm) = -135.47 (dd,3JF-F = 25.3 Hz, 5JF-F = 11.9 Hz, 4F, 5,10-(2,6- or 3,5-PhF)), -139.61 (dd, 3JF-F = 23.4 Hz, 5JF-F = 8.11 Hz, 4F, 15,20-(2,6-PhF)), -139.98 (dd, 3JF-F = 24.8 Hz, 5JF-F = 11.4 Hz, 4F, 5,10-(3,5- or 2,6-PhF)), -155.18 (t, 3JF-F = 20.0 Hz, 2F, 15,20-(4-PhF)), -164.22 (dt,3JF-F = 21.5 Hz (t), 5JF-F = 6.36 Hz (d), 4F, 15,20-(3,5-PhF)). UV-vis (c = 2 μM, DMSO, path length = 1 cm, 25 °C): λ/nm (ε × 10-3/M-1 cm-1) = 413.0 (322), 506.0 (22.6), 537 (2.82), 580.5 (7.27).2.3.4. 5,10,15-Tris(4-(2-Hydroxyethylthio)-2,3,5,6-Tetrafluorophenyl)-20-Pentafluorophenylporphyrin (3ME)Purity(HPLC): N99%. TLC (silica gel, CHCl3/CH3OH= 9/1, v/v): Rf =0.46. ESI-TOF HRMS: m/z for C50H25N4F17O3S3Na ([M+Na]+) calcd1171.07150; found 1171.07134 (error - 0.16 mmu, -0.14 ppm). 1HNMR (acetone-d6, 500 MHz, acetone-d5H = 2.04 ppm): δ (ppm) =9.34 (s, 8H, β-pyrroleH), 4.24 (t, 3J = 5.68 Hz, 3H, -OH), 4.01 (q, 3J =6.10 Hz, 6H, -CH2OH), 3.43 (t, 3J = 6.30 Hz, 6H, -SCH2-), -2.89 (s,2H, NH). 19F NMR (acetone-d6, 470.34 MHz, CF3CO2H = -76.55 ppm): δ (ppm) = -135.47 (dd, 3JF-F = 24.8 Hz, 5JF-F = 11.4 Hz,6F, 5,10,15-(2,6- or 3,5-PhF)), -139.60 (dd, 3JF-F = 23.4 Hz, 5JF-F =8.11 Hz, 2F, 20-(2,6-PhF)), -139.97 (dd, 3JF-F = 25.3 Hz, 5JF-F =11.9 Hz, 6F, 5,10,15-(3,5- or 2,6-PhF)), -155.18 (t, 3JF-F = 20.5 Hz, 1F,20-(4-PhF)), -164.22 (dt, 3JF-F = 21.5 Hz (t), 5JF-F = 6.36 Hz (d), 2F,20-(3,5-PhF)). UV-vis (c = 2 μM, DMSO, path length = 1 cm, 25 °C):λ/nm (ε × 10-3/M-1 cm-1) = 414.5 (334), 506.5 (23.0), 538 (2.91),581.0 (7.37).2.3.5. 5,10,15,20-Tetrakis(4-(2-Hydroxyethylthio)-2,3,5,6-Tetrafluorophenyl) Porphyrin (4ME)Purity(HPLC): 99%. TLC (silica gel, CHCl3/CH3OH = 9/1, v/v): Rf =0.34. ESI-TOF HRMS: m/z for C52H30N4F16O4S4Na ([M+Na]+) calcd1229.07921; found 1229.07932 (error 0.12 mmu, 0.09 ppm). 1H NMR(acetone-d6, 500 MHz, acetone-d5H = 2.04 ppm): δ (ppm) = 9.33 (s,8H, β-pyrroleH), 4.24 (t, 3J = 5.65 Hz, 4H, -OH), 4.01 (q, 3J = 6.08 Hz,8H, -CH2OH), 3.43 (t, 3J = 6.30 Hz, 8H, -SCH2-), -2.88 (s, 2H, NH).19F NMR (acetone-d6, 470.34 MHz, CF3CO2H = -76.55 ppm): δ(ppm)= -135.48 (dd, 3JF-F=24.8Hz, 5JF-F = 11.4 Hz, 8F, 5,10,15,20-(2,6- or 3,5-PhF)), -139.95 (dd, 3JF-F = 25.3 Hz, 5JF-F = 11.9 Hz, 8F,5,10,15,20-(3,5- or 2,6-PhF)). UV-vis (c=2μM, DMSO, path length =1 cm, 25 °C): λ/nm (ε × 10-3/M-1 cm-1) = 415.5 (333), 507.0(22.6), 539 (3.12), 581.5 (7.25).
