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[ CAS No. 23927-40-4 ] {[proInfo.proName]}

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Chemical Structure| 23927-40-4
Chemical Structure| 23927-40-4
Structure of 23927-40-4 * Storage: {[proInfo.prStorage]}
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Product Details of [ 23927-40-4 ]

CAS No. :23927-40-4 MDL No. :MFCD00184346
Formula : C16H14Br2 Boiling Point : -
Linear Structure Formula :- InChI Key :QDMAXRJHDMKTQH-UHFFFAOYSA-N
M.W : 366.09 Pubchem ID :5200652
Synonyms :

Calculated chemistry of [ 23927-40-4 ]

Physicochemical Properties

Num. heavy atoms : 18
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.25
Num. rotatable bonds : 0
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 83.92
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.4 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.97
Log Po/w (XLOGP3) : 5.82
Log Po/w (WLOGP) : 5.1
Log Po/w (MLOGP) : 5.77
Log Po/w (SILICOS-IT) : 6.0
Consensus Log Po/w : 5.13

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -6.27
Solubility : 0.000197 mg/ml ; 0.000000537 mol/l
Class : Poorly soluble
Log S (Ali) : -5.59
Solubility : 0.00094 mg/ml ; 0.00000257 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -7.68
Solubility : 0.00000772 mg/ml ; 0.0000000211 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 3.69

Safety of [ 23927-40-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 23927-40-4 ]

* 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 [ 23927-40-4 ]

