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CAS No. : | 102-08-9 | MDL No. : | MFCD00004921 |
Formula : | C13H12N2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FCSHMCFRCYZTRQ-UHFFFAOYSA-N |
M.W : | 228.31 | Pubchem ID : | 700999 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 72.37 |
TPSA : | 56.15 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.15 cm/s |
Log Po/w (iLOGP) : | 2.77 |
Log Po/w (XLOGP3) : | 2.17 |
Log Po/w (WLOGP) : | 3.11 |
Log Po/w (MLOGP) : | 3.01 |
Log Po/w (SILICOS-IT) : | 3.27 |
Consensus Log Po/w : | 2.87 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.91 |
Solubility : | 0.279 mg/ml ; 0.00122 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.98 |
Solubility : | 0.238 mg/ml ; 0.00104 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.18 |
Solubility : | 0.00152 mg/ml ; 0.00000665 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.91 |
Signal Word: | Danger | Class: | 6.1 |
Precautionary Statements: | P501-P270-P264-P301+P310+P330-P405 | UN#: | 2811 |
Hazard Statements: | H301 | Packing Group: | Ⅱ |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 95 - 96℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 95 - 96℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In acetonitrile at 25℃; for 0.166667h; Milling; | |
99% | In dichloromethane at 20℃; | |
99% | With [{Ph2P(Se)NCH2CH2NPPh2(Se)}Ti(NMe2)2] In toluene at 25℃; for 1h; Schlenk technique; Glovebox; Inert atmosphere; |
99% | In dichloromethane at 20℃; for 24h; | 3.3. General Procedures for the Preparation of CompoundsI-V General procedure: To a solution of amines (1 equiv) in (10 mL) of CH2Cl2,was added the corresponding isothiocyanate or phenylisocyanate(1 equiv), and the resulting solution was stirred at roomtemperature until TLC indicated the reaction was complete(24 h for (thio)ureas) and (4h for ureas). The solvent wasremoved in vacuum. The crude product was purified by columnchromatography to afford (thio)ureas I-V. The pureproducts I-III and V were obtained by recrystallization fromCH2Cl2. Compound IV was purified by chromatography on acolumn of silica gel with AcOEt/Acetone (9:1). 3.3.1. N-phenyl -N'-(2-pyridynyl)thiourea (I)Colorless solid; 99% yield; mp 176-178°C IR (v, cm-1KBr): 3172 (NH), 3037 (C-H), 1594 (C=C), 1547 (NH),1188 (C=S). 1H NMR (400 MHz, CDCl3) δ: 13.70 (1H,broad, H-9), 9.17 (1H, broad, H-2), 8.23 (1H, dd, J=5.3, 1.1Hz, H-5), 7.67 (2H, dd, J=7.9, 2.3 Hz, H-11, 15), 7.63 (1H,d, J=8.1 Hz, H-7), 7.43 (2H, t, J=7.9 Hz, H-12, H-14), 7.27(1H, m, H-13), 7.00 (1H, ddd, J=7.3, 5.3, 0.8 Hz, H-6), 6.92(1H, d, J=8.1 Hz, H-8). 13C NMR (100 MHz, CDCl3) δ:178.7 (C=S), 153.1 (C-3), 145.6 (C-5), 139.0 (C-7), 138.6(C-10), 128.7 (C-12, 14), 126.3 (C-13), 124.9 (C-11, 15),118.2 (C-6), 112.4 (C-8). EI MS (70eV) m/z: [M-1]+ 228.17(10), 227.14 (56), 78.03 (100), 77.05 (20) [24]. |
98% | In ethanol for 1h; Heating; | |
98% | With C64H52CaN6 In neat (no solvent) at 60℃; for 12h; Schlenk technique; Glovebox; Inert atmosphere; | |
97% | In <i>tert</i>-butyl alcohol for 4h; Reflux; | Preparation of Thioureas 3a-z General procedure: Method B; To a solution of isothiocyanate 1 (1.0 mmol) in tert-butanol (10 mL) was added the corresponding amine 2 (1.2 mmol), andthe mixture was refluxed until isothiocyanate was consumed(TLC). Then, the solvent was evaporated, 10 mL of CH2Cl2 was added and the same work up used in method A was followed. |
96% | With 2-(2,4,5,7-tetrabromo-3,6-dihydroxy-9H-xanthen-9-yl)benzoic acid; oxygen In water; dimethyl sulfoxide at 20℃; for 8h; Schlenk technique; Sealed tube; Irradiation; Green chemistry; | |
96% | In neat (no solvent) at 20℃; for 0.166667h; Schlenk technique; Green chemistry; | |
95% | In dichloromethane at 20℃; for 3h; | 4.1.1 1,3-Diphenylthiourea [35] To a stirred solution of 60 phenylisothiocyanate (1.00mmol; 135mg) in 61 dichloromethane (0.5mL) at room temperature, was added dropwise a solution of 62 aniline (1.00mmol; 93mg) in dichloromethane (0.5mL). The reaction was followed by TLC (dichloromethane) and completed in 3h. The resulting suspension was filtered and washed with diethyl ether; Yield 95%; white crystals; mp 142-144°C (lit [59]. 140-142°C); IR υmax (cm-1) 3202, 3053, 1598, 1526, 1491, 1449, 1342, 1313, 1288, 1242, 1171, 1069, 1021, 1003, 933, 756, 694, 642, 629, 610; 1H NMR (400MHz, DMSO-d6) δ (ppm) 9.79 (s, 2H, 2×NH), 7.48 (d, J= 7.4Hz, 4H, 2′ and 6′-ArCH), 7.33 (t, J= 8.2 and 7.6Hz, 4H,3′ and 5′-ArCH), 7.12 (t, J= 7.4Hz, 2H, 4′-ArCH); 13C NMR (101MHz, DMSO-d6) δ (ppm) 179.63 (2-CS), 139.46 (1′-ArC), 128.45 (ArCH), 124.44 (4′-ArCH), 123.66 (ArCH). |
95% | In dichloromethane at 20℃; for 3h; | 4.1.1. 1,3-Diphenylthiourea [13] To a stirred solution of phenyl isothiocyanate (1 mmol;135 mg) in dichloromethane (0.5 mL) at room temperaturewas added dropwise a solution of aniline (1 mmol; 93 mg)in dichloromethane (0.5 mL). The reaction was followed bythin-layer chromatography (dichloromethane) andcompleted in 3 h. The product so formed in suspensionwasfiltered and washed with ethyl ether; 217 mg (95%); whitecrystals; mp 142e144 C (lit. [14], 140e142 C). 1H NMR(400 MHz, DMSO-d6) d (ppm) 9.79 (s, 2H), 7.48 (d,J 7.4 Hz, 4H), 7.33 (t, J 8.2 and 7.6 Hz, 4H), 7.12 (t,J 7.4 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) d (ppm)179.6, 139.5, 128.5, 124.4, 123.7. |
95% | With [κ2-{(Ph2P-(=Se))}2NCH2(C5H4N)ZnCl2] In toluene at 25℃; Schlenk technique; Inert atmosphere; | General Procedure for the Catalytic Addition of Amines with RNCO and RNCS. General procedure: A solution of primary or secondary amine (0.276 mmol) in toluene (1.0 mL) was added drop wise into the reaction mixture of RNCO (0.276 mmol) or RNCS (0.276 mmol) and zinc complex [{Ph2P(Se)2N-CH2C5H4N}ZnCl2] 2 (0.0138 mmol) to a 25 mL dry Schlenk flask. The reaction mixture was stirred for 2 hours at room temperature. Solvent was evaporated under vacuo. White solid compound obtained in each case. The conversion of amines was calculated from isolated pure products. The products were identified by 1H NMR spectroscopy and MS analysis; the values were compared with previous literature. |
93% | In dichloromethane at 20℃; for 24h; | |
93% | for 0.00833333h; Microwave irradiation; Neat (no solvent); | |
92% | In chlorobenzene at 70℃; for 2h; Sealed tube; | |
92% | In dichloromethane at 20℃; | 4.1.2. Synthesis of model compounds General procedure: In a dry flask equipped with a stirring bar under nitrogen atmosphere,1 mmol of aniline or p-trifluoromethylaniline or o-toluidinewas dissolved in 12 mL of dry DCM. 1 mmol of theappropriate isothiocyanate was added dropwise to the correspondinganiline solution at room temperature. The reactionmixture was left to stir overnight and then was evaporated todryness. The thiourea products were purified by column chromatographyon a short column, using pentane/EtOAc as eluent. |
90% | In ethyl acetate for 1h; Reflux; | |
90% | In tetrahydrofuran at 50℃; for 48h; | |
89% | In benzene for 0.5h; Ambient temperature; | |
88% | In tetrahydrofuran at 20℃; for 40h; Inert atmosphere; | |
87% | In benzene at 20 - 25℃; | |
85% | In dichloromethane at 20℃; for 16h; Inert atmosphere; | |
84.4% | With pyridine at 20℃; Inert atmosphere; | |
84% | In dichloromethane at 20℃; for 24h; | 1.1 Step 1: Preparation of 1,3-diphenylthiourea Phenyl isothiocyanate (phenyl isothiocyanate, 1.0 mL, 1.1 mmol) and aniline (aniline, 1.6 mL, 1.3 mmol) were dissolved in dry DCM (dry dichloromethane, 10 mL) at room temperature, followed by reaction for 24 hours. After completion of the reaction, the solvent was removed and filtered with a solution (100 mL) in which chloroform and n-hexane were mixed in a volume ratio of 2:8 to obtain 1,3-diphenylthiourea as a white solid (2.1 g, yield, 84%). |
84% | In dichloromethane at 20℃; for 24h; Inert atmosphere; | Preparation of S-Benzyl-N,N'-diphenyl isothiouronium iodide catalyst(1c) Phenyl isothiocyanate (40 mmol) was added to a solution of aniline (40 mmol) in dry dichloromethane at room temperature. The reaction mixture was stirred for 24 hr, filtered, then washed with dichloromethane and dried, to give a white solid1,3-diphenylthiourea (5.03 g, yield 84%). Then, 1,3-diphenylthiourea (4.4 mmol) was added to a solution of benzyl iodide (13.2 mmol) in drydichloromethaneat room temperature. The reaction mixture was then stirred for 24 hr. The reaction mixture was concentrated in vacuo. The residue was purified via flash chromatography (hexane:ethyl acetate = 8:2), to give a yellow solidS-benzyl-N,N'-diphenyl isothiouronium iodide(1.14 g, yield 58%).mp1C;1H NMR (300MHz, DMSO):δ7.207~7.387(m, 15H),δ 4.445(s. 2H); HR TOF-MS for C20H18N2S: calcd 318.1186(M+), found 318.1185(M+). |
82% | In ethanol for 0.0833333h; Ambient temperature; | |
82% | In toluene | |
75% | With triethylamine In dichloromethane at 20℃; Cooling with ice; | |
75% | With sodium hydrogencarbonate; (1-bromoethyl)benzne In 1,2-dichloro-benzene at 120℃; for 24h; | General procedure for 4a General procedure: A clean washed boiling tube equipped with a magnetic stir bar was charged with aniline 1a (0.0930g, 1 mmol), phenyl isothiocyanates 2a (0.1350 g, 1 mmol), 0.5 mmol of NaHCO3 and dichloroethane (1mL), the above mixture was stirred for 24 h at 120 °C temperature. After completion of the reaction, the mixture was poured into 10 mL of NaHCO3 solution. The product was extracted with ethyl acetate (10 mL × 3) and dried with anhydrous Na2SO4. Removal of the solvent under reduced pressure, the left-out residue was purified through column chromatography using silica gel (20% EtOAc/hexane) to obtained (Z)-N,3-diphenylthiazolidin-2-imine 4a in 82 % yield (0.2082g). |
27% | With triethylamine In dichloromethane | |
In acetone Heating; | ||
In diethyl ether Yield given; | ||
In ethanol Ambient temperature; | ||
In dichloromethane for 2h; Ambient temperature; | ||
In acetic acid at 69.85℃; | ||
In N,N-dimethyl acetamide at 20℃; for 0.25h; ultrasound irradiation; | ||
In dichloromethane | ||
In acetone at 20℃; for 6h; | ||
In benzene at 20℃; for 3h; | ||
In benzene at 25℃; | ||
In dichloromethane for 120h; Inert atmosphere; | ||
In acetonitrile at 20℃; for 1h; | ||
In N,N-dimethyl-formamide at 20℃; for 0.333333h; | ||