  • 71
  • [ 4869-59-4 ]
  • [ 25440-14-6 ]
  • C72H30F16N4O8S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% In a round-bottom flask, 0.24 mmol of <strong>[4869-59-4]3-mercaptobenzoic acid</strong>were dissolved in 20 mL of DMF with 1.0 mL of pyridine and keptunder magnetic stirring at room temperature for 30 min. After thistime the porphyrin P1 (0.035 mmol) was added and the reactionmixture was kept under magnetic stirring for 48 h. The reactionwas monitored by TLC and the reaction was stopped when no P1was detected. The solvent was evaporated under reduced pressure and the crude material dissolved in CH2Cl2:CH3OH was purified bycolumn chromatography using silica as the stationary phase andCH2Cl2:CH3OH (9:1 v/v) as eluent. Porphyrin P3 was obtained in85% yield, after crystallization from a mixture ofCH2Cl2:CH3OH:hexane.Porphyrin P3, mp > 300 C: deltaH ppm (DMSO-d6): -3.13 (s, 2H,NH), 7.72 to 7.67 (t, J = 7.8 Hz, 4H, S-C6H4-CO2H), 8.06 to 7.97 (m,8H, S-C6H4-CO2H), 8.23 (s, 4H, S-C6H4-CO2H) and 9.50 (s, 8H, H-b).19F NMR: dF ppm (DMSO-d6) -161.2 to 161.1 (dd, J = 11.4 and26.6 Hz, 8F, F-meta), and -156.7 to -156.6 (dd, J = 11.4 and 26.6 Hz,8F, F-ortho) (see ESI). UV-VIS (DMF) lmax, nm(log epsilon): 412 (5.14), 504(4.07), 582 (3.57). HRMS-ESI: calcd. for C72H29F16N4O8S4 [M - H]+.1509.0764 found 1509.0657; calcd. for C72H30F16N4O8S4 [M+.]1510.0691 found 1510.0683; calcd. for C72H31F16N4O8S4 [M+H]+1511.0725 found 1511.0687.
  • 72
  • [ 557-34-6 ]
  • [ 25440-14-6 ]
  • [ 72076-08-5 ]
YieldReaction ConditionsOperation in experiment
100% In methanol; chloroform at 60℃; for 0.25h; 3.2.1. 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinatozinc(II) (Zn2) Prepared as in [73]. Zinc acetate (28.2 mg, 0.154 mmol) was added to a solution of 2 (50.0 mg,51.3 mol) in chloroform/methanol (2:1) and the resulting mixture was stirred at 60 °C for 15 min.After cooling down to ambient temperature, the reaction mixture was washed with distilled water.The organic phase was dried (Na2SO4) and the solvent was evaporated under reduced pressure. TheZn2 complex was obtained in quantitative yield. UV-Vis (toluene): λmax (log ε) 421 (5.5), 546 (4.2), 581(3.7) nm. MS (MALDI-TOF): m/z 1036.0 [M]+.
85% In N,N-dimethyl-formamide for 0.00833333h; Reflux; [5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinato]zinc(II) (2). A mixture of 0.04 g(0.0412 mmol) of tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin and 0.076 g (0.412 mmol) of zinc(II)acetate in 8 mL of DMF was refluxed for 30 s. Themixture was then treated as described above for complex1. Yield 0.036 g (0.0347 mmol, 85%). 1H NMRspectrum (CDCl3): δ 8.99 ppm, s (8H, β-H). Massspectrum: m/z 1037.2 (Irel 98%) [M]+. Calculated forC44H8F20N4Zn: 1037.9.