[ 23927-40-4 ] Synthesis Path-Downstream   1~20

  • 1
  • [ 1633-22-3 ]
  • [ 196316-31-1 ]
YieldReaction ConditionsOperation in experiment
71% Stage #1: [2.2]Paracyclophan With bromine; iron Reflux; Stage #2: With Triethylene glycol dimethyl ether
50% With bromine In tetrachloromethane at 60℃; for 2h;
42.6% With bromine; iron In dichloromethane; para-xylene for 4h; Reflux; 1.5 5,4,16-dibromo [2.2] polydyrene (Compound 5) To the reaction flask was added bromine (0.863 g, 20.3 mmol)And iron powder (48 mg, 1.86 mmol)16 ml of dichloromethane was added,The reaction was stirred at room temperature for 1 hour.The addition of the raw material dimer p-xylene (2.08 g, 10 mmol)In 3 mL of dichloromethane solution, heated to reflux,A solution of 2.4 g of bromine in 5 ml of dichloromethane was slowly added dropwise,Plus,Reflux reaction for 3 hours,Lower to room temperature overnight.Add methylene chloride dilution,Followed by washing with 5% sodium thiosulfate, water, saturated brine,Dried over anhydrous sodium sulfate, concentrated by filtration,Toluene to give 1.56 g of compound 5,Yield 42.6%.
40% With bromine; iron In dichloromethane at 20℃;
40% With bromine; iron In dichloromethane at 20℃; for 72h;
40% With bromine In dichloromethane at 20℃; for 72h; Inert atmosphere;
38% With bromine; iron In dichloromethane Heating;
37% With bromine; iron In dichloromethane at 20℃; for 72h;
36% Stage #1: [2.2]Paracyclophan With iron In dichloromethane for 0.5h; Reflux; Inert atmosphere; Stage #2: With bromine In dichloromethane for 4h; Reflux; Inert atmosphere;
35% With bromine In tetrachloromethane at 60℃; for 6h;
31% With bromine In tetrachloromethane at 20 - 60℃; for 3h; Inert atmosphere;
28% With bromine; iron In dichloromethane
25% With bromine In tetrachloromethane; dichloromethane for 5h; Heating;
25% With bromine In dichloromethane for 0.5h; Reflux;
19% With bromine; iron In dichloromethane at 77.5℃;
With bromine In tetrachloromethane at 40 - 50℃;
With bromine; iron In tetrachloromethane; dichloromethane
With bromine; iron
(bromination);
With bromine In tetrachloromethane
Stage #1: [2.2]Paracyclophan With bromine; iron In dichloromethane at 2℃; for 20h; Reflux; Stage #2: With Triethylene glycol dimethyl ether for 6h; Reflux;
With bromine; iron In dichloromethane at 20℃; for 3h; 3.5 A mixture of Br2 (82.8 g) and iron powder (4.6 g) in DCM (1.6 L) was stirred at rt for 1 h. To this mixture was added, in one portion, a slurry of [2.2]paracyclophane (200 g, 1.0 equiv) in DCM. The resulting mixture was heated to reflux, and to it was added slowly a solution of Br2 (228 g) in DCM (400 mL) over a 3-h period. After this addition was complete, the reaction mixture continued to reflux for 3 h, was allowed to cool to rt with stirring overnight, was washed with 5% w/v aq Na2S2O3 (2 L) and water (2 L), dried (MgSO4), and evaporated to dryness. The isolated crude solid was dissolved in hot toluene (1.2 L, 100° C.), allowed to cool slowly overnight to rt with stirring, and further cooled to 5° C. for 3 h. The resulting solid was collected and washed with cold toluene (100 mL) to afford 4,16-dibromo[2.2]paracyclophane (17) (83 g). 1H NMR (300 MHz, CDCl3, rt): δ 2.79-3.00 (m, 4H), 3.10-3.21 (m, 2H), 3.44-3.54 (m, 2H), 6.44 (d, J=8.0 Hz, 2H), 6.51 (d, J=2.0 Hz, 2H), 7.14 (dd, J=8.0 Hz, 2.0 Hz, 2H).
With bromine; iron In dichloromethane
1.21 g Stage #1: [2.2]Paracyclophan With bromine; iron In dichloromethane at 40℃; for 20h; Inert atmosphere; Stage #2: In Triethylene glycol dimethyl ether at 230℃; for 10h; Inert atmosphere; rac-PHANOL (1) To a suspension of Fe powder (67.0 mg, 1.20 mmol) in CH2Cl2 (20.0mL) was added a solution of Br2 in CH2Cl2 (3.94 M, 1.8 mL, 7.0 mmol) at r.t. After stirring for 1 h at r.t., this mixture was slowly added to a solution of commercially available [2.2]paracyclophane (5.00 g, 24.0mmol) in CH2Cl2 (14.0 mL) at 40 °C over 12 min. When the addition was complete, a solution of Br2 in CH2Cl2 (3.94 M, 12.2 mL, 48.0mmol) was slowly added to the reaction mixture at 40 °C over 10min. After stirring for 20 h at 40 °C, the reaction mixture was cooled to r.t. and the resulting solid was filtered to give the pseudo-para-dibromide derivative (3.49 g, 40%) as a black solid. A suspension of the above pseudo-para-dibromide (2.77 g, 7.57mmol) in triglyme (11.0 mL) was heated in a MW apparatus at 230 °C for 10 h. After cooling to r.t., the resulting solid was washed with Et2O (41.5 mL). This solid material was recovered s2 (1.12 g, 41%). The filtrate was successively washed with H2O (×3), brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography (silica gel; hexane) to give pseudo-ortho-dibromide (1.21g, 44%) as a white solid. To a solution of the above pseudo-ortho-dibromide (303 mg, 0.829mmol) in Et2O (24.0 mL) was added n-BuLi (1.60 M in hexane, 1.40mL, 2.24 mmol) at 0 °C. The mixture was stirred for 1 h at 0 °C, and B(OMe)3 (0.50 mL, 4.48 mmol) was added to the reaction mixture at0 °C. After stirring for 3 h at r.t., aqueous NaOH (0.50 M, 1.2 mL, 0.60mmol) and H2O2 (34.5%, 1.1 mL, 9.7 mmol) were added to the reaction mixture. After stirring for 3 h, the reaction was stopped by addition of H2O at 0 °C. The reaction mixture was extracted with CH2Cl2 (×3) and the combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography (silica gel; hexane/EtOAc, 2:1) to give 1.Yield: 166 mg (83%); pale-yellow solid.
Multi-step reaction with 2 steps 1: bromine; iron / dichloromethane / 72 h / 20 °C 2: Triethylene glycol dimethyl ether / 4 h / 0 °C / Reflux
Stage #1: [2.2]Paracyclophan With ferric(III) bromide; bromine In dichloromethane at -20℃; for 2h; Stage #2: In dodecane at 217℃; for 12h; 2; 3 In an Erlenmeyer flask, dissolve 15 mL of bromine in 80 mL of methylene chloride; 2 g of Ferric bromide,30g [2.2]paracyclophanewith100mL of methylene chloride was added to a 500mL three-necked bottle,A bromine solution in methylene chloride was added dropwise at -20°C in an ice-salt bath at a rate of 0.2 mL/min.-20°C for 2 h; add 100 mL of aqueous sodium bisulfite (0.03 g/mL),Room temperature reaction 1.5h; After vacuum filtration, drying at 60°C to obtain crude product,Recrystallized from chloroform to give 4,16-dibromo[2.2]paracyclophane, the yield was 45%, (3) Add 100 g of 4,16-dibromo[2.2]-paracyclophanate and 500 mL of n-dodecane to a 1000-mL three-vial flask.217 °C heated to reflux, the reaction 12h, the reaction is completed, cooled to room temperature; vacuum filtration, to obtain the filtrate,The yellow solid obtained by steam distillation of the filtrate is the crude 4,12-dibromo[2.2]cycloparadiene.The crude product was recrystallized from ethanol at 100°C to give 4,12-dibromo[2.2]paracyclophane, yield 92%,
83 g With bromine; iron In dichloromethane for 6h; Reflux; 1.5 Step 5. Preparation of Compound 6 6 A mixture of Br2(82.8 g) and iron powder (4.6 g) in DCM (1.6 L) was stirred at room temperature for 1 hour. A slurry of [2.2]paracyclophane (200 g, 1.0 equiv) in DCM was added in one portion to the mixture. The resulting mixture was heated to reflux, and a solution of Br2(228 g) in DCM (400 mL) was added slowly over a 3 hour period. After this addition was complete, the reaction mixture continued to reflux for 3 hours and was allowed to cool to room temperature with stirring overnight. The mixture was washed with 5% w/v aqueous Na2S2Cb (2 L) and water (2 L), dried (MgS04), and evaporated to dryness. The isolated crude solid was dissolved in hot toluene (1.2 L, approximately 100 °C), allowed to cool slowly overnight to room temperature with stirring, and further cooled to 5 °C for 3 hours. The resulting solid was collected and washed with cold toluene (approximately 100 mL) to afford 4,16-dibromo[2.2]paracyclophane (6) (83 g). ΝΜΚ (300 MHz, CDCh): 5 2.79-3.00 (m, 4H), 3.10-3.21 (m, 2H), 3.44-3.54 (m, 2H), 6.44 (d, J=8.0 Hz, 2H), 6.51 (d, J=2.0 Hz, 2H), 7.14 (dd, J=8.0 Hz, 2.0 Hz, 2H).
With bromine; iron
With bromine; iron
With bromine 4,16-Dibromo[2.2]paracyclophane (1) A solution of Br2 (5.50 mL, 17.0 g, 106 mmol, 2.20 equiv.) in CH2Cl2 (50 mL) was prepared.A suspension of iron powder (0.14 g, 2.4 mmol, 0.05 equiv.) in 6.25 mL of the Br2/CH2Cl2 solution wasdiluted in 50 mL of CH2Cl2 and stirred at room temperature for 1 h. The solution was then brought toreflux for 2 h. CH2Cl2 (50 mL) and [2.2]paracyclophane (10.0 g, 48.0 mmol, 1.00 equiv.) were added tothe mixture subsequently. After the remaining bromine solution was added dropwise over a period of4 h, the mixture was stirred at room temperature for 3 d. Saturated Na2S2O3 solution was added andthe reaction mixture was stirred at room temperature until the bromine color disappeared. The organicphase was separated and filtrated, the precipitate was recrystallized from hot toluene to obtain the titleproduct as an o-white solid, 5.40 g, 14.8 mmol, 31%. 1H-NMR (400 MHz, CDCl3) δ/ppm = 7.14 (dd, J = 7.8, 1.8 Hz, 2H, 2 x CArH), 6.51 (d, J = 1.8 Hz,2H, 2 x CArH), 6.44 (d, J = 7.8 Hz, 2H, 2 x CArH), 3.50 (ddd, J = 12.8, 10.3, 2.0 Hz, 2H, 2 CHPC), 3.16(ddd, J = 12.1, 10.2, 4.6 Hz, 2H, 2 CHPC), 2.95 (ddd, J = 12.1, 11.4, 2.0 Hz, 2H, 2 CHPC), 2.85 (ddd,J = 13.0, 10.6, 4.6 Hz, 2H, 2 CHPC). 13C-NMR (101 MHz, CDCl3) δ/ppm = 141.3 (Cq, 2 x CAr), 138.6(Cq, 2 x CAr), 137.4 (+, CH, 2 x CAr), 134.2 (+, CH, 2 x CAr), 128.4 (+, CH, 2 x CAr), 126.8 (Cq, 2 x CAr-Br), 35.5 (, 2 x CH2), 32.9 51 (, 2 x CH2). IR (ATR): v/cm1 = 2932 (vw), 2849 (vw), 1895 (vw),1583 (vw), 1532 (vw), 1474 (vw), 1449 (vw), 1432 (vw), 1390 (w), 1313 (vw), 1185 (vw), 1104 (vw), 1030(w), 947 (vw), 899 (w), 839 (w), 855 (w), 830 (w), 706 (w), 669 (w), 647 (w), 522 (vw), 464 (w), 393 (vw).MS (EI, 70 eV), m/z (%): 364/366/368 (3/6/3) [M]+, 184/182 (18/18) [M C8H7Br]+, 104 (100) [C8H8]+.HRMS (EI, C16H1479Br2) calc. 363.9457, found 363.9455.
With bromine; iron In dichloromethane

