* 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.
Phosphorus oxychloride(24 mL, 315 mmol)was added dropwise to DMF (30 mL) at 0 C, andthe mixture was stirred for 1 h at this temperature. Then triphenylamine(10 g, 40 mmol) was added, and the reaction mixture wasstirred at 100 C for 6 h. When the reaction was finished themixture was cooled to room temperature, poured into ice water,and neutralized to pH 7 with 5percent NaOH aqueous solution. The solutionwasextracted with ethyl acetate. The organic layer was driedwith anhydrous magnesium sulfate and concentrated by vacuumevaporation. The crude product was purified by column chromatographyusing the mixture of petroleum and dichloromethane(vol. ratio 2:1) as an eluent to get the desired compound as a paleyellow