85% In N,N-dimethyl-formamide for 0.00833333h; Reflux; Zn(II)-5,10,15,20-tetra-(2,3,4,5,6-pentafluorophenyl)porphyrin(II). A mixture of tetra-(2,3,4,5,6-pentafluorophenyl)porphyrin (0.04g, 0.0412mmol) and Zn(OAc)2 (0.076g, 0.412mmol) in DMF (8mL) was heated to reflux, it was refluxed for 30s. The treatment was similar to I. Yield is 0.036g (0.0347mmol, 85%). UV-Vis spectrum in toluene, λ, nm, (lgε): 400 (4.69), 421 (5.544), 551 (4.33), 583sh. 1H NMR (δ, ppm, CDCl3): 8.99s (8H, pyrrole). Mass-spectrum, m/z (Ie,%): 1037.2 (98) [M]+ (calculated for C44H8F20N4Zn 1037.9).
76.7% In methanol; chloroform for 2h; Reflux; Inert atmosphere;
Inert atmosphere;

  • 73
  • [ 653-37-2 ]
  • [ 155796-90-0 ]
  • C45H14F15N5 [ No CAS ]
  • C46H18F10N6 [ No CAS ]
  • 5,15-bis(4-cyanophenyl)-10,20-bis(pentafluorophenyl) porphyrin [ No CAS ]
  • C47H22F5N7 [ No CAS ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
1: 6% 2: 8% 3: 14% 4: 6% 5: 4% Stage #1: perfluorobenzaldehyde; 4-(di-1H-pyrrol-2-ylmethyl)benzonitrile With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 1h; Inert atmosphere; 2 Synthesis of porphyrins using 5-(4-cyanophenyl)dipyrromethane and pentafluorobenzaldehyde with BF3·OEt2 as catalyst 5-(4-cyanophenyl)dipyrromethane (0.5 g, 2.02 mmol) and pentafluorobenzaldehyde (0.25 mL, 2.02 mmol) were taken in 500mL RB flask containing 350mL of CH2Cl2, and it was purged with N2 gas for 10 min followed by the addition of BF3·OEt2 (0.1 mL, 2.5 M). Then, the resultant solution was stirred under N2 atmosphere at room temperature for 1 h followed by the addition of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (460 mg, 2.02 mmol). The solution stirred further for 1h. Finally, the solvent was removed by rotary evaporator and it was found that there were five porphyrins, 1, B4; 2, AB3; 3, cis-A2B2; 4, trans-A2B2 and 5, A3B which are separated out by column chromatography (silica, hexane/chloroform) and yielded in 6% (60 mg); 8% (73 mg); 14% (120 mg); 6% (50 mg) and 4% (30 mg) respectively. UV-vis data in CH2Cl2, λmax (log): 1, 411 (5.74), 505 (4.59), 580 (4.07); 2, 413 (5.78), 508 (4.60), 588 (4.07); 3, 415 (5.97), 508 (4.77), 544 (4.20), 588 (4.28), 645 (4.08); 4, 415 (5.87), 508 (4.65), 544 (3.92), 588 (4.13), 638 (3.30); 5, 418 (5.67), 462 (4.88), 516 (4.63), 587 (4.34), 631 (4.04). Mass (FAB) data: 2, 911.18 (calc: 909.60); 3, 845.37 (calc: 844.66). 1H NMR data in CDCl3 (δ in ppm): 1, -2.92 (s, 2H), 8.91 (s, 8H); 2, -2.92 to -2.89 (br, 2H), 8.11-8.13 (d, 2H), 8.34-8.36 (d, 2H), 8.56-8.90 (m, 8H); 3, -2.90 to -2.86 (br, 2H), 8.10-8.12 (m, 4H), 8.33-8.36 (m, 4H), 8.80 to 8.90 (m, 8H); 4, -2.88 (br, 2H), 8.10-8.12 (m, 4H), 8.33-8.36 (m, 4H), 8.85 (s, 8H); 5, -2.85 (br, 2H), 8.09-8.11 (m, 6H), 8.32-8.35 (m, 6H), 8.79-8.84 (m, 8H).