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  • 2
  • [ 23927-40-4 ]
  • [ 1016984-08-9 ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: With Trimethyl borate In tetrahydrofuran at -78 - 25℃; for 20h; Inert atmosphere; Stage #3: With water; dihydrogen peroxide; sodium hydroxide In tetrahydrofuran for 1h; Inert atmosphere;
84% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: With Trimethyl borate at -78 - 20℃; Stage #3: With dihydrogen peroxide; sodium hydroxide at 20℃;
72% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 14h; Inert atmosphere; Stage #3: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; hexane; water at 20℃; for 2h; Preparation of Bromohydroxy Derivative 69a,10b To a solution of pseudo-ortho-dibromide (176 mg, 0.482 mmol) in THF (9.0 mL) was added n-BuLi (1.60 M in hexane, 0.36 mL, 0.578mmol) at -78 °C. The mixture was stirred for 0.5 h at -78 °C, and B(OMe)3 (0.15 mL, 1.34 mmol) was added to the reaction mixture, then the reaction was gradually warmed to r.t. After stirring the mixture for 14 h at r.t., aqueous NaOH (0.50 M, 0.25 mL, 0.12 mmol) andH2O2 (34.5%, 0.25 mL, 21.7 mmol) were added. After stirring the mixture for 2 h, the reaction was quenched by addition of H2O at 0 °C. The aqueous solution was extracted with CH2Cl2 (×3) and the combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography(silica gel; hexane/EtOAc, 2:1) to give 6.Yield: 105 mg (72%); pale-yellow solid; mp 149-152 °C (Lit.9c 149-153 °C).IR (KBr): 3444, 2927, 1574, 1477, 1415, 1217, 1093, 1032, 976,862 cm-1.1H NMR (400 MHz, CDCl3): δ = 2.57-2.68 (m, 1 H), 2.76-2.87 (m, 1 H),2.90-3.08 (m, 4 H), 3.31-3.43 (m, 2 H), 4.66 (br s, 1 H), 6.24 (d, J =8.0 Hz, 2 H), 6.42 (dd, J = 2.0, 8.0 Hz, 1 H), 6.46 (d, J = 8.0 Hz, 1 H), 6.52(d, J = 8.0 Hz, 1 H), 7.06 (d, J = 2.0 Hz, 1 H).
72% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 14h; Inert atmosphere; Stage #3: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; hexane; water at 20℃; for 2h; Preparation of Monomethoxy Derivative 8 To a solution of 1 (57.6 mg, 0.24 mmol) in DMF (4.0 mL) was added NaH (55% oil, 24.3 mg, 0.557 mmol) at 0 °C. After stirring the mixture for 30 min, MeI (18 μL, 0.29 mmol) was added at 0 °C. After stirring the mixture for 3 h at 0 °C, the reaction was quenched by addition of1 M aqueous HCl at 0 °C. The crude products were extracted withCH2Cl2 (×3) and the combined organic extracts were successively washed with H2O, brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by preparative TLC (silica gel; hexane/EtOAc,5:1) to give 8.Yield: 19.3 mg (32%); pale-yellow oil.IR (neat): 3398, 2929, 2852, 1597, 1568, 1496, 1464, 1415, 1321,1251, 1146, 1113, 1095, 1038, 980, 864 cm-1.1H NMR (400 MHz, CDCl3): δ = 2.51-2.70 (m, 2 H), 2.88-3.08 (m, 4 H),3.19-3.41 (m, 2 H), 3.74 (s, 3 H), 4.52 (br s, 1 H), 6.02 (d, J = 1.2 Hz,1 H), 6.13 (dd, J = 1.2, 8.0 Hz, 1 H), 6.18 (dd, J = 1.2, 8.0 Hz, 1 H), 6.32(s, 1 H), 6.38 (d, J = 8.0 Hz, 1 H), 6.46 (d, J = 8.0 Hz, 1 H).13C NMR (CDCl3, 100 MHz): δ = 30.5, 31.2, 33.5, 33.8, 54.5, 112.5,117.8, 123.9, 124.5, 125.4, 127.0, 135.2, 135.5, 142.2, 143.0, 153.6,157.6.HRMS (TOF): m/z [M + Na]+ calcd for [C17H18NaO2]+: 277.1199; found:277.1211.
69% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium Stage #2: With Trimethyl borate Stage #3: With dihydrogen peroxide; sodium hydroxide
68% Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 16h; Inert atmosphere; Stage #3: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; hexane; water at 0 - 20℃; for 1h; Inert atmosphere;
(i) KOtBu, DMSO, (ii) aq. HCl, AcOH; Multistep reaction;
71 % Stage #1: 4,12-dibromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 0℃; Inert atmosphere; Stage #2: With Trimethyl borate In diethyl ether; hexane at 0 - 20℃; Inert atmosphere; Stage #3: With dihydrogen peroxide; sodium hydroxide In diethyl ether; hexane; water at 20℃; Inert atmosphere;