In acetonitrile at 20℃; | Synthesis of 2 General procedure: To the solution of phenylisothiocyante 5 (0.1 mol) in acetonitrile (10 mL), added corresponding amine 6 and the resulting mixture was allowed to stir for 3-4 h at room temperature. The reaction mixture was evaporated under reduced pressure and resulting solid was poured in to water. The compound was separated by using methylenechloride (50 mL) which was dried over Na2SO4. The organic layer was concentrated and the crude product was purified using column chromatography. 2k: Yield 94%; viscous solid; Rf= 0.45 (Ethyl acetate/hexane; 1:4), IR (neat): 3200, 3163, 1665, 1600, 1554, 1471, 1455 cm-1; 1H NMR (CDCl3): δ 1.1 (m, 12H, 2C(CH3)2)), 2.99 (m, 2H, 2(CH(CH3)2)), 6.00 (bs, 1H, NH), 7.13 (t, J = 8.0 Hz, 2H, Ar-H), 7.28 (t, J = 7.6 Hz, 1H, Ar-H), 7.52 (t, J = 8.0 Hz, 2H, Ar-H), 7.81 (bs, 1H, NH). HRMS calcd for C13H20N2S m/z 236.1347, found 236.1339. | |
With 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.333333h; | ||
In dimethyl sulfoxide at 80℃; for 0.166667h; Inert atmosphere; | ||
In neat (no solvent) at 90℃; | ||
In ethanol Reflux; | ||
In toluene at 24.84℃; | ||
82 %Spectr. | With [(ImDippN)Th{N(SiMe3)2}3] In benzene-d6 at 80℃; for 12h; Glovebox; Sealed tube; | |
In ethanol Reflux; | ||
In acetone at 60℃; Reflux; | 4. Synthesis of Ligands L1 - L4 General procedure: Ligands L1 - L4 were synthesized according to the previous reported method.5b p-Methoxyaniline acetone solution (12 mmol p-methoxyaniline in 20 mL acetone) was added dropwise to the solution of phenyl isothiocyanate (12 mmol) in acetone (20 mL). The reaction mixture was heated to 60 °C and refluxed for 2-3 hours and the reaction was monitored by TLC. After completion of the reaction, the resulting precipitate was collected by filtration and washed with water and ethanol to afford the pure L4. | |
In methanol Reflux; | ||
In acetonitrile at 20℃; | Thioureas were prepared according to the reported procedure General procedure: To a solution of aniline (10 mmol) in CH3CN (10 mL) was added isothiocyanate (10mmol). The reation was then stirred until complete conversion of the starting material monitored by TLC. The solvent was removed under reduced pressure and the residue was recrystallized from EtOH to get the desired thioureas 1. | |
Inert atmosphere; | ||
1.497 g | In dichloromethane for 0.75h; Cooling with ice; | 1 Place aniline (11 mmol),Triethylamine (36.2 mmol) and tetrahydrofuran 10 mL were placed in the flask,Stir for 10 minutes in an ice bath.Carbon disulfide (11 mmol) was then added dropwise to the mixture over 30 minutes; after the addition was complete,The mixture was stirred at room temperature for a further 10 hours; then cooled on an ice bath.Slowly added TsCl (12.1 mmol),After stirring for another 1h,Phenyl isothiocyanate to give 0.965 g.Dissolve 0.965 g of phenyl isothiocyanate in methylene chloride.Under ice bath conditions,Add 0.665 grams of aniline,After stirring the reaction for 45 minutes, the reaction is complete.Filter; filter cake washed with methylene chloride several times,Dried N,N-diphenyl thiourea 1.497 g will be dried. 1.497 g of N,N-diphenylthiourea and methylene chloride are mixed in a round bottom flask.Then add 7 mmol of malonyl chloride,Heat to reflux for 1 hour,After the reaction is complete,Spin off the solvent,Then 1 ml of 1.0 M hydrochloric acid was added to quench the reaction.washing,dry,Column chromatography,A barbituric acid derivative was obtained.The barbituric acid derivative and ethanol were mixed in a flask.Stir well,Add excess furfural and 0.5 ml pyridine,Stir for 2-3 hours at room temperaturefilter,Column chromatography,The target product 1,3-diphenyl-5(2-furylmethylene)thiobarbituric acid (1,3-diphenyl-5-(2-furanmethylene)thiobupiva) was obtained. (Acid acid) (structure shown in Formula 4) 0.346 g. |
In dichloromethane at 20℃; | ||
In acetone at 20℃; | 2.2. General Procedure for the Synthesis of Compounds-1-14 General procedure: Phenyl isothiocyanate (3 mmol) and 3 mmol of anilineswere taken in 6 mL of acetone. The reaction mixture wasstirred at room temperature for 6-8 hours. Progress of thereaction was monitored by thin layer chromatography (0.2mm silica gel 60). After completion of the reaction, resultingsolid product was subjected to the column chromatography(16-063-02 mm, mesh 70-230) with Hex: EtOAc (8:2) forpurification [11]. | |
In N,N-dimethyl-formamide at 20℃; for 5h; | ||
In ethanol at 20℃; | ||
In toluene for 1h; | 1.1(e) Example 1(e) Synthesis of N,N′ disubstituted thioureas A solution of alkylamine (3.0 mmol) in toluene (2.5 mL) was added to a solution of alkyl or aryl isothiocyanate (3.0 mmol) in toluene (2.5 mL). The resulting liquid was pumped under vacuum while stirring for 60 minutes to remove toluene, producing a powder. To produce thiourea crystals suitable for X-ray crystallography, the powder was dissolved in 10 mL of diethyl ether or toluene and allowed to evaporate. For N,N′-diphenyl-thiourea, the volume of toluene was increased to 5 mL for each, resulting in 10 mL total. | |
at 20℃; for 24h; | ||
With sodium hydroxide In water at 20℃; for 1h; | ||
In dichloromethane at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With di-tert-butyl peroxide; potassium hydroxide In water at 90℃; for 5h; Schlenk technique; Sealed tube; Green chemistry; | General procedure for the synthesis of thiourea General procedure: Condition C: A mixture of phenyl isothiocyanate (0.2 mmol), DTBP (35 uL, 0.2 mmol), KOH (0.20 mmol), and deionized water (1.0 mL) was heated under an air atmosphere in a screw-cap Schlenk test tube at 90° C for 5 h. After the reaction was completed, the reaction mixture was cooled to room temperature and quenched with water. The mixture was extracted with ethyl acetate (3.0mL 3), and the combined organic phases were dried over anhydrous Na2SO4 and the solvent was evaporated under vacuum. The residue was purified by column chromatography to give the corresponding products ethyl acetate/dichloromethane 1:10-1:15, 5-99%). |
97% | With water; triethylamine In 1,4-dioxane at 20℃; for 0.166667h; | |
95% | With dmap; copper(l) iodide In N,N-dimethyl-formamide at 90℃; for 12h; Sealed tube; |
91% | With titanium tetrachloride; zinc at 100℃; for 2h; | |
84% | With copper(l) iodide; caesium carbonate; 2-bromo-4,5-dimethoxy-benzamide; N,N`-dimethylethylenediamine In toluene at 20 - 120℃; Inert atmosphere; | |
58% | With sodium hydroxide In water; acetone for 48h; | 9. Synthesis of N,N’-diphenylthiourea by the self-reaction of phenyl isothiocyanate in basic aqueous conditions A solution of NaOH (2.34 g) in distilled water (20 mL) was added to a solution of phenyl isothiocyanate (7.89 g) in acetone (70 mL). The resulting clear yellow solution was left to sit for 48 h, followed by acidification with glacial acetic acid to a pH of 4. The product was separated as a white solid by precipitation with excess distilled water (approx. 200 mL) and recovered by filtration. The resulting white solid was dried in vacuum (7.6 g, 58%). ESI MS: capillary exit voltage 90 V,m/z [M + H]+ 229. |
With water at 150℃; | ||
With water | ||
With diethyl ether; aluminium amalgam; water | ||
With toluene; Benzaldoxime | ||
With toluene; Benzaldoxime | ||
With diethyl ether; aniline | ||
With hydrogen sulfide | ||
With aniline | ||
Multi-step reaction with 2 steps 1: 6 g / toluene / Ambient temperature 2: 500 mg / xylene / 12 h / Heating | ||
Multi-step reaction with 2 steps 1: alcohol 2: 170 °C | ||
Multi-step reaction with 3 steps 1: dichloromethane / 20 °C 2: dmap / tetrahydrofuran-d8 / 3 h / 60 °C 3: dichloromethane / 20 °C | ||
Multi-step reaction with 3 steps 1: dichloromethane / 20 °C 2: dmap / tetrahydrofuran-d8 / 72 h / 60 °C 3: dichloromethane / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sodium acetate In ethanol at 60℃; for 6h; | 2 Preparation of 3-phenyl-2- (phenylimino) thiazolidin-4-one 1,3-diphenylthiourea (1.14 g, 4.0 mmol, lequiv)Anhydrous sodium acetate (1.64 g, 20.0 mmol, 5 equiv)0.85 mL of ethyl chloroacetate (0.98 g, 8.0 mmol, 2 equiv) in 20 mL of absolute ethanol,The mixture was stirred at 60 ° C for 6 h. The reaction solution was cooled to room temperature and precipitated.The precipitate was filtered and washed with ethanol and recrystallized from ethyl acetate to give 0.68 g of an orange solid in 64% yield without further purification and used directly in the next reaction |
64% | With sodium acetate In ethanol at 60℃; | |
With ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With PEG-400 In water for 0.0333333h; microwave irradiation; | |
92% | With iodine at 90 - 95℃; for 0.166667h; | |
92% | With zinc(II) chloride at 80 - 85℃; for 0.133333h; Neat (no solvent); |
65% | for 0.0416667h; Irradiation; | |
62% | With citric acid-coated magnetic Fe3O4 nanoparticles In neat (no solvent) at 120℃; for 8h; Inert atmosphere; | General procedure for the synthesis of products 3a-ac General procedure: To a mixture of catalyst (25.0 mg) and amide (1.0 mmol),amine was added (1.0 mmol) under an argon atmosphere,and the mixture was stirred at 120 °C for 8 h. After completion,the reaction mixture was allowed to cool to roomtemperature. It was then diluted with EtOAc and the catalystwas separated from the reaction mixture using an externalmagnet and washed twice with EtOAc, then all volatileswere removed under vacuum, and the resulting residue waspurified by column chromatography on silica gel to affordthe desired product. |
58% | at 180℃; for 0.0666667h; Microwave irradiation; Neat (no solvent); | |
58% | With Fe(OH)3 supported on Fe3O4 magnetic nanoparticles In para-xylene for 10h; Inert atmosphere; Reflux; Green chemistry; | |
With pentan-1-ol | ||
With hydrogenchloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethanolamine; Lac sulfur; water for 1.5h; Heating; | |
98% | In N,N-dimethyl-formamide at 100℃; for 0.116667h; Microwave irradiation; | |
97.1% | With sulfur; sodium hydroxide In water at 60℃; for 8h; Sonication; | 5 Example 5 (1) 165 g of aniline and 260 g of a 30 wt% aqueous solution of sodium hydroxide,In the ultrasonic conditions mixed evenly,And then into the reactor; (2) take 75g of carbon disulfide and 70g of sulfur,In the ultrasonic conditions mixed evenly,And then into the reactor,Mixing with the material of step (1); (3) open the reactor stir,Stirring speed control at 100 rpm,And then heated to 60 ° C reaction 8h. (4) After the completion of the reaction, the mixture was filtered, washed with water and dried to obtain 196.4 g of DPTU product,Purity (HPLC) was 99.1%The yield was 97.1%. |