  • 74
  • [ 6046-93-1 ]
  • [ 25440-14-6 ]
  • [ 27882-93-5 ]
YieldReaction ConditionsOperation in experiment
95% In N,N-dimethyl-formamide for 1h; Reflux; Preparation of the complexes General procedure: TFPP (60 mg, 61.6 lmol) was dissolved in DMF (30 mL). Cu(OAc)2*H2O (200 mg, 1 mmol) was added, and the solution was heated to reflux for 1 h, then left to cool. The solution was extracted with dichloromethane (DCM)/water(V/V = 1/2), and the organic phase was collected and washed 6-7 times with water. Solvent was evaporated to dryness to obtain the crude product CuTFPP. This was purified by column chromatography using DCM/MeOH (V/V = 100/5). Recrystallization from DCM/hexane afforded complex 1 as a red solid (63 mg, yield 95%). Complexes 2 and 3 were synthesized by the same procedure, but replacing Cu(OAc)2*H2O with Co(OAc)2*4H2O and Zn(OAc)2*2H2O, respectively. HRMS of the complexes and given in the Supplementary Materials. CuTFPP: UV-Vis (CH2Cl2) λmax (relatively intensity): 409 (1.000), 535 (0.049), 570 (0.022) nm. HRMS, calcd for C44H8CuF20N4: 1035.9798, found for C44H8CuF20N4: 1035.9795.
89% In methanol; chloroform at 20℃; for 2h;
71% In N,N-dimethyl-formamide at 200℃; for 0.166667h; Microwave irradiation;
In methanol; chloroform for 0.5h; Reflux; Synthesis of copper complexes General procedure: The ligand, 2, AB3 (50 mg, 0.06 mmol) was dissolved in CHCl3 and copper acetate monohydrate (55mg, 0.27mmol) in methanol was added to it, refluxed for 30min. The solvent was removed and the complex was purified by column chromatography (silica, hexane/chloroform). The yield was found to be (94%, 48 mg). Similar procedure was followed for making the copper complex of other ligands, 1, 3, 4, and 5 and found in almost quantitative yields (92-96%). UV-vis data in CH2Cl2, λmax (log): Cu-B4, 408 (6.06), 534 (4.68), 573 (4.27); Cu-AB3, 409 (6.28), 537 (4.95), 570 (4.48); Cu-cis-A2B2, 413 (6.21), 537 (4.85), 624 (4.52); Cu-trans-A2B2, 411 (6.17), 537 (4.95), 573 (4.65); Cu-A3B, 411 (6.26), 537 (5.01), 620 (4.60).
In methanol; chloroform for 0.5h; Reflux; 2.4. Synthesis of copper complexes General procedure: The ligand, 3, (50 mg, 0.05 mmol) was dissolved in CHCl3 and copper acetate monohydrate (45 mg, 0.25 mmol) in methanol was added to it, refluxed for 30 min. The solvent was removedand the complex, Cu-3 was purified by column chromatography(silica, hexane/chloroform). The yield was found to be (94%,45 mg). Similar procedure was followed for making other copper complexes of ligands, 1, 6, 7, 8, 9, 10, 11 and 12 and found in almost quantitative yields (92-96%). UV-Vis data in CH2Cl2, λmax (log ε): Cu-1, 489 (6.06), 534 (4.68), 573 (4.27); Cu-6, 409 (6.18), 537 (4.81), 573 (4.33); Cu-7, 413 (6.14), 537 (4.79), 573 (4.11); Cu-8,411 (6.05), 537 (4.53), 595 (4.18); Cu-9, 413 (6.15), 537 (4.83), 560.6 (4.30); Cu-10, 417 (6.24), 537 (4.92), 570 (4.14); Cu-11, 417 (6.19), 541 (5.17), 613 (4.38); Cu-12, 417 (6.19), 541 (5.17),613 (4.38).