  • 3
  • [ 23927-40-4 ]
  • [ 24262-20-2 ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 0℃; for 1h; Stage #2: With Trimethyl borate In diethyl ether; hexane at 0 - 20℃; for 3h; Inert atmosphere; Stage #3: With dihydrogen peroxide; sodium hydroxide In diethyl ether; hexane; water at 20℃; for 3h; rac-PHANOL (1) To a suspension of Fe powder (67.0 mg, 1.20 mmol) in CH2Cl2 (20.0mL) was added a solution of Br2 in CH2Cl2 (3.94 M, 1.8 mL, 7.0 mmol) at r.t. After stirring for 1 h at r.t., this mixture was slowly added to a solution of commercially available [2.2]paracyclophane (5.00 g, 24.0mmol) in CH2Cl2 (14.0 mL) at 40 °C over 12 min. When the addition was complete, a solution of Br2 in CH2Cl2 (3.94 M, 12.2 mL, 48.0mmol) was slowly added to the reaction mixture at 40 °C over 10min. After stirring for 20 h at 40 °C, the reaction mixture was cooled to r.t. and the resulting solid was filtered to give the pseudo-para-dibromide derivative (3.49 g, 40%) as a black solid. A suspension of the above pseudo-para-dibromide (2.77 g, 7.57mmol) in triglyme (11.0 mL) was heated in a MW apparatus at 230 °C for 10 h. After cooling to r.t., the resulting solid was washed with Et2O (41.5 mL). This solid material was recovered s2 (1.12 g, 41%). The filtrate was successively washed with H2O (×3), brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography (silica gel; hexane) to give pseudo-ortho-dibromide (1.21g, 44%) as a white solid. To a solution of the above pseudo-ortho-dibromide (303 mg, 0.829mmol) in Et2O (24.0 mL) was added n-BuLi (1.60 M in hexane, 1.40mL, 2.24 mmol) at 0 °C. The mixture was stirred for 1 h at 0 °C, and B(OMe)3 (0.50 mL, 4.48 mmol) was added to the reaction mixture at0 °C. After stirring for 3 h at r.t., aqueous NaOH (0.50 M, 1.2 mL, 0.60mmol) and H2O2 (34.5%, 1.1 mL, 9.7 mmol) were added to the reaction mixture. After stirring for 3 h, the reaction was stopped by addition of H2O at 0 °C. The reaction mixture was extracted with CH2Cl2 (×3) and the combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography (silica gel; hexane/EtOAc, 2:1) to give 1.Yield: 166 mg (83%); pale-yellow solid.
80% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 0℃; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at 0 - 20℃; Stage #3: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; hexane; water for 0.5h;
45% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78 - 20℃; Stage #2: With nitrobenzene In tetrahydrofuran at -78 - 20℃; Further stages.;
(i) nBuLi, (ii) PhNO2; Multistep reaction;
With n-butyllithium; nitrobenzene In tetrahydrofuran