95% | at 100℃; for 12h; Ionic liquid; Green chemistry; | 3.1. General procedure for the synthesis of thiourea General procedure: In a test tube equipped with magnet stirrer, an aromatic or aliphatic amine (3 mmol), carbon disulfide (5 mmol), and ionic liquid (0.5 g) were added and the reaction mixture was stirred for 12 h at 100C. After completion, the product was extracted with diethyl ether or ethyl acetate(3 × 15 ml) and the organic phase was washed with water and aqueous hydrochloric acid solution (2 M) to remove unreacted amines. Then, the organic phase was dried with anhydrous sodium sulfate and evaporated under reduced pressure to give pure thioureas in most of the cases. Further purifications have been done by recrystallization in ethanol. Cross-condensation of amines with carbon disulfide had been done by using 1.5 mmol of each amine. All the products are known and were characterized by their 1H and 13C NMR and melting points compared with those reported in the literature. |
94% | With Cyclohexyl isocyanide In ethanol at 20℃; for 3h; | |
90% | With sulfonated polystyrene for 2h; Heating; | |
86% | With potassium hydroxide at 20℃; for 0.75h; Milling; Green chemistry; | |
83% | at 100℃; for 2h; | |
82% | In neat (no solvent) at 160℃; for 0.0833333h; Microwave irradiation; Green chemistry; | |
80% | With carbon tetrabromide In N,N-dimethyl-formamide at 20℃; for 1.5h; Cooling with ice; | |
80% | With choline chloride–urea In water at 100℃; for 5h; Cooling with ice; Green chemistry; | 2.2. General procedure for the synthesis of thiourea derivatives from one amine General procedure: In a 10mL round-bottom flask (equipped with a basic gas trap to neutralize exhausted hydrogen sulfide), 2 mmol amine was added to 3 mL distilled water and 0.1 mmol of DES (ChCl-urea). The flask was placed in an ice bath over the magnetic heater-stirrer and the mixture was stirred vigorously. Then, 1 mmol carbon disulfide was added to the mixture during the stirring. The reaction was monitored by TLC, with ethyl acetate-hexane (3:7) mixture as eluent, up to the completion of the reactant. The ice bath was then removed and replaced with an oil bath, the flask was equipped with a condenser and the reaction was heated to 100°C and stirred for 3 h with refluxing. Then, the heating was stopped and the reaction was allowed to reach to room temperature. The precipitated product (during the cooling), was purified by recrystallization in ethanol and used for the next analyses. All products are known compounds and their structures were confirmed by comparison of their mass specta, IR, 1H-NMR and 13C-NMR spectra, and melting points with the reported values in the literature [26-30]. The selected physical properties, GC-Mass results and spectroscopic data for all products are listed in section 2.4 and all original spectral data (IR, NMR and mass spectrometry) are shown in the supplementary information. |
76% | With cholin hydroxide at 80℃; Cooling with ice; Ionic liquid; | Typical procedure for the preparation of thiourea derivatives (2a-2m) General procedure: A mixture of aliphatic or aromatic amines (2mmol), carbon disulfide (1.2mmol) and ChOH (0.5 mL) was added into a test tube with a magnetic stirring bar under an ice cold condition. The test tube was stirred at room temperature (aliphatic amines) or 80°C (aromatic amines) until TLC showed completion. After the completion of the reaction, the reaction mixture was cooled to room temperature and water was added that in most cases resulted in formation of solid products. The crude product was washed with water (10mL) and purified by recrystallization from hot ethanol or washing with a mixture of EtOAc/hexane to obtain the pure product. |
72% | at 90℃; for 15h; | |
51% | With triethanolamine; sulfur In water for 6h; Reflux; | 1 Preparation of 1,3-diphenylthiourea aniline (2.33 g, 25 mmol, 2 equiv) was weighed, Carbon disulfide (1.24 g, 16.25 mmol, 2 equiv), Triethanolamine (2.5 mL) and sulfur powder (100 mg) in 50 mL of water were stirred and refluxed for 6 h. The reaction solution was cooled to room temperature and precipitated with white precipitate. Filtered and washed with cold water to give 1.46 g of a white solid, yield: 51%. |
51% | With triethanolamine; sulfur In water for 6h; Reflux; | |
With zinc(II) sulfate | ||
With sodium hydroxide | ||
With nickel(II) sulphate | ||
With pyridine | ||
With pyridine; iodine | ||
With nitrobenzene | ||
With orthoarsenic acid | ||
With ethanol; sulfur | ||
With sodium hydroxide | ||
With pyridine Darstellung; | ||
With dmap In ethanol for 18h; Reflux; | ||
With triethanolamine In water for 6h; Reflux; | ||
With sodium hydroxide at 60℃; | ||
In ethanol Reflux; | ||
With water; sulfur at 60℃; unter Ruecfluss; | ||
With sodium hydroxide | ||
With frankonitol | ||
With pyrographite |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 20℃; | General experimental procedure for guanidines (entries 11-18) General procedure: Method B: To a stirred solution of 1,3-disubstituted thiourea (5 mmol) and amine (5 mmol) in acetonitrile (10 mL) was added drop wise a solution of IBX (5.5 mmol), in triethylamine (15 mmol) at rt over a period of 10 min. After completion of reaction as analysed by TLC (reaction time 30 min) the mixture was extracted with (2 × 15 mL) ethyl acetate. The organic layer was washed with 10% aqueous sodium bicarbonate solution (2 × 15 mL), evaporated and chromatographed to afford the pure product. |
70% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 19h; Irradiation; | |
With ethanol; iodine |
With ethanol; lead(II) oxide | ||
With ethanol; lead(II) oxide die von PbS befreite Loesung wird mit Wasser gefaellt; | ||
With sodium hydroxide; zinc(II) sulfate | ||
With basic lead(II) carbonate; lead(II) oxide | ||
With water; lead(II) oxide; toluene | ||
With lead(II) hydroxide on calcium carbonate; ethanol | ||
With ethanol; mercury(II) oxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With acetyl chloride at 60℃; for 0.5h; | 4.1.2 1,3-Diphenylthiobarbituric acid (1a) A stirred solution of 59 1,3-diphenylthiourea (1.00mmol; 228mg), 64 malonic acid (1.30mmol; 135mg) and 65 acetyl chloride (3.00mmol; 235mg; 214μL) was heated at 60°C for 30min. The solid 66 product obtained was ground into finer powder, filtered, washed with water and recrystallized from acetic acid; Yield 95%; needle-like yellow crystals; mp 252-253°C (lit [36] 258-259°C); IR υmax (cm-1) 3053, 2895, 1727, 1707, 1594, 1490, 1454, 1381, 1338, 1260, 1212, 1165, 1169, 1037, 1003, 927, 747, 696, 687, 667; 1H NMR (400MHz, CDCl3) δ (ppm) 7.55 (m, 6H, ArCH), 7.21 (d, J= 7.3Hz, 4H, 6′ and 2′-ArCH), 4.10 (s, 2H, 5-CH2); 13C NMR (101MHz, CDCl3) δ (ppm) 181.64 (2-CS), 163.32 (4 and 5-CO), 138.75 (ArC), 129.68 (ArCH), 129.20 (ArCH), 128.64 (ArCH), 41.23 (5-CH2). |
95% | With acetyl chloride at 60℃; for 0.5h; | 4.1.2. 1,3-Diphenylthiobarbituric acid (1b) [6] A stirred solution of 1,3-diphenylthiourea (1 mmol;228 mg), malonic acid (1.3 mmol; 135 mg), and acetylchloride (3 mmol; 235 mg; 214 mL) was heated at 60 C for30 min. The solid product so obtained was divided intofiner pieces, filtered, washed with water, and recrystallizedfrom acetic acid; 282 mg (95%); needle yellow crystals; mp252e253 C (lit. [6], 258e259 C). 1H NMR (400 MHz,CDCl3) d (ppm) 7.55 (m, 6H), 7.21 (d, J 7.3 Hz, 4H), 4.10 (s,2H); 13C NMR (101 MHz, CDCl3) d (ppm) 181.6, 163.3, 138.8,129.7, 129.2, 128.6, 41.2. |
90% | With acetyl chloride for 2h; Heating; |
90% | With acetyl chloride for 0.0152778h; Irradiation; | |
With trichlorophosphate | ||
With acetyl chloride | ||
With acetyl chloride | ||
With acetyl chloride at 60℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: N,N-diphenylthiourea With N-<(trimethylsiloxy)methyl>dimethylamine In dichloromethane at 20℃; Inert atmosphere; Stage #2: methyl iodide In dichloromethane at 20℃; for 2.25h; Inert atmosphere; | Reaction of 1-[(dimethylamino)methyl]-1,2-diphenylthiourea (8) with MeI. A 20 mL round-bottom flask was charged with a solution of 0.24 g (1.27 mmol) of 1 and 0.29 g (1.27 mmol) of 1,3-diphenylthiourea in 10 mL of dichloromethane. The solution was stirred overnight at room temperature. Excess of MeI (1 mL) was then added with a syringe to the reaction mixture. After 15 min of stirring, a white solid started to precipitate, and the reaction mixture was further stirred for 2 h. The solvent and triethylsilanol were removed under vacuum. The white solid was treated twice with 15 mL of hexane, the extract was filtered, and the solvent was removed to obtain methyl N,N-diphenylcarbamimidothioate PhN=C(SMe)NHPh (13), yield 62% yield, mp 106°C (107°C [13]). |
das jodwasserstoffsaure Salz entsteht; die freie Base erhaelt man durch Faellen der waessr.Loesung des Salzes mit Natronlauge; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium permanganate; gold; oxygen In dichloromethane at 80℃; for 4h; | |
90% | With iodine; oxygen In chlorobenzene at 120℃; for 10h; Schlenk technique; Green chemistry; | |
82% | With ruthenium trichloride; Oxone In 1,2-dichloro-ethane Inert atmosphere; Schlenk technique; Heating; |
81% | With disulfur dichloride at 60℃; | |
80% | With polymer-supported tribromide at 100℃; for 0.333333h; Microwave irradiation; | |
50% | With oxygen; palladium dichloride In 1-methyl-pyrrolidin-2-one at 140℃; | |
50% | With pyridine; iron(III) chloride; sodium persulfate In dimethyl sulfoxide at 80℃; for 3h; Inert atmosphere; | |
With chloroform; bromine Behandeln des entstandenen Perbromids mit schwefliger Saeure oder Disulfit-Loesung; | ||
With bromine folgend Reduktion; | ||
With sulfur; aniline | ||
With lead(II) dihydrogen orthophosphate; H2<Pb(H2PO4)2(HPO4)2>; buffer solution In methanol for 1.5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.1% | With ammonium hydroxide; oxygen; copper diacetate; In ethyl acetate; acetone; at 60℃; under 1875.19 Torr; for 0.05h; | (1) 400 g of diphenyl thiourea, 0.5 g of catalyst copper acetate and 372 mL of concentration 24wt.% ammonia water, Then, the slurry is mixed with 3500 mL of a mixed solvent of acetone and ethyl acetate (volume ratio of acetone to ethyl acetate of 3:1) under stirring to obtain a reaction raw material mixture; (2) The reaction raw material mixture and oxygen are 2.9 mL/min according to the raw material mixture. oxygen gas flow rate of 14.3mL / min into the microchannel reactor for oxidation reaction, Reaction temperature 60 C, The residence time is 3 min, and the reaction pressure is 0.25 MPa; The microchannel reactor is 10 pieces in series. The volume of the single piece is 1.86 mL, and the full volume is 18.6 mL; (3) The product solution obtained by the reaction is subjected to distillation under reduced pressure to recover an organic solvent, and the obtained solid material is subjected to alkali washing, washing with water, and drying to obtain a vulcanization accelerator DPG.According to the calculation, the DPG yield of this example was 96.1% (calculated as CA dosage), and the appearance was white microcrystalline powder. |