  • 76
  • [ 107-21-1 ]
  • [ 25440-14-6 ]
  • C50H25F17N4O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
47% Stage #1: ethylene glycol With sodium hydride In tetrahydrofuran for 0.5h; Inert atmosphere; Stage #2: tetrakis(pentafluorophenyl)porphyrin In tetrahydrofuran for 24h; Reflux; Inert atmosphere; (i) Improved synthesis of the free-base porphyrin P3: Ethyleneglycol (8.6 mmol) was dissolved in 15 mL of dry THF, andNaH (0.95 mmol) was then added. The reaction mixturewas kept under magnetic stirring and nitrogen atmospherefor 30 min. A solution of H2(TPFPP) in THF (15.4 mmol/L)was added and the reaction mixture was heated at refluxtemperature until the total consumption of the starting porphyrin(24 h, monitored by TLC). After cooling to ambienttemperature, the mixture was diluted with dichloromethaneand washed 3 times with 10 mL of water. The solvent wasevaporated under reduced pressure and the crude solidwas purified by preparative TLC using dichloromethane:methanol (9:1 v/v) as the eluent. The fourth fraction wasidentified as the porphyrin P3 (47% yield), mp > 300 C. 1HNMR: dH ppm (CD3OD); 9.10 (broad s, 8H, H-b); 4.11 (t,J = 4.4, 6H, CH2) and 4.70 (t, J = 4.4, 6H, CH2). 19F NMR: dFppm (CD3OD) 188.63 (dt, J = 7.3 and 21.3, 2F, F-meta),182.84 (dd, J = 7.3 and 21.3, 6F, F-meta), 179.13
  • 77
  • [ 653-37-2 ]
  • 5-(pentafluorophenyl)dipyrromethane [ No CAS ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
5% Stage #1: perfluorobenzaldehyde; 5-(pentafluorophenyl)dipyrromethane With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 1h; Inert atmosphere; 2.3.1. Synthesis of porphyrins using 5-(pentafluorophenyl)dipyrromethane and methyl 4-formylbenzoate with BF3*OEt2 as catalyst General procedure: 5-(2,3,4,5,6-Pentafluorophenyl)dipyrromethane (0.5 g, 1.60mmol) and methyl 4-formylbenzoate (0.26 g, 1.60 mmol) were taken in 500 mL RB flask containing 350 mL of CH2Cl2, purged with N2 gas for 10 min and BF3*OEt2 (0.1 mL, 2.5 M) was added to it. The resultant solution was stirred under N2 atmosphere for 1 h at room temperature followed by the addition of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (360 mg, 1.60 mmol). Then, it was stirred further for one hour and the solvent was removed. It is seen that there are six porphyrins namely, 1, 6, 7, 8, 9 and 10 were separated outby column chromatography using silica gel as solid support. The eluent used for the separation of six porphyrins are 9:1 (v:v) hexane/chloroform, 7:3 (v:v) hexane/chloroform, 4:6 (v:v) hexane/chloroform, 3:7 (v:v) hexane/chloroform, 100% chloroform and1% acetone in chloroform respectively which yielded in 5%(40 mg); 5% (37 mg); 11% (80 mg); 10% (70 mg); 4% (30 mg) and 4% (25 mg). The characterization of ligands, 1-5 were done and reported previously by us [8]. UV-Vis data in CH2Cl2, λmax (logε): 1, 411 (5.74), 505 (4.59), 580 (4.07); 6, 413 (5.87), 508 (4.71), 588 (4.22), 652 (3.56); 7, 415 (5.93), 508 (4.71), 544 (4.08), 588(4.21), 645 (3.66); 8, 415 (5.91), 508 (4.66), 544 (3.94), 588 (4.10), 652 (3.51); 9, 417 (5.88), 512 (4.66), 544 (4.18), 587(4.22), 645 (3.84) and 10, 418 (5.93), 516 (4.59), 552 (4.23), 587(4.00), 645 (3.77). 1H NMR data in CDCl3 (δ in ppm): 1, 2.93 (s,2H), 8.92 (s, 8H); 6, 2.87 (br, 2H), 4.13 (s, 3H), 8.30-8.32 (d, 2H,J = 8.00 Hz), 8.47-8.49 (d, 2H, J = 8.00 Hz), 8.83-8.90 (m, 8H); 7,2.87 (s, 2H), 4.13 (s, 6H), 8.30-8.32 (d, 4H, J = 8.00 Hz), 8.46-8.48 (d, 4H, J = 8.00 Hz), 8.83-8.91 (m, 8H); 8, 2.87 to 2.82 (br,2H), 4.13 (s, 6H), 8.30-8.32 (d, 4H, J = 8.00 Hz), 8.47-8.49 (d, 4H,J = 8.00 Hz), 8.82-8.90 (m, 8H); 9, 2.81 (br, 2H), 4.12 (br, 9H),8.29-8.31 (d, 6H, J = 8.00 Hz), 8.45-8.47 (d, 6H, J = 8.00 Hz), 8.82-8.90 (m, 8H) and 10, 2.82 (br, 2H), 4.12 (br, 12H), 8.29-8.31 (d, 8H, J = 8.00 Hz), 8.44-8.46 (d, 8H, J = 8.00 Hz), 8.82 (s, 8H).