  • 4
  • [ 23927-40-4 ]
  • [ 1499-21-4 ]
  • [ 192525-87-4 ]
YieldReaction ConditionsOperation in experiment
94% With copper(l) iodide; isopropylmagnesium bromide In tetrahydrofuran at 30℃; Inert atmosphere; 1-4 Example 4 Under the protection of argon, add o-dibromo-[2.2]p-cycloarane (366g, 1mol) and 1.5L of tetrahydrofuran to the reactor, and add a solution of isopropyl magnesium bromide in tetrahydrofuran (2.5 L, 2.5mol), and react at a temperature of 30, then add cuprous iodide (190g, 1mol) and diphenylphosphonyl chloride (260g, 1.1mol), and then increase the temperature to reflux reaction, after the reaction is completed, add water to quench Extinguish, add dichloromethane and ammonia water to wash and separate the liquid, dry, distill, add n-heptane to crystallize to obtain 4,12-bis(diphenylphosphineoxy)-[2.2]-p-cycloarane (572g, 94%)
68% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In diethyl ether Stage #2: With magnesium bromide ethyl etherate In diethyl ether Stage #3: Diphenylphosphinic chloride In diethyl ether
Multistep reaction;
  • 5
  • [ CAS Unavailable ]
  • [ 23927-40-4 ]
  • [ 152520-28-0 ]
YieldReaction ConditionsOperation in experiment
97% With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 100℃; for 23h;
90% With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 100℃; for 24h;
  • 6
  • [ 23927-40-4 ]
  • [ 68-12-2 ]
  • [ 320749-00-6 ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; Further stages.;
75% With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 3h; Inert atmosphere;
60% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; for 16h;
60% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; Inert atmosphere;