90% | With ammonia; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In water; acetonitrile; at 20℃; | General procedure: Method A: To a stirred solution of 1,3-disubstituted thiourea (5 mmol) in acetonitrile (10 mL) was added drop wise a solution of IBX (5.5 mmol), in aqueous ammonia (10 mL of a 28-30% solution) at rt over a period of 10 min. After completion of reaction as analysed by TLC (reaction time 30 min) the mixture was extracted with (2 × 15 mL) ethyl acetate. The organic layer was washed with 10% aqueous sodium bicarbonate solution (2 × 15 mL), evaporated and chromatographed to afford the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dmap; methanesulfonyl chloride; triethylamine In dichloromethane for 0.0833333h; Ambient temperature; | |
95% | With dicarbonyl(cyclopentadienyl)methyliron(II); Triethoxysilane In tetrahydrofuran at 60℃; for 24h; Schlenk technique; Inert atmosphere; | |
95% | With iodine; triethylamine; triphenylphosphine In dichloromethane for 0.0833333h; Sonication; | General procedure for the synthesis of carbodiimide General procedure: To a solution of 0.0844 g iodine (0.33 mmol) and 0.0872 g triphenylphosphine (0.33 mmol) in 2 cm3 CH2-Cl2 was added a solution of thiourea or urea(0.275 mmol) and 0.0701 g triethylamine (0.69 mmol) in2 cm3 CH2Cl2 under sonication. The reaction mixture was further sonicated until completion of the reaction as indicated by TLC. The crude mixture was concentrated under reduced pressure then purified by column chromatography using hexane to give the carbodiimide (see supporting information for characterization data of all products). |
94% | With 1,1'-Thiocarbonyldi-2(1H)-pyridone In toluene for 0.3h; Heating; | |
90% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dichloromethane at 0℃; for 0.166667h; | |
89% | With p-methoxybenzenetellurinic acid anhydride In dichloromethane for 1h; Ambient temperature; | |
86% | With 2-chloro-1,3-dimethylimidazolinium chloride; triethylamine In dichloromethane at 20℃; for 4h; | |
86% | With iodine; triethylamine In ethyl acetate at 0 - 5℃; for 0.5h; | |
85% | With di-2-pyridyl sulfite In dichloromethane for 0.166667h; Ambient temperature; | |
85% | With [hydroxy(tosyloxy)iodo]benzene; triethylamine In ethyl acetate for 5h; Cooling with ice; | |
83% | With dmap; di-<i>tert</i>-butyl dicarbonate In ethyl acetate at 20℃; for 0.5h; | General procedure for the preparation of crabodiimides (at room temperature) General procedure: To a mixture of thiourea (0.5 mmol) and DMAP (0.1 mmol) in ethyl acetate (2 mL) was added (Boc)2O (0.55 mmol, 126 μL) under stirring. The mixture was stirred at room temperature until the completion of reaction determined by TLC. The solvent was evaporated in vacuo and the residue was purified by column chromatography on silica gel eluted with CH2Cl2/PE (1:5) to give the corresponding products. |
82% | Stage #1: N,N-diphenylthiourea With dmap; triethylamine In dichloromethane at 0℃; Stage #2: With methanesulfonyl chloride In dichloromethane at 20℃; for 1h; | |
80% | With iodine; triethylamine In ethyl acetate at 0℃; for 0.5h; Inert atmosphere; | |
62% | With diethoxydisulfane; 4 A molecular sieve In dichloromethane for 5h; Heating; | |
62% | With 2,4-Dichloro-5-nitropyrimidine In acetonitrile for 0.333333h; Ambient temperature; | |
62% | With iodine; triethylamine In ethyl acetate at 0℃; for 1h; | |
41% | With methyl azodicarboxylate polystyrene resin 3b; triphenylphosphine In tetrahydrofuran at 20℃; for 24h; | |
25% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dichloromethane at 0℃; for 0.5h; | N,N'-methanediylidenedianiline (2c). Prepared according to literature procedure. To round bottom flask was added IBX (560.0 mg, 2.0 mmol) in CH2Cl2 (9.0 mL) at 0 C, then added triethylamine (506 µL, 4.0 mmol). A 1,3-diphenylthiourea (456.0 mg, 2.0 mmol) was added to the mixture. The reaction mixture was maintained at 0 °C for 30 minutes to provide a light yellow mixture, then filtered the white solid with cotton and concentrated with vacuum. The crude mixture was diluted with hexanes, then dropped a hexane layer. The hexane layer dried over anhydrous Na2SO4, filtered and concentrated. The crude mixture was purified by column chromatography (100% hexanes) to provide coloress oil in 100 mg (25 % yield). 1H NMR (300 MHz, CDCl3) δ 7.35-7.29 (m, 6H), 7.19-7.17 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 138.4, 136.2, 129.2, 125.2, 124.0. Other data was identical to the literature values. |
With mercury(II) oxide; benzene | ||
With mercury(II) oxide man verdunstet sofort die benzolische Loesung und destilliert im Vakuum; | ||
With calcium chloride; mercury(II) oxide; benzene | ||
With arsenic(III) trioxide | ||
With lead(II) oxide In acetone | ||
With mercury(II) diacetate; formic acid hydrazide In N,N-dimethyl-formamide; acetonitrile | ||
With lead(II,IV) oxide In benzene Heating; | ||
With triethylamine; triphenylphosphine In tetrachloromethane; hexane; dichloromethane | 5 Diphenylcarbodiimide Preparation 5 Diphenylcarbodiimide 1,3-Diphenylthiourea (22.8 g), triphenylphosphine (10.1 g) triethylamine (10.1 g) and carbon tetrachloride (21.6 g) were refluxed for 4 hours in methylene chloride (300 ml). The solvent was removed under vacuum. The residue was shaken with hexane (300 ml); the hexane solution was evaporated and the residue was distilled to afford the title compound as an oil bp 115°-120°/0.3 mm. | |
With sodium sulfate; mercury(II) oxide In dichloromethane at 20℃; for 2h; | ||
With calcium chloride; mercury(II) oxide In acetone for 1h; Reflux; | ||
With mercury(II) oxide In acetone for 1h; Reflux; Schlenk technique; Glovebox; | ||
With iodine; triethylamine; triphenylphosphine In dichloromethane Inert atmosphere; Sonication; | ||
With 1,3,5-trichloro-2,4,6-triazine; sodium carbonate; triphenylphosphine In dichloromethane at 20℃; Sonication; | 2. General procedure for guanylation of amine General procedure: Unless otherwise specified, thiourea (0.271 mmol), TCT (0.0200 g, 0.108 mmol), PPh3 (0.0071 g, 0.027 mmol), Na2CO3 (0.1436 g, 1.355 mmol), and dichloromethane (250 L) were added into a 5 mL glass vial. The mixture was then irradiated in water bath of the 37 kHz ultrasonic cleaner (Elmasonic S 30H) at room temperature for 10 min. After that, an amine (0.298 mmol) was added, followed by ultrasonic irradiation until the reaction completion. The crude material was purified by column chromatography using ethyl acetate/hexanes as the eluent to afford pure product. | |
With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium hydroxide; copper(l) chloride In water; acetonitrile at 25℃; for 0.333333h; | |
98% | With quinolinium monofluorochromate(VI) In acetonitrile for 3.5h; Heating; | |
98% | With trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane; water; potassium hydroxide In acetonitrile at 20℃; for 0.0166667h; | 4.2. Typical procedure for desulfurization of thiourea derivatives 1a-1s to oxoanalogs 2a-2s To a stirred solution of phenylthiourea 1 (1mmol) and 5% aq. KOH (5 mL) in acetonitrile (5 mL) was added DHPDMDO (0.332 g, 2mmol). The resulting mixture was allowed to stir at room temperature for an appropriate time (Table 2). After completion of the reaction as monitored by TLC, the reaction mixture was diluted with water (10mL) and the product was extracted in dichloromethan (3×5mL). The combined organic layer was washed with water (2×5mL) and dried over anhydrous Na2SO4. Evaporation of the solvent under reduced pressure gave almost pure products. Structures of the known products were established on the basis of their physical and spectroscopic (IR, 1H-NMR and 13C-NMR) data, which were consistent with those reported.[34,61] |
97% | With bismuth(III) nitrate In acetonitrile for 0.333333h; Heating; | |
96% | With Celite; silver carbonate In acetonitrile at 20℃; for 3h; | |
96% | With 3-carboxypyridinium chlorochromate In acetonitrile for 0.0333333h; microwave irradiation; | |
94% | With polystyrene-bound diaryl telluroxide In dichloromethane for 3.5h; Ambient temperature; | |
92% | With sodium periodate for 0.333333h; Ambient temperature; further reagents; | |
90% | With benzyltriphenylphosphonium peroxodisulfate In acetonitrile for 0.25h; Heating; | |
85% | With potassium superoxide In dimethyl sulfoxide for 8h; Ambient temperature; | |
82% | With polystyrne-bound selenoxide In methanol; dichloromethane for 12h; Ambient temperature; | |
82% | With Oxone for 0.333333h; | |
80% | With bis(tri-n-butyltin)oxide In benzene for 2h; Heating; | |
80% | With Oxone In acetonitrile for 0.416667h; Heating; | |
72% | With copper(I) oxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; di-tert-butyl peroxide; tetrabutylammomium bromide In water at 110℃; for 15h; Schlenk technique; Sealed tube; Green chemistry; | |
69% | With potassium superoxide; 18-crown-6 ether for 1h; Ambient temperature; | |
61% | With C15H12N4O3; potassium carbonate In ethanol; water for 5h; Irradiation; | |
55% | With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol for 10h; Heating; further halogens as catalysts; | |
39% | With benzeneseleninic anhydride In tetrahydrofuran for 5h; Ambient temperature; | |
With ammonium acetate; acetic acid at 100℃; | ||
With potassium carbonate | ||
With ethanol; mercury(II) oxide | ||
With alkaline potassium ferricyanide | ||
With acetic acid at 100℃; | ||
With hydroxylamine hydrochloride; acetic acid | ||
With acetic acid; guanidine nitrate | ||
With sodium peroxide | ||
With acetic acid at 130 - 140℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In water at 25℃; for 0.1h; Green chemistry; | Procedure for the synthesis of thiazolidines 2-11 General procedure: Thiourea derivative (1, 2 mmol) was dissolved in 2 mL of a mixture (see Table 1) of ethyl L-lactate and water. To this dialkyl acetylenedicarboxylate was added and the contents were stirred. A solid product was formed after a few minutes (Table 1), which was then filtered and washed with water. In case of oily product, the solvent was decanted and the residue was subjected to silica gel column chromatography (Hexanes/ethyl acetate: 90/10). All known compounds were characterized by using 1H NMR and 13C NMR and the data was compared with that of reported compounds. |