  • 78
  • [ 109-97-7 ]
  • [ 19842-76-3 ]
  • [ 25440-14-6 ]
YieldReaction ConditionsOperation in experiment
10% Stage #1: pyrrole; 2,3,5,6-tetrafluorobenzaldehyde With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: With pyridine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane
  • 79
  • [ 6147-53-1 ]
  • [ 25440-14-6 ]
  • [ 52242-06-5 ]
YieldReaction ConditionsOperation in experiment
Ca. 75% With acetic acid; In chloroform; for 24h;Reflux; A mixture of F20TPPH2 (0.5g, 0.5mmol) and Co(OAc)2.4H2O (1.25g, 5mmol) was refluxed in CHCl3 (10mL) and acetic acid (10mL) for 24h. The reaction was stopped and 100mL water was added. The crude product was extracted with CHCl3 and dried in vacuo. Recrystallisation from CH2Cl2 resulted red crystals of complex 1. Yield: ~ 0.4g (ca. 75%). Elemental analyses for C44H8N4F20Co, Calcd. (%):C, 51.24; H, 0.78; N, 5.43, found (%): C, 51.15; H, 0.76; N, 5.37. UV-visible (CH2Cl2): 404nm (ε/M-1cm-1, 2.06×105); 525nm (ε/M-1cm-1, 1.14×104) and 555nm (ε/M-1cm-1, 9.53×103). FT-IR (in KBr): 1522, 1495, 1431, 1349, 1262, 1083, 1057, 990, 942, 807, 764 and 706cm-1. ESI-mass (m/z): Calcd. 1030.98; found: 1030.92 (molecular ion peak). Crystal data: complex 1, CCDC No. 2112473. C44H8F20N4Co, M=1031.47, trigonal (R-3), a=20.3537(13), b=20.3537(13), c=24.165(2) Å, α=90, β=90, γ=120, V=8669.9(14) Å3, Z=9, Dc=1.778gcm-3, μ=0. 0.584mm-1, T=293(2) K, 3391 reflections, 2224 independent, R(F)=0.0549 [I>2δ(I)], R(int)=0.0911, wR(F2)=0.1787 (all data), GOF=0.958.
In N,N-dimethyl-formamide; for 1h;Reflux; General procedure: TFPP (60 mg, 61.6 lmol) was dissolved in DMF (30 mL). Cu(OAc)2*H2O (200 mg, 1 mmol) was added, and the solution was heated to reflux for 1 h, then left to cool. The solution was extracted with dichloromethane (DCM)/water(V/V = 1/2), and the organic phase was collected and washed 6-7 times with water. Solvent was evaporated to dryness to obtain the crude product CuTFPP. This was purified by column chromatography using DCM/MeOH (V/V = 100/5). Recrystallization from DCM/hexane afforded complex 1 as a red solid (63 mg, yield 95%).