  • 8
  • [ 23927-40-4 ]
  • [ 137219-83-1 ]
  • [ 936475-00-2 ]
YieldReaction ConditionsOperation in experiment
74% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #2: With magnesium bromide In tetrahydrofuran; pentane at -78 - 10℃; Stage #3: (3-(chloro(3,5-dimethylphenyl)phosphoryl)-5-methylphenyl)methylium In tetrahydrofuran; pentane at 20℃; for 18h; Further stages.;
  • 9
  • [ 23927-40-4 ]
  • [ 809281-31-0 ]
YieldReaction ConditionsOperation in experiment
31% With nitric acid In 1,1-dichloroethane; water at 20 - 70℃; for 21h; 1.b; 3 Sc(OTf)3 (100 mg, 0.2 mmol) was suspended in dichloroethane (2.5 mL) and HNO3 70% (0.1 mL) was added to give a clear solution at room temperature. 4,12-Dibromo-[2.2] paracyclophane (366 mg, 1 mmol) was added and the reaction was heated to 70°C and stirred for 20 hours. After this time, thin-layer chromatographic (TLC) analysis (eluant : hexane/MTBE 95/5) indicated that the reaction was not complete and more Sc(OTf)3 (100 mg, 0.2 mmol) and HNO3 70% (0.1 mL) were added. After 1 hour at 70°C all the starting material was consumed and the reaction was diluted with dichloromethane (50 mL) and washed with brine (2x50 mL). The organic phase was dried over anhydrous Na2SO4 and evaporated to give a yellow oil. The crude material was dissolved in 2 mL dichloromethane and eluted through a pad of silica gel (eluant hexane/MTBE 9/1). Evaporation of the solvent gave 4,12-dibromo-7-nitro[2.2]paracyclophane (190 mg, 31 % yield) as a yellow solid. 4,12-dibromo-7-nitro[2.2]paracyclophane :1H NMR (CDCl3, 400 MHz): 2.75 (1 H, m,-CH2-), 3.0 (4H, m,-CH2-), 3.4 (2H, m,-CH2-), 3.3 (1 H, m,-CH2-), 6.4 (1 H, d, CH arom), 6.6 (1 H, d, CH arom), 7.1 (1 H, s, CH arom), 7.25 (1 H, s, CH arom), 7.3 (1 H, s, CH arom) ppm. 13C NMR (CDCl3, 400MHz) : 32.1 (-CH2-), 32.6 (-CH2-), 35.1 (-CH2-), 35.2 (-CH2-). 127.0 (C arom), 130.9 (CH arom), 131.2 (CH arom), 132.0 (CH arom), 132.6 (C arom), 133.3 (CH arom), 136.2 (CH arom), 137.7 (C arom), 138.9 (C arom), 140.9 (C arom), 141.4 (C arom), 148.6 (C-NO2 arom) ppm. 4,12-dibromo-7,15-dinitro[2.2]paracyclophane :1H NMR (CDCl3, 400 MHz): 3. 1 (4H, m,-CH2-), 3.4 (2H, m,-CH2-), 3.8 (2H, m,-CH2-), 7.3 (4H, s, broad, CH arom) ppm. 13C NMR (CDCl3, 400MHz) : 30.9 (-CH2-), 33.4 (-CH2-), 126.9 (CH arom), 131.6 (C arom), 135.5 (CH arom), 135.7 (C arom), 140.4 (C arom), 147.4 (C-NO2 arom) ppm.
  • 10
  • [ 23927-40-4 ]
  • [ 25291-17-2 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
88% With tributyl-amine; 4-methoxy-phenol In N,N-dimethyl-formamide at 100℃; for 48h; 3 A Heck coupling reaction was performed as illustrated in FIG. 2A to produce an intermediate paracyclophane having a pendent fluoro-alkene. A 250 ml reactor was charged under argon atmosphere with a solvent, N,N-Dimethyl-formamide (DMF). The educts as listed in Table 4 were also charged into the reactor. After heating and stirring for about forty-eight hours at a temperature of about 100° C., the mixture a precipitate as produce about adding an about 2% aqueous HCl. The crude product was filtered and recrystallized twice using ethanol. The yield of the intermediate product was about 88%. This intermediate product had an observed melting point of about 93° C. The observed characteristics of the intermediate product are listed in Table 5.
  • 11
  • [ 196316-30-0 ]
  • [ 23112-96-1 ]
  • [ 1126387-08-3 ]
YieldReaction ConditionsOperation in experiment
86% With potassium phosphate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In toluene; for 24h;Heating / reflux; Example 1. Synthesis of a monophosphine ligand: (a) preparation of a substituted bromoparacyclophaneTo a Schlenk tube were added (rac)-4,12-dibromoparacyclorhohane 1.83g (5.0 mmol), 2,6- dimethoxyphenylboronic acid 1.37g (7.5 mmol, 1.5 equiv), Pd(dppf)CI2 164mg (0.20 mmol, 4 mol %), and K3PO42.12g (10.0 mmol, 2.0 equiv). The flask was evacuated and backfilled with nitrogen three times. Fresh distilled toluene (20 mL) was introduced, and the flask was sealed, stirred at reflux for 24 h. The reaction mixture was cooled, diluted with toluene (30 mL), and hydrolyzed with 10 % NaOH (30 mL). Separated and extracted the water phase with EtOAc (3 x 25 mL). The organic layers were dried over MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography (EtOAc/hexane, 30:1) on silica <n="11"/>gel to afford white solid products 1.82g (86 % yields). 1H NMR {400 MHz, CDCI3) S7.24 (t, J = 8.4 Hz, 1 H), 7.10 (s, 1H), 7.75 (d, J = 8.4 Hz, 1 H), 6.73 (s, 1H), 6.67 (s, 2H), 6.54 - 6.51 (m, 2H), 6.39 (d, J = 7.6 Hz, 1 H), 4.10 (s, 3H), 3.60 - 3.51 (m, 1 H), 3.48 (s, 3H), 3.22 - 3.10 (m, 2H), 2.95 - 2.75 (m, 4H), 2.65 - 2.55 (m, 1 H); 13C NMR (100 MHz, CDCl3) delta 158.6, 158.5, 141.5, 140.8, 139.7, 137.4, 137.1 , 134.6, 133.5, 133.0, 131.6, 131.2, 129.8, 129.0, 126.9, 118.5, 105.1, 105.0, 56.5, 55.8, 37.3, 34.9, 34.8, 32.9; MS m/z 442: 440 = 1 :1 (M+NH3, 100), 425: 423 = 1:1 (M+H, 72).
  • 12
  • [ 23927-40-4 ]
  • [ 68-12-2 ]
  • [ 87325-14-2 ]
YieldReaction ConditionsOperation in experiment
93% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane at 0 - 20℃;
93% With n-butyllithium In diethyl ether; hexane at 0 - 20℃; Inert atmosphere; Sealed tube;
83% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With n-butyllithium In tetrahydrofuran; diethyl ether at 0℃; for 1h; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane at 0 - 20℃; Stage #3: With hydrogenchloride; lithium hydroxide monohydrate In diethyl ether; hexane for 2h;
80% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With sec.-butyllithium In tetrahydrofuran; cyclohexane at -65℃; for 2h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; cyclohexane for 1h;
73% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 8h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane at 0 - 20℃; for 15h; Inert atmosphere;
70% With sec.-butyllithium In tetrahydrofuran at -78 - 20℃; for 3h;
61% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 2h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane for 16h; Inert atmosphere;
55% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With iso-butyllithium In tetrahydrofuran; diethyl ether at -78℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; diethyl ether at 20℃; for 16h; Inert atmosphere;
50% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With sec.-butyllithium In tetrahydrofuran; diethyl ether at -78℃; for 0.333333h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; diethyl ether at -78 - 20℃; Inert atmosphere;
31% Stage #1: 5,11-dibromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 25℃; for 24h; Inert atmosphere;
With n-butyllithium Inert atmosphere;