83% | In acetone at -10℃; for 0.5h; stereoselective reaction; | |
62.3% | In methanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With triethylamine In acetonitrile for 1.5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 5 - 10℃; for 0.5h; | |
82% | With triethanolamine; lac sulfur on alumina In tetrahydrofuran for 1h; Heating; | |
82% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 72h; Irradiation; Green chemistry; |
80% | With sodium chlorite In water; N,N-dimethyl-formamide at 80 - 85℃; for 1.5h; | |
With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 5 - 10℃; for 0.5h; | |
92% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 15h; Irradiation; | |
84% | With sodium periodate In water; N,N-dimethyl-formamide for 0.5h; Ambient temperature; |
80% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 20℃; | General experimental procedure for guanidines (entries 11-18) General procedure: Method B: To a stirred solution of 1,3-disubstituted thiourea (5 mmol) and amine (5 mmol) in acetonitrile (10 mL) was added drop wise a solution of IBX (5.5 mmol), in triethylamine (15 mmol) at rt over a period of 10 min. After completion of reaction as analysed by TLC (reaction time 30 min) the mixture was extracted with (2 × 15 mL) ethyl acetate. The organic layer was washed with 10% aqueous sodium bicarbonate solution (2 × 15 mL), evaporated and chromatographed to afford the pure product. |
78% | With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 5 - 10℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 15h; Irradiation; | |
87% | With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 5 - 10℃; for 0.5h; | |
76% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; Green chemistry; |
0.1016 g | With [bis(acetoxy)iodo]benzene; sodium hydroxide In water at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | at 60℃; for 1h; | |
100% | In acetic acid for 0.25h; Heating; | |
95% | In water at 20℃; for 0.75h; Green chemistry; | General procedure of reactions: General procedure: A reaction mixture of ninhydrin (1), (10 mmol) and weak nitrogen nucleophiles [urea (2a), thiourea (2b), diphenyl thiourea (2c), guanidine (2d), cyanoacetamide (2e) and diphenyl amine (2f)] (10 mmol) in1:1 molar ratio were well dissolved in water (2a-2c) and ethanol (2d-2f). Then the mixture was stirred over water bath at room temperature for 40-75 min. The solvent was removed by filtration to give the solid product which was then recrystallized from water (3a-3c) and ethanol (3d-3f), respectively. The physico-chemical data of the synthesized compounds are given in Table-1. |
52% | In water at 50 - 60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With iodine; potassium carbonate In ethanol; water at 20℃; | 4.2. General procedure for the preparation of N,4-disubstituted-4H-1,2,4-triazol-3-amine from symmetrical thioureas 1-7 General procedure: To a suspension of 1,3-disubstituted thioureas 1-7 (1 mmol) in ethanol (2 mL) were added sequentially formic hydrazide (2.5 mmol) and aqueous K2CO3 (2.5 mmol in 0.5 mL water) and the mixture was stirred at room temperature. Under this stirring condition iodine (1.2 mmol) was added pinch wise over a period of 10 min. Disappearance of iodine colour was associated with the precipitation of colloidal sulfur. The reaction mixture was stirred for a further period of 20-40 min. During this period complete disappearance of 1,3-disubstituted thiourea was observed with the appearance of a new product having lower Rf. Precipitated elemental sulfur was filtered off and the filtrate ethanol was removed in a rotary evaporator. The reaction mixture was treated with a 5% hypo solution (5 mL) and the product was extracted with ethyl acetate (2×10 mL). The combined ethyl acetate layer was washed with water (1×5 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The reaction product was purified over a column of silica gel and eluted with hexane/ethyl acetate mixture to give the corresponding products 1a-7a. |
80% | With Oxone; iodobenzene; triethylamine In methanol at 20℃; for 3h; | Typical experimental procedure to synthesize 3-amino-1,2,4-triazoles General procedure: A mixture of iodobenzene (2 equiv) and Oxone (4 equiv) in methanol was stirred at rt for 20 min followed by the addition of TEA (3 equiv) and substrate (1 equiv) and after 5 min formyl hydrazide (3 equiv) was added at rt and stirred for 3 h. The reaction mixture was diluted with H2O and then extracted twice with EtOAc. The organic layer was washed successively with 10% NaHCO3 (2 × 20 mL)and H2O (2 × 20 mL) and dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to give the crude product. The product was purified using silica gel column chromatography (20% EtOAc-hexane). |
72% | With mercury(II) diacetate In N,N-dimethyl-formamide; acetonitrile at 20℃; for 2h; |
72% | Stage #1: N,N-diphenylthiourea With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In N,N-dimethyl-formamide Stage #2: formic acid hydrazide In N,N-dimethyl-formamide at 20℃; for 3h; | |
212 mg | With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; for 4h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: N,N-diphenylthiourea With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In N,N-dimethyl-formamide Stage #2: With sodium azide In N,N-dimethyl-formamide at 20℃; for 3h; | |
88% | With Oxone; sodium azide; iodobenzene; triethylamine In water; acetonitrile at 20℃; for 3h; | Typical experimental procedure to synthesize 5-aminotetrazoles General procedure: A mixture of iodobenzene (2 equiv) and Oxone (3 equiv) in ACN/water was stirred at rt for 20 min followed by the addition of TEA (3 equiv) and substrate (1 equiv) and after 5 min NaN3 was added at rt and stirred for 3 h. The reaction mixture was diluted with H2O and then extracted twice with EtOAc. The organic layer was washed successively with 10% NaHCO3 (2 × 20 mL) and H2O (2 × 20 mL) and dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to give the crude product. The product was purified using silica gel column chromatography (20% EtOAc-hexane). |
Multi-step reaction with 2 steps 1: potassium hydroxide; alcohol; hydrazine hydrate / 110 - 115 °C 2: hydrochloric acid; sodium nitrite |
356 mg | With sodium azide; iodine; triethylamine In N,N-dimethyl-formamide for 4.58333h; | |
199 mg | With copper(l) iodide; sodium azide; caesium carbonate In dimethyl sulfoxide at 80℃; for 5h; regioselective reaction; | |
With sodium azide; potassium carbonate; mercury dichloride In water at 100℃; regioselective reaction; | ||
With sodium azide; iodine; triethylamine In N,N-dimethyl-formamide at 20 - 70℃; for 14h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfur at 220 - 300℃; | 2; 4 Example 2 (After stationary state was reached by multiple recycling of a part of aniline filtrates); 100 g of aniline filtrate from crystallization (containing 78 % of aniline, 9.5 % of 2-mercaptobenzothiazole) were charged into a pressure 300 ml reactor together with 27 g of sulphur, 67 g of carbon disulphide and 9 g of volatile fractions from the preceding purging of the melt (containing 30 % of aniline and 65 % of benzothiazole). Under conditions usual for this synthesis (220 to 300 °C/6 to 11.1 MPa) a melt of the raw product was prepared. After reaction the reactor was cooled down to 180 to 200 °C and the reactor content was purged at 200 °C by nitrogen stream, removing the volatile fractions. 162.3 g of purged melt were obtained containing 91.0 % of 2- mercaptobenzothiazole, 2.0 % of benzothiazole, 1.5 % of sulphur, 0.9 % of anilidobenzothiazole, 0.1 % of thiocarbanilide, 0.07 % of 2-methylbenzothiazole and 4.43 % of pitches, which melt was dissolved in a mixture of 222 g of liquid phase (filtrate) from the preceding crystallization and 200 g of liquid phase (filtrate) from the preceding final purification by wash separation. After cooling down the crystallized 2-mercaptobenzothiazole product was filtered off, from-295 g of the filtrate 5 % were removed out of the process (waste), 100 g were used as a charge of the next batch in the reactor and the remaining filtrate was used in the next crystallization. Wet aniline cake containing 2-mercaptobenzothiazole was wash separated in 91 g of pure aniline, filtered off, aniline was removed from it by wash separation in hot water and by purging with water steam, and dried. The filtrate from wash separation, consisting in general only of aniline and 2-mercaptobenzothiazole, was used in the next crystallization. 136.9 g of the product containing 98.2 % of active substance, i. e. 91 % yield with respect to 2-mercaptobenzothiazole in the melt, were obtained.; Example 4; 20 g of aniline, 80 g of aniline filtrate from crystallization of the same composition as in Example 1 (78 % of aniline, 9.5 % of 2-mercaptobenzothiazole) were charged into the reactor together with 28 g of sulphur, 71 g of carbon disulphide and 9 g of benzothiazole from purging (volatile fractions). The reactor was heated to working temperature, after reaction it was cooled to 180 to 200 °C, accumulated hydrogen sulphide was released through a pressure control valve and the reactor content was evacuated at 200 °C. At a reduced pressure of 20 Torr and a temperature of 200 °C, volatile fractions were distilled off from the melt. 161 g of purged melt were obtained containing 92.2 % of 2- mercaptobenzothiazole, 1.8 % of benzothiazole, 1.3 % of sulphur, 0.7 % of anilidobenzothiazole, 0.1 % of thiocarbanilide, 0. 05 % of 2-methylbenzothiazole and 3.85 % of unidentified substances. The melt was dissolved in a mixture of 222 g of filtrate from the preceding crystallization and 200 g of filtrate from the preceding refinement. After cooling down the crystallized 2- mercaptobenzothiazole was filtered off, from the filtrate 20 % were removed out of the process, 80 g were separated for the next batch in the reactor and the rest for the next crystallization. Wet aniline product cake was wash separated in 115 g of pure aniline, filtered off, cleared of aniline, and dried. The filtrate from wash separation was used in the next crystallization. 129.2 g of the product with purity of 99.4 % were obtained, i. e. 86.5 % yield with respect to 2-mercaptobenzothiazole in the melt. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium hydrogencarbonate In ethyl acetate at 20℃; for 0.25h; | |