  • 80
  • [ 5970-45-6 ]
  • [ 25440-14-6 ]
  • [ 72076-08-5 ]
YieldReaction ConditionsOperation in experiment
87% In methanol; chloroform at 50℃; for 12h;
In N,N-dimethyl-formamide for 1h; Reflux; Preparation of the complexes General procedure: TFPP (60 mg, 61.6 lmol) was dissolved in DMF (30 mL). Cu(OAc)2*H2O (200 mg, 1 mmol) was added, and the solution was heated to reflux for 1 h, then left to cool. The solution was extracted with dichloromethane (DCM)/water(V/V = 1/2), and the organic phase was collected and washed 6-7 times with water. Solvent was evaporated to dryness to obtain the crude product CuTFPP. This was purified by column chromatography using DCM/MeOH (V/V = 100/5). Recrystallization from DCM/hexane afforded complex 1 as a red solid (63 mg, yield 95%).
With silica gel for 0.416667h; Milling;
  • 81
  • [ 1295-35-8 ]
  • [ 25440-14-6 ]
  • [ 445487-66-1 ]
  • nickel-tetrakis(pentafluorophenyl)chlorin [ No CAS ]
  • 82
  • [ 25440-14-6 ]
  • [ 627509-60-8 ]
  • C58H29F19N4O9S [ No CAS ]
YieldReaction ConditionsOperation in experiment
41.2 mg With diethylamine In N,N-dimethyl-formamide at 20℃; for 24h; 14 TFPP (192.2 mg, 197 lmol), 2-Ac-S-AcGlc (117.8 mg, 290lmol), and diethylamine (DEA, 60 lL, 580 lmol) were dissolvedin DMF (40 mL). The reaction mixture was stirred at room temperaturefor 24 h, diluted with CH2Cl2 (15 mL) and washed with distilledwater (15 mL 5). The extract was dried over Na2SO4 andthe solvent was removed under reduced pressure. The crude productwas separated by column chromatography (silica gel, CH2Cl2to CH2Cl2/EtOAc = 100-90:10) to give acetylated TFPP-glucose conjugate2Ac (41.2 mg).
  • 83
  • 1,2,4,6-tetra-O-acetyl-3-S-acetyl-3-thio-α/b-D-galactopyranoside [ No CAS ]
  • [ 25440-14-6 ]
  • C58H29F19N4O9S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With diethylamine In N,N-dimethyl-formamide at 20℃; for 24h; 14 General procedure: TFPP (192.2 mg, 197 lmol), 2-Ac-S-AcGlc (117.8 mg, 290lmol), and diethylamine (DEA, 60 lL, 580 lmol) were dissolvedin DMF (40 mL). The reaction mixture was stirred at room temperaturefor 24 h, diluted with CH2Cl2 (15 mL) and washed with distilledwater (15 mL 5). The extract was dried over Na2SO4 andthe solvent was removed under reduced pressure. The crude productwas separated by column chromatography (silica gel, CH2Cl2to CH2Cl2/EtOAc = 100-90:10) to give acetylated TFPP-glucose conjugate2Ac (41.2 mg).
  • 84
  • 1,2,3,6-tetra-O-acetyl-4-S-acetyl-4-thio-D-glucopyranose [ No CAS ]
  • [ 25440-14-6 ]
  • C58H29F19N4O9S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With diethylamine In N,N-dimethyl-formamide at 20℃; for 24h; 14 General procedure: TFPP (192.2 mg, 197 lmol), 2-Ac-S-AcGlc (117.8 mg, 290lmol), and diethylamine (DEA, 60 lL, 580 lmol) were dissolvedin DMF (40 mL). The reaction mixture was stirred at room temperaturefor 24 h, diluted with CH2Cl2 (15 mL) and washed with distilledwater (15 mL 5). The extract was dried over Na2SO4 andthe solvent was removed under reduced pressure. The crude productwas separated by column chromatography (silica gel, CH2Cl2to CH2Cl2/EtOAc = 100-90:10) to give acetylated TFPP-glucose conjugate2Ac (41.2 mg).
Same Skeleton Products
Historical Records