Reference: [1]Delcourt, Marie-Léonie; Felder, Simon; Turcaud, Serge; Pollok, Corina H.; Merten, Christian; Micouin, Laurent; Benedetti, Erica [Journal of Organic Chemistry, 2019, vol. 84, # 9, p. 5369 - 5382]
[2]Benedetti, Erica; Bousquet, Manon H. E.; Crassous, Jeanne; Delcourt, Marie-Léonie; Favereau, Ludovic; Felder, Simon; Jacquemin, Denis; Micouin, Laurent; Rodríguez, Rafael [Journal of Organic Chemistry, 2022, vol. 87, # 1, p. 147 - 158]
[3]Meyer-Eppler, Georg; Vogelsang, Elisabeth; Benkhaeuser, Christian; Schneider, Andreas; Schnakenburg, Gregor; Luetzen, Arne [European Journal of Organic Chemistry, 2013, # 21, p. 4523 - 4532]
[4]Location in patent: experimental part Bier, Anna K.; Bognitzki, Michael; Schmidt, Alexander; Greiner, Andreas; Gallo, Emanuela; Klack, Patrick; Schartel, Bernhard [Macromolecules, 2012, vol. 45, # 2, p. 633 - 639]
[5]Biswas, Sourav; Tabasi, Zahra A.; Dawe, Louise N.; Zhao, Yuming; Bodwell, Graham J. [Organic Letters, 2022, vol. 24, # 28, p. 5009 - 5013]
[6]Limwongyut, Jakkarin; Liu, Yang; Chilambi, Gayatri Shankar; Seviour, Thomas; Hinks, Jamie; Mu, Yuguang; Bazan, Guillermo C. [RSC Advances, 2018, vol. 8, # 70, p. 39849 - 39853]
[7]Stahlberger, Mareen; Schwarz, Noah; Zippel, Christoph; Hohmann, Jens; Nieger, Martin; Hassan, Zahid; Bräse, Stefan [Chemistry - A European Journal, 2022, vol. 28, # 3]
[8]Wielopolski, Mateusz; Molina-Ontoria, Agustin; Schubert, Christina; Margraf, Johannes T.; Krokos, Evangelos; Kirschner, Johannes; Gouloumis, Andreas; Clark, Timothy; Guldi, Dirk M.; Martin, Nazario [Journal of the American Chemical Society, 2013, vol. 135, # 28, p. 10372 - 10381]
[9]Morisaki, Yasuhiro; Lin, Lin; Chujo, Yoshiki [Chemistry Letters, 2009, vol. 38, # 7, p. 734 - 735]
[10]Eisterhold, Andrew M.; Puangsamlee, Thamon; Otterbach, Steffen; Bräse, Stefan; Weis, Patrick; Wang, Xiqu; Kutonova, Ksenia V.; Miljanić, Ognjen Š. [Organic Letters, 2021, vol. 23, # 3, p. 781 - 785]
[11]Liang, Hao; Guo, Weicong; Li, Junxuan; Jiang, Jijun; Wang, Jun [Angewandte Chemie - International Edition, 2022, vol. 61, # 26][Angew. Chem., 2022, vol. 134, # 26]
  • 13
  • [ 23927-40-4 ]
  • [ 23927-40-4 ]
  • [ 23927-40-4 ]
YieldReaction ConditionsOperation in experiment
With Chiralcel OD column In hexane; isopropyl alcohol Resolution of racemate;
1: >99.9 % ee 2: 99.8 % ee With CHIRALPAK IA In n-heptane; dichloromethane Resolution of racemate;
With chiralpak AZ-H column In acetonitrile at 25℃; Resolution of racemate;
With chiralpak AZ-H column In acetonitrile at 25℃; Resolution of racemate;
With chiralpak AZ-H column In acetonitrile at 25℃; Resolution of racemate; (Rp)-4,12-Dibromo[2.2]paracyclophane (Rp-2)/ (Sp)-4,12-Dibromo[2.2]paracyclophane (Sp-2) Separation of (rac)-4,12-dibromo[2.2]paracyclophane 75 via semi-preparative chiral HPLC:Conditions:Semi-preparative chiralpak AZ-H column (20 × 250 nm, particle 5 μm), 100% CH3CN, 25 mL/min,25 °C, 254 nm UV detecter, 100 mg racemate per run. tR (RP) = 6.97 min, tR (SP) = 8.00 min. The spectraof the racemate as well as the enationpure (Rp-4,12-dibromo-[2.2]paracyclophane) 75 are shown inFigure 1.