100% | With sodium hydrogencarbonate In ethyl acetate at 20℃; for 0.25h; | Syntheses of 4-(arylimino)-1,3-thiazetidin-2-ones 1a-1j General procedure: To a mixture of ethyl acetate (25 mL), sodium bicarbonate (11.5 mmol, 0.97 g) and thioureas (5 mmol), BTC [bis(trichloromethyl)carbonate] (1.7 mmol, 0.5 g) was added carefully in portions. The reaction mixture was stirred at room temperature for 15 min. After completion (by TLC), the mixture was filtered, the organic solvent was condensed and the compounds 1 were obtained as crystal almost quantitative. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In water at 25℃; for 0.1h; Green chemistry; | Procedure for the synthesis of thiazolidines 2-11 General procedure: Thiourea derivative (1, 2 mmol) was dissolved in 2 mL of a mixture (see Table 1) of ethyl L-lactate and water. To this dialkyl acetylenedicarboxylate was added and the contents were stirred. A solid product was formed after a few minutes (Table 1), which was then filtered and washed with water. In case of oily product, the solvent was decanted and the residue was subjected to silica gel column chromatography (Hexanes/ethyl acetate: 90/10). All known compounds were characterized by using 1H NMR and 13C NMR and the data was compared with that of reported compounds. |
64% | In acetone at -10℃; for 0.5h; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With sodium acetate In dichloromethane at -20 - 20℃; for 5h; | 4.2.1. 4-Hydroxy-4-methoxycarbonyl-3,5-diphenyl-2-(pyridin-2-ylimino)thiazolidine (1b) and 4-hydroxy-4-methoxycarbonyl-5-phenyl-2-phenylimino-3-(pyridin-2-yl)thiazolidine (1'b) General procedure: Sodium acetate (3.6 g, 43.8 mmol) was added to the solution N-(pyrid-2-yl)-N'-phenylthiourea 5b (4 g, 17.5 mmol) in 150 mL of dry CH2Cl2 then cooled to the temperature from -15 to -20 °C, methyl chloro(phenyl)pyruvate104a (3.7 g, 17.5 mmol) was added dropwise. The reaction mixture was stirred for 5 h at ∼20 °C and poured into water (150 mL). The organic layer was separated, and the aqueous layer was extracted with CHCl3 (2×20 mL). The organic layer and the extract were combined and dried with MgSO4, and the solvent was removed in vacuo. A crude yellow oil was obtained and a mixture of 4-hydroxy-4-methoxycarbonylthiazolidines (1b+1'b) was obtained after recrystallization from i-PrOH in a yield 3.4 g (50%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 20℃; | General experimental procedure for guanidines (entries 11-18) General procedure: Method B: To a stirred solution of 1,3-disubstituted thiourea (5 mmol) and amine (5 mmol) in acetonitrile (10 mL) was added drop wise a solution of IBX (5.5 mmol), in triethylamine (15 mmol) at rt over a period of 10 min. After completion of reaction as analysed by TLC (reaction time 30 min) the mixture was extracted with (2 × 15 mL) ethyl acetate. The organic layer was washed with 10% aqueous sodium bicarbonate solution (2 × 15 mL), evaporated and chromatographed to afford the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With triethylamine; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 20℃; | General experimental procedure for guanidines (entries 11-18) General procedure: Method B: To a stirred solution of 1,3-disubstituted thiourea (5 mmol) and amine (5 mmol) in acetonitrile (10 mL) was added drop wise a solution of IBX (5.5 mmol), in triethylamine (15 mmol) at rt over a period of 10 min. After completion of reaction as analysed by TLC (reaction time 30 min) the mixture was extracted with (2 × 15 mL) ethyl acetate. The organic layer was washed with 10% aqueous sodium bicarbonate solution (2 × 15 mL), evaporated and chromatographed to afford the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; | |
With benzyl(triethyl)ammoniumpermanganate In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With MCM-41 mesoporous silica In ethanol; water at 80 - 90℃; for 15h; Green chemistry; | General synthetic procedure for preparation of thioamide (4): General procedure: In a typical reaction a solution of amide (1 mmol), rhodanine (1.2 mmol) and Morpholine (1.2 mmol) in EtOH/water (2 + 2 ml) were refluxed at 80-90 °C till completion using 40 mg of MCM-41 catalyst. The completion of the reaction was indicated by the disappearance of the starting material in thin layer chromatography. After completion of the reaction the solvent was evaporated in a rotary evaporator and the crude product was taken in dichloromethane and filtered to separate the products as filtrate from the catalyst (residue). Then the crude product was purified by silica gel column chromatography where the compound (5) came out from the column with 25%EtOAc/75% petroleum ether, but thioamide (4) came out with 65%EtOAc/35% petroleum ether making their separation easy. The thioamides (4) were characterized by IR, 1H NMR, 13C NMR, CHN and X-ray single crystal analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With choline chloride; urea at 80℃; for 1h; | General Procedure for the Synthesis of Bisthiazolidinones General procedure: A mixture of dialdehyde (1 mmol), N,N'-diarylthiourea(2 mmol) and choloroacetyl chloride (2.2 mmol) inChCl.2urea (0.3 mL) was added into a test tube with a magnetic stirring bar. The test tube was heated in an oil bath at80 °C for 60-120 minutes and then was cooled to room temperature slowly and ethanol, in some cases MTBE (10 mL)was added slowly and filtered off to extract the product from the deep eutectic solvent. All compounds were characterized on the basis of their spectroscopic data (IR, NMR) and elemental analyses. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With water In acetonitrile at 20℃; for 24h; | General procedure for the preparation of compounds 4a-h General procedure: To a stirred solution of the alkyl isocyanide (2 mmol) and alkylchloroglyoxalate (2 mmol) in MeCN (2 mL) was added a solution ofthe thiourea derivative (2 mmol) in MeCN (1 mL) at room temperature.The mixture was then allowed to stir for 24 h. The solidproduct was removed by filtration and the precipitate was separatedand washed with a mixture of hexane-Et2O (1:2), and neutralizedwith Et3N in a mixture of H2O-MeOH (1:2). The powderobtained was dried and used for further analysis withoutrecrystallization. White powder; yield 0.36 g (88%); mp = 258-264 °C. IR (KBr) (νmax/cm-1): 3350 (NH), 1764 (C=O), 1649 (C=O), 1514, 1491, 1402, 1313, 1132. 1H NMR: (DMSO-d6, 250.1 MHz) δ (ppm): 0.99-1.58 (m, 10H, 10CH cyclohexyl), 3.44-3.45 (m, 1H, CH cyclohexyl), 7.29-7.57 (m, 10H, 2Ph), 7.99 (d, 1H, 3JHH = 8.5 Hz, NH), 8.89 (d, 1H, 3JHH = 8.5 Hz, OH). 13C NMR (DMSO-d6, 62.9 MHz) δ (ppm): 25.1 (CH2), 25.3 (2CH2), 31.9 (2CH2), 48.6 (N-CH), 88.8 (C), 129.0 (2CH), 129.2 (CH), 129.3 (CH), 129.4 (CH), 129.5 (CH), 129.6 (CH), 129.7 (CH), 129.8 (CH), 129.9 (CH),133.7 (C), 135.8 (C), 163.3 (C=O), 170.2 (C=O), 183.1 (C=S). MS: m/z (%): 409 (M+, 3), 284 (100), 136 (13), 120 (8), 77 (10). Anal. Calcd for C22H23N3O3S (409.51): C, 64.53; H, 5.66; N, 10.26. Found: C, 64.40; H, 5.50; N, 10.46. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With water In acetonitrile at 20℃; for 24h; | General procedure: To a stirred solution of the alkyl isocyanide (2 mmol) and alkylchloroglyoxalate (2 mmol) in MeCN (2 mL) was added a solution ofthe thiourea derivative (2 mmol) in MeCN (1 mL) at room temperature.The mixture was then allowed to stir for 24 h. The solidproduct was removed by filtration and the precipitate was separatedand washed with a mixture of hexane-Et2O (1:2), and neutralizedwith Et3N in a mixture of H2O-MeOH (1:2). The powderobtained was dried and used for further analysis withoutrecrystallization. White powder; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With water In acetonitrile at 20℃; for 24h; | General procedure: To a stirred solution of the alkyl isocyanide (2 mmol) and alkylchloroglyoxalate (2 mmol) in MeCN (2 mL) was added a solution ofthe thiourea derivative (2 mmol) in MeCN (1 mL) at room temperature.The mixture was then allowed to stir for 24 h. The solidproduct was removed by filtration and the precipitate was separatedand washed with a mixture of hexane-Et2O (1:2), and neutralizedwith Et3N in a mixture of H2O-MeOH (1:2). The powderobtained was dried and used for further analysis withoutrecrystallization. White powder; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With sodium acetate In ethanol at 78℃; for 5h; | 1.2 (2) compound2a synthesis: 250 ml round-bottom flask by adding white solid 2-bromo-2-benzoic acid1a (1.74mol), C13H12N2S (1.74mol), sodium acetate (1.74mol) and anhydrous ethanol (80 ml), in 78 °C heating to reflux, the reaction under stirring 5 hours, after the reaction, the solvent turns on lathe does, adding saturated sodium carbonate aqueous solution to the reaction the bottle is straight to pH= 7, then adding ethyl ether (150 ml)-hexane (150 ml) in continuing to stir at room temperature 15 minutes, a white solid precipitated, filtering, drying, to obtain white solid2a (71% yield). |
71% | With sodium acetate In ethanol for 5h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With nickel(II) acetylacetonate In acetone at 50℃; for 1h; | 1.1 1) Preparation of triazine thiazole derivative 3a Diphenyl thiourea (0.6 mmol, 137 mg), cyclohexylisonitrile (1.50 mmol, 164 mg) was added to a 25 mL single-necked flask, and catalyst Ni (acac) 2 (0.018 mmol, 5 mg) was added as a catalyst, 2 mL of acetone as a solvent, and stirred at 50 ° C for 1 h. The system precipitated solid, filtered to obtain a white powder as a solid, washed with methanol solution to get the pure target product. NMR and HRMS were confirmed to be triisothiazole derivative 3a in a yield of 93%. |
91% | With bis(acetylacetonate)nickel(II) In acetone at 50℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 55% 2: 45% | With cyanomethanide In acetonitrile at 20℃; Inert atmosphere; | 6. Experimental procedure General procedure: Products 3a-3g were prepared following a previously reported procedure [16]. Electrolysis of 100 mL of dry acetonitrile in the presence of TBABF4 0.1 M as supporting electrolyte was carried out under galvanostatic conditions (I = 80 mA) and maintained under an inert atmosphere of nitrogen. The solution was placed in an undivided electrochemical cell cooled at -20°C, with a stainless steel grid cathode (apparent area about 20 cm2) and a magnesium rod as a sacrificial anode (9 cm2). After the consumption of 2,2 faradays per mole of thiourea, the current imposed was switched of and immediately 4×10-3 mol of N,N-disubstituted thiourea was added to the reaction medium. Finally, 4×10-3 mol of dialkyl acetylene dicarboxylate (2) was introduced and the solution was kept under stirring overnight at room temperature. Once the reaction was finished, the solvent was removed under reduced pressure. The residue was extracted with ether and the organic phase concentrated by evaporation. The resulting residue was chromatographed on a silicagel column using petroleum ether/ethyl acetate (9/1v/v) as eluent. Elemental analyses and spectroscopic descriptions of compounds 3 are given below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.5% | With oct-1-ene In diethylene glycol dimethyl ether at 95℃; for 0.0166667h; Inert atmosphere; Glovebox; Sealed tube; Schlenk technique; | 3.2 Example 3.2. Large-scale synthesis of 3.4 nm PbS nanocrystals: In a nitrogen- filled glove box, lead oleate (8.812 g, 1 1.44 mmol, 1.5 equiv) and 1-octene (105.5 g, 147.5 mL) were added to a 250 mL 3 -neck round bottom flask equipped with a stir bar, the flask sealed with two rubber septa and an air-free vacuum adapter. In a 20 mL scintillation vial, Ν,Ν'- diphenylthiourea (1.742 g, 7.63 mmol) and diglyme (5 mL) were mixed and the vial sealed with a rubber septum. Both vessels were transferred to a Schlenk line where they were attached to an argon inlet and brought to 95 °C in an oil bath. After the temperature of the reaction vessel was stable (15 minutes), the solution of thiourea was quickly injected into the clear colorless solution. The stirring was vigorous and the injection completed prior to the darkening of the mixture (< 1 second). (0394) Simultaneous injection using two syringes was helpful . The reaction was allowed to run for 60 seconds before the flask was removed from the hot oil bath. Once cooled to room temperature, the septa were replaced with glass stoppers under positive argon flow and the volatiles removed under vacuum. The flask was sealed under vacuum and brought into a glove box whereupon toluene (40 mL) was added. The resulting slurry was split between four 50 mL centrifuge tubes and centrifuged (7000 rpm, 10 minutes). The dark nanocrystal solution was decanted and any remaining solids discarded. Methyl acetate (120 mL) was then added to the toluene solution to precipitate the nanocrystals. After centrifugation (7000 rpm, 10 minutes), the clear, pale brown solution was discarded and the remaining nanocrystal residue redissolved in toluene (40 mL), The cycle of precipitation from toluene with methyl acetate was performed six times in total to reach a ligand coverage of 5.7 oleate ligands per square nanometer as measured by UV-Visible- TR absorption and 'H NMR spectroscopy. Yield of (PbS)(Pb(oleate)2)0.26 : 2.67 g (79.5%). Commercially available anhydrous octane (b.p, =:: 125-126°C) was also successfully used in place of 1-octene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With lipase from Aspergillus niger; iron oxide In 1,4-dioxane at 60℃; for 4h; Green chemistry; diastereoselective reaction; | 3.1. General procedure for the preparation of 2,5-dioxopyrrolidines General procedure: A mixture of coumarin-3-carboxylic acid derivative (1 mmol), alkyl isocyanide (1 mmol), thiourea derivative (1 mmol), and NBC (25 mg) in 10 mL of dioxane was stirred at 60 °C for 4 h. When the reaction (TLC, eluent: AcOEt/n-hexane 2/3) was completed, the NBC was separated using a magnet. The solvent was removed under reduced pressure and the residue was separated by chromatography plates using n-hexane/AcOEt as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With lipase from Aspergillus niger; iron oxide In 1,4-dioxane at 60℃; for 4h; Green chemistry; diastereoselective reaction; | 3.1. General procedure for the preparation of 2,5-dioxopyrrolidines General procedure: A mixture of coumarin-3-carboxylic acid derivative (1 mmol), alkyl isocyanide (1 mmol), thiourea derivative (1 mmol), and NBC (25 mg) in 10 mL of dioxane was stirred at 60 °C for 4 h. When the reaction (TLC, eluent: AcOEt/n-hexane 2/3) was completed, the NBC was separated using a magnet. The solvent was removed under reduced pressure and the residue was separated by chromatography plates using n-hexane/AcOEt as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With lipase from Aspergillus niger; iron oxide In 1,4-dioxane at 60℃; for 4h; Green chemistry; diastereoselective reaction; | 3.1. General procedure for the preparation of 2,5-dioxopyrrolidines General procedure: A mixture of coumarin-3-carboxylic acid derivative (1 mmol), alkyl isocyanide (1 mmol), thiourea derivative (1 mmol), and NBC (25 mg) in 10 mL of dioxane was stirred at 60 °C for 4 h. When the reaction (TLC, eluent: AcOEt/n-hexane 2/3) was completed, the NBC was separated using a magnet. The solvent was removed under reduced pressure and the residue was separated by chromatography plates using n-hexane/AcOEt as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With lipase from Aspergillus niger; iron oxide In 1,4-dioxane at 60℃; for 4h; Green chemistry; diastereoselective reaction; | 3.1. General procedure for the preparation of 2,5-dioxopyrrolidines General procedure: A mixture of coumarin-3-carboxylic acid derivative (1 mmol), alkyl isocyanide (1 mmol), thiourea derivative (1 mmol), and NBC (25 mg) in 10 mL of dioxane was stirred at 60 °C for 4 h. When the reaction (TLC, eluent: AcOEt/n-hexane 2/3) was completed, the NBC was separated using a magnet. The solvent was removed under reduced pressure and the residue was separated by chromatography plates using n-hexane/AcOEt as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In dichloromethane at 20℃; for 72h; Inert atmosphere; | |
85% | In dichloromethane at 20℃; for 16h; Inert atmosphere; | 2.1 Step 1. Synthesis of 1 ,3-Diphenyl-2-thiobarbituric acid (Intermediate 1 , Scheme 1) Under N2 atmosphere, Methyl 3-chloro-3-oxopropionate (2.1 ml, 18.9 mmol) was dropwise added to a solution of N,N'-Diphenylthiourea (2.0 g, 8.6 mmol) in dry DCM (100 ml) and the reaction crude stirred at room temperature for 1 6 hours. Afterwards, the reaction crude was concentrated to dryness at low pressure and the resulting oil stored under vacuum at room temperature until converted into a solid, total time 72 hours. Finally, resulting solid was solved in the minimum DCM volume (10 ml) and slowly poured onto cold cyclohexane (100 ml). Resulting yellowish solid filtration yielded 2.1 6 g of title compound (yield 85 %). Characterization: Rt = 1 .32 min; MS (ESI) m/z: 295.1 [M-H]-, [M-H]- calculated: 295.1 . 1 H-NMR (400 MHz, CDC ) δ 7.57 - 7.39 (m, 6H), 7.25 - 7.18 (m, 4H), 4.1 1 (s, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With potassium dichloroiodate In water; acetonitrile at 20℃; for 0.5h; | General procedure: To a solution of thiourea 2a-n (0.5 mmol) in 5 mL of acetonitrile was added 1.3 mL (10equiv) of an aqueous solution of potassium dichloroiodate (~2 M; pH=3) and 0.5 mmolof butyl or cyclohexylamine (acyclic guanidines) or no external amine addition (cyclicguanidines). The mixture was stirred at room temperature for 30 minutes. Then, the reaction was quenched with saturated aqueous NaHSO3 (15 mL). The aqueous mixture was extracted with ethyl acetate (4 x 10 mL), dried over anhydrous Na2SO4, filtrated and concentrated under reduced pressure to give the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | General procedure: A mixture of isatins 1a-g (1 mmoL) with an equimolar amount of N,N'-diphenyl/(p-tolyl)thiourea2a,b (1 mmoL) and bromoacetic acid 3 (0.14 g, 1 mmoL) in glacial acetic acid (10 mL) in the presenceof sodium acetate (0.16 gm, 2 mmoL), was heated under reflux for 3 h. The formed solid was filteredoff while hot, washed with hot ethanol, dried and recrystallized from DMF to furnish the targethybrids 4a-n. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | In methanol; acetone at 25℃; for 1h; | 5 2.3 General synthesis of [Pd(C2,N-aphox)(Cl)(L)] complexes General procedure: All complexes were obtained by similar methodology to that reported by Moro et al. [24]. Briefly, a 10.0mL methanol solution of the suitable thiourea/thioamide (1.80mmol) is added dropwise to a suspension containing the complex [Pd(C2,N-aphox)(μ-Cl)]2 (0.90mmol) in a 1:1 mixture of acetone:methanol (25.0mL, 25°C). The resulting yellow solution was stirred for 1h. Afterwards, the solvent was removed under reduced pressure and the resulting solid was washed thoroughly with an 1:1 ethanol:water mixture (3×2.0mL) and n-pentane (1×2.0mL) and dried in vacuo to afford compounds of the type [Pd(C2,N-aphox)(Cl)(L)]. Fig. 1 shows the numbering scheme for the [Pd(C2,N-aphox)(Cl)(L)] complexes. 2.3.5 [Pd(C2,N-aphox)(Cl)(dptu)] (5) Reddish brown solid. Yield: 73%. M.p.>139.3°C (dec.). Anal. Calc. For C21H20ClN3OPdS (%): C 50.0; H 4.00; N 8.33; Found. C 50.1; H 4.15; N 8.16%. FT-IR (cm-1, KBr): 3436m (νOH); 3336m (νNH); 1513s (δNH); 1437 sh (δasCH3); 1050m (νNO); 1018m (βCH); 900 w (νC=S); 755s (γCH). 1H NMR in acetone-d6 {multiplicity, integration, assignment, J (Hz)}: δ 2.30 {s, 3H, H8}; δ 6.97 {td, 1H, H3, J32=J34=7.4 and J35=1.6}; δ 7.08 {td, 1H, H4, J43=J45=7.4 and J42=1.0}; δ 7.25 {m, 2H, H5+Har.}; δ 7.35 {m, 2H, H2+Har.}; δ 7.47 {m; 9H; NH+8Har.}; δ 10.20 {br, 1H, NH}; δ 10.43 {s, 1H, H9}. 13C{1H} NMR in acetone-d6 (assignment): δ 11.04 (C8); δ 119.35 (CLig.); δ 122.87 (CLig.); δ 125.71 (C4); δ 126.77 (C5); δ 128.29 (CLig.); δ 129.41 (C3); δ 129.54 (CLig.); δ 130.29 (CLig.); δ 132.83 (C2); δ 137.96 (CLig.); δ 144.40 (C6); δ 151.68 (C1); δ 166.05 (C7); δ 176.56 (C=S). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | In methanol at 20℃; for 2h; | Synthesis of [Pd(tu)2(tmbiimH2)]Cl2 · 3H2O (2) General procedure: To a yellow suspension of 1 (60.0 mg, 0.163 mmol) in 20.0mL of MeOH, thiourea (24.8 mg, 0.33 mmol) in 10.0 mLof methanol was added slowly, affording a red brownishsolution. The resulting solution was stirred for 2 h andthen filtered to eliminate some impurities. The solutionwas evaporated to dryness and cooled diethyl ether (10.0mL) added to the residue. The red brownish solid was filtered,washed with diethyl ether (5.0 mL) and dried undervacuum. The yield was 80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In ethyl acetate at 20℃; for 12h; | Pseudothiohydantoins 8a-c; General procedure General procedure: 1,3-Diphenylthiourea (1.5 mmol, 342 mg) was added to a suspension of FPD 1a,l,m (1.5 mmol) in anhydrous ethyl acetate (10 mL).The mixture was stirred at room temperature for 12 h. The formed solid was filtered off and recrystallized from methanol or toluene toafford the desired pseudothiohydantoin 8a-c (if the product still contains impurities after the recrystallization, it can be purified bystirring it in ethyl acetate (5 mL) for 12-24h, and the subsequent filtration of the solid gives the desired pseudothiohydantoin). 9-Benzoyl-8-hydroxy-6-(2-hydroxyphenyl)-3-phenyl-2-(phenylimino)-1-thia-3,6-diazaspiro[4.4]non-8-ene-4,7-dione (8a)Yield: 641 mg (78%); yellow solid; mp 155-157 °C (decomp.).1H NMR (400 MHz, DMSO-d6 ): δ = 9.73 (br.s, 1 H), 7.84 (m, 2 H), 7.66-7.48 (m, 6 H), 7.43-7.31 (m, 3 H), 7.24 (m, 2 H), 7.13-6.98(m, 4 H), 6.60 (m, 2 H).13C NMR (100 MHz, DMSO-d6 ): δ = 188.1, 170.1, 164.7, 155.0, 154.2, 152.0, 147.2, 137.5, 135.2, 132.9, 131.1, 129.3 (2 C), 129.2 (2C), 128.9 (2 C), 128.3, 128.1 (2 C), 127.9 (2 C), 124.5, 123.6, 120.3 (2 C), 120.0, 119.4, 117.1, 116.3, 77.4.IR (mineral oil): 3195, 1713, 1666, 1641 cm-1.MS (ESI+): m/z calcd for C31H21N3O5S+H+: 548.13 [M+H+]; found: 548.13.Anal. Calcd (%) for 10C31H21N3O5S · C7H8: C 68.38; H 3.95; N 7.55. Found: C 68.21; H 3.81; N 7.66. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In ethyl acetate at 20℃; for 12h; | Pseudothiohydantoins 8a-c; General procedure General procedure: 1,3-Diphenylthiourea (1.5 mmol, 342 mg) was added to a suspension of FPD 1a,l,m (1.5 mmol) in anhydrous ethyl acetate (10 mL).The mixture was stirred at room temperature for 12 h. The formed solid was filtered off and recrystallized from methanol or toluene toafford the desired pseudothiohydantoin 8a-c (if the product still contains impurities after the recrystallization, it can be purified bystirring it in ethyl acetate (5 mL) for 12-24h, and the subsequent filtration of the solid gives the desired pseudothiohydantoin). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | In ethyl acetate at 20℃; for 12h; | Pseudothiohydantoins 8a-c; General procedure General procedure: 1,3-Diphenylthiourea (1.5 mmol, 342 mg) was added to a suspension of FPD 1a,l,m (1.5 mmol) in anhydrous ethyl acetate (10 mL).The mixture was stirred at room temperature for 12 h. The formed solid was filtered off and recrystallized from methanol or toluene toafford the desired pseudothiohydantoin 8a-c (if the product still contains impurities after the recrystallization, it can be purified bystirring it in ethyl acetate (5 mL) for 12-24h, and the subsequent filtration of the solid gives the desired pseudothiohydantoin). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In dichloromethane at 20℃; Inert atmosphere; | Reaction of Et3SiOCH2NMe2 with 1,3-diphenylthiourea. A 20 mL round-bottom flask was charged with 0.165 g (0.88 mmol) of Et3SiOCH2NMe2 and 0.2 g (0.88 mmol) of 1,3-diphenylthiourea in 10 mL of dichloromethane. The solution was stirred overnight at room temperature, after which the solvent and triethylsilanol were removed under vacuum to obtain 1-[(dimethylamino)methyl]-1,2-diphenylthiourea Ph· NH(C=S)NPhCH2NMe2 (8), yield 80%. This new material is thermally labile and undergoes slow transformation even at room temperature. The reaction between 1 and 1,3-diphenyl thiourea in 2 : 1 molar ratio, too, resulted in exclusive formation of 8; unexpectedly, no disubstituted product was obtained. Due to the limited thermal stability of 8, we could not perform its CHN analysis. 1 H NMR spectrum, δ, ppm: 2.30 s (6H, NMe2), 4.40 s (2H, CH2), 7.20-7.41 m (10H), 7.80 br.s (1H, NH). 13C NMR spectrum, δ, ppm: 41.4 (Me), 41.9 (Me), 77.3 (CH2), 124.6, 125.1, 125.3, 127.5, 128.2, 128.5, 129.5, 139.5 (Ph), 184.7 (C=S). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; Green chemistry; | |
72% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 22h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; | |
80% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; | |
66% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | Stage #1: toluene-4-sulfonamide With sodium hydroxide In water; acetone for 0.166667h; Stage #2: phenyl isothiocyanate In water; acetone at 20℃; for 48h; | Synthesis of p-TolSO2NHC(S)NHPh 1a The thiourea was synthesised using a procedure adapted from that of Shah et al.[37] p-Toluenesulfonamide (10 g) was dissolved in acetone (70 mL) and a solution of NaOH (2.34 g) dissolved in distilled water (20mL) was added. The resulting slightly cloudy pale-yellow solution was stirred for 10 min., followed by the portionwise addition of phenyl isothiocyanate (7.89 g). The resulting yellow solution was stirred at room temperature for 48 h, filtered to remove any unwanted solids, followed by acidification of the filtrate with glacial acetic acid to achieve a pH of 4. A white solid precipitate was obtained by addition of excess distilled water (approx. 200 mL). The product was isolated by suction filtration and washed with distilled water (2 × 30 mL) followed by cold ethanol (2 × 30 mL). The solid was recrystallised from hot ethanol to give a white crystalline solid (6 g, 35%). M.p. 145-148 °C (lit.[38]144-146 °C). ESI MS: Capillary exit voltage 90 V, m/z [M + H]+ 307, [M+ Na]+ 330; 1H NMR (400.13 MHz, chloroform-d1), δ ppm 2.47 (3H, s, CH3), 7.30-7.86 (m, 9H, aromatic CH), 8.86 (1H, s, NH), 9.79 (1H, s, NH); FTIR (cm-1): υ(NH) 3304(m) and 1597(w), υ(S- -O) 1381(s) and 1146(s), υ(CN) 1481(m) and 1179(m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: methanesulfonamide With sodium hydroxide In water; acetone for 0.25h; Stage #2: phenyl isothiocyanate In water; acetone at 20℃; for 48h; | 11. Synthesis of MeSO2NHC(S)NHPh 1b Methanesulfonamide (5 g, 0.052 mol) was dissolved in acetone (50mL) and sodium hydroxide (1.5 g dissolved in 5 mL water) was added. The mixture was stirred for 15 min. followed by the addition of phenylisothiocyanate (7.1 g, 0.052 mol, in approximately 1 mL portions). The mixture was allowed to stand at room temperature for 48 h, followed by acidification with glacial acetic acid (15 mL). A white solid was precipitated using excess water (200 mL), filtered under suction, and washed with cold ethanol (2 × 25 mL). Yield 7.38 g, 60%. ESI MS: Capillary exit voltage 90 V, m/z [M + H]+ 231.06 (calculated m/z 231.03). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | In dichloromethane at 20℃; for 24h; | 1.2 Step 2: Preparation of S-benzyl-N,N'-diphenylisothiouronium iodide 1,3-diphenylthiourea (1.0 g, 4.4 mmol) and benzyl iodide (2.80 mL, 13.2 mmol) were dissolved in dry DCM (10 mL) at room temperature, followed by reaction for 24 hours. After completion of the reaction, the precipitated solid was washed with DCM, and then recrystallized with methanol to obtain S-benzyl-N,N'-diphenylisothiouronium iodide as a yellow transparent solid (1.1 g, yield 58%) |
58% | In dichloromethane at 20℃; for 24h; Inert atmosphere; | Preparation of S-Benzyl-N,N'-diphenyl isothiouronium iodide catalyst(1c) Phenyl isothiocyanate (40 mmol) was added to a solution of aniline (40 mmol) in dry dichloromethane at room temperature. The reaction mixture was stirred for 24 hr, filtered, then washed with dichloromethane and dried, to give a white solid1,3-diphenylthiourea (5.03 g, yield 84%). Then, 1,3-diphenylthiourea (4.4 mmol) was added to a solution of benzyl iodide (13.2 mmol) in drydichloromethaneat room temperature. The reaction mixture was then stirred for 24 hr. The reaction mixture was concentrated in vacuo. The residue was purified via flash chromatography (hexane:ethyl acetate = 8:2), to give a yellow solidS-benzyl-N,N'-diphenyl isothiouronium iodide(1.14 g, yield 58%).mp1C;1H NMR (300MHz, DMSO):δ7.207~7.387(m, 15H),δ 4.445(s. 2H); HR TOF-MS for C20H18N2S: calcd 318.1186(M+), found 318.1185(M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In dichloromethane at 20℃; for 24h; | 2 [Preparation Example 2] Preparation of S-methyl-N,N'-diphenylisothiouronium iodide 1,3-diphenylthiourea (1.4 g, 6.1 mmol) and methyl iodide (18.3 mmol) were dissolved in dry DCM (10 mL) at room temperature, followed by reaction for 24 hours. After completion of the reaction, the precipitated solid was washed with DCM, and then recrystallized with methanol to obtain S-methyl-N,N'-diphenylisothiouronium iodide as a yellow solid (1.8 g, yield 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 36h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 36h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 36h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 20h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 15h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 15h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 17h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 20h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 24h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C15H12N4O3; potassium carbonate In ethanol; water at 20℃; for 20h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sulphur; potassium fluoride In dimethyl sulfoxide at 40℃; for 18h; Inert atmosphere; Sealed tube; | 3-4 192 mg (6 mmol) of elemental sulfur M1, 141 mg (1.5 mmol) of chloroacetic acid M2, 186 mg (2 mmol) of aniline M5 and 290 mg (2.5 mmol) of potassium fluoride were added to a 10 mL polymerization tube, and the nitrogen was replaced by vacuum 3 times. Inject 2 mL of dimethyl sulfoxide with a syringe, heat up to 40 degrees Celsius, and stir under airtight conditions for 18 hours; after the reaction, 30 mL of ethyl acetate and 30 mL of water were added, extracted three times, and then the organic layer was collected and dried. Separation and purification were carried out by silica gel chromatography with a mixed eluent of petroleum ether and ethyl acetate in a volume ratio of 3:1, and after drying, the yellow solid thiourea Compound 3 was obtained in a yield of 81%. |
Tags: 102-08-9 synthesis path| 102-08-9 SDS| 102-08-9 COA| 102-08-9 purity| 102-08-9 application| 102-08-9 NMR| 102-08-9 COA| 102-08-9 structure
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