  • 14
  • [ 23927-40-4 ]
  • [ 876395-50-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: n-butyllithium / hexane; tetrahydrofuran / 1 h / -78 °C / Inert atmosphere 1.2: 11 h / -78 - 20 °C / Inert atmosphere 2.1: tert.-butyl lithium / tetrahydrofuran; pentane / 0.5 h / -78 °C / Inert atmosphere 2.2: 7.25 h / -78 - 20 °C / Inert atmosphere
  • 15
  • [ 23927-40-4 ]
  • [ 157018-15-0 ]
  • [ 1016984-08-9 ]
YieldReaction ConditionsOperation in experiment
37% Stage #1: 4,16-dibromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 20℃; for 4.5h; Stage #2: With Trimethyl borate In diethyl ether; hexane at 20℃; Stage #3: With dihydrogen peroxide; sodium hydroxide In diethyl ether; hexane; water at 20℃; for 1h;
  • 16
  • [ 23927-40-4 ]
  • [ 339990-69-1 ]
YieldReaction ConditionsOperation in experiment
68% With ammonia; sodium t-butanolate In 1,4-dioxane at 80℃; for 16h; Schlenk technique; Inert atmosphere; 1.1 (1) o-CP-2Br to o-CP-2NH2: In a 500-mL Schlenk flask, were placed o-CP-2Br (3.67 g), NaOtBu (2.90 g), and Pd-tBuDavePhos-OMs (0.36 g). The flask was evacuated/refilled with argon three times and then NH3 solution in 1,4-dioxane (0.5 M, 161 mL) was transferred under argon. The mixture was stirred at 80 °C for 16 h. For work- up, the mixture was diluted with ethyl acetate and then filtered through silica gel. After removing the volatiles of the filtrate, flash chromatography (gradient 0-15% ethyl acetate in hexanes) was used to purify the product. Yield: 1.62 g, 68%.
With copper(I) oxide; sodium azide; rac-Pro-OH In dimethyl sulfoxide at 100℃; for 48h; Sealed tube; Inert atmosphere; Microwave irradiation;
Multi-step reaction with 2 steps 1.1: tert.-butyl lithium / tetrahydrofuran; hexane / 1 h / -78 °C / Inert atmosphere 1.2: 20 h / 20 °C 2.1: sodium tetrahydroborate / tetrahydrofuran; methanol / 5 h / Inert atmosphere; Reflux
  • 17
  • [ 23927-40-4 ]
  • [ 56438-86-9 ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: 4,16-dibromo[2.2]paracyclophane With Benzophenone imine; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate In toluene at 100℃; for 2h; Stage #2: With hydrogenchloride In tetrahydrofuran at 20℃; for 4h; 4 24g of 4,12-dibromo[2.2]-paracyclophane, 7g of sodium tert-butoxide, 560mg of PdCl2(dppf),11 mL of benzophenone imine and 45 mL of dry toluene were added to a 100 mL single-mouth bottle.The reaction was heated at 100°C for 2 hours. After the reaction was completed, it was naturally cooled to room temperature.To the system was added 10 mL of glacial acetic acid and stirred at room temperature for 30 minutes;After being extracted with dichloromethane, the solvent is removed by rotary evaporation.Add 50 mL of tetrahydrofuran and 8 mL of concentrated hydrochloric acid with a concentration of 38%, stir at room temperature for 4 hours, and spin down to remove the solvent.Add 100 mL of ether and filter to obtain 4-amino-12-bromo[2.2]-p-cyclofluoride hydrochloride;The above hydrochloride was dissolved in 50 mL of ethanol, and the solution was adjusted to pH 8 with a saturated aqueous solution of NaOH of 50% in mass, stirred at room temperature for 20 minutes, and filtered.Column chromatography, racemic 4-amino-12-bromide [2.2] paracyclophane, the yield of 85%,
Multi-step reaction with 6 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 0.92 h / -78 °C / Inert atmosphere 1.2: -78 - 20 °C / Inert atmosphere 2.1: potassium hydroxide / methanol / Inert atmosphere; Reflux 3.1: N,N-dimethyl-formamide; oxalyl dichloride / dichloromethane / 3 h / 0 - 20 °C / Inert atmosphere 4.1: sodium azide / acetone; water / 2 h / 0 °C / Inert atmosphere 5.1: toluene / 3 h / Inert atmosphere; Reflux 6.1: ethanol / 2 h / Inert atmosphere; Reflux 6.2: 45 h / Reflux
  • 18
  • [ 23927-40-4 ]
  • [ 187344-92-9 ]
  • [ 936475-00-2 ]
YieldReaction ConditionsOperation in experiment
96% With (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide; Cs2CO3 In acetonitrile at 20℃; Inert atmosphere; 6 Example 6 Under N2 atmosphere, to a dry reaction flask was added bis(3,5-dimethylphenyl)phosphine oxide (0.193g, 0.75mmol), 4,16-dibromo[2.2]paracyclophane (0.183g, 0.5mmol), Cs2CO3 (0.325 g, 1 mmol), (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide (0.029 g, 5 mmol%), the solvent CH3CN (5 mL) was added and stirred at room temperature until the reaction of 4,16-dibromo[2.2]paracyclophane was completed as monitored by TLC, and the stirring was stopped. The reaction solution was poured into water, extracted with dichloromethane (20 mL×3), the organic phases were combined, washed with saturated NaCl solution (40 mL×3), dried over anhydrous Na2SO4, filtered and concentrated. The crude product was crystallized by cooling with n-hexane to obtain compound 6 as a white powder (0.346 g, 96%).
  • 19
  • [ 23927-40-4 ]
  • [ 4559-70-0 ]
  • [ 192525-87-4 ]
YieldReaction ConditionsOperation in experiment
93% With (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide; Cs2CO3 In acetonitrile at 20℃; Inert atmosphere; 2; 4; 1-5 Example 2 The present embodiment is a synthetic method of a trisubstituted phosphine oxide compound, and the steps are as follows: Under N2 atmosphere, add diphenylphosphine oxide to the dry reaction flask (0.15g, 0.75mmol), 4,16-dibromo[2.2]paracyclophane (0.183g, 0.5mmol), Cs2CO3 (0.325g, 1mmol), (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide (0.029 g, 5 mmol%) was added solvent CH3CN (5 mL) and stirred at room temperature until the reaction of 4,16-dibromo[2.2]paracyclophane was completed as monitored by TLC, and the stirring was stopped. The reaction solution was poured into water, extracted with dichloromethane (20 mL×3), the organic phases were combined, washed with saturated NaCl solution (40 mL×3), dried over anhydrous Na2SO4, filtered and concentrated. The crude product was crystallized by cooling with n-hexane to obtain compound 2 as a white powder (0.283 g, 93%).
  • 20
  • [ 23927-40-4 ]
  • [ 15754-51-5 ]
  • [ 2760728-33-2 ]
YieldReaction ConditionsOperation in experiment
90% With (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide; Cs2CO3 In acetonitrile at 20℃; Inert atmosphere; 5 Example 5 Under N2 atmosphere, to a dry reaction flask, add bis(4-methoxyphenyl)phosphine oxide (0.196g, 0.75mmol), 4,16-dibromo[2.2]paracyclophane (0.183g, 0.5mmol), Cs2CO3 (0.325 g, 1 mmol), (1,10-phenanthroline)(triphenylphosphine)copper(I) bromide (0.029 g, 5 mmol%), added solvent CH3CN (5 mL) and stirred at room temperature, the stirring was stopped until the reaction of 4,16-dibromo[2.2]paracyclophane was complete as monitored by TLC. The reaction solution was poured into water, extracted with dichloromethane (20 mL×3), the organic phases were combined, washed with saturated NaCl solution (40 mL×3), dried over anhydrous Na2SO4, filtered and concentrated. The crude product was crystallized by cooling with n-hexane to obtain compound 5 as a white powder (0.31 g, 90%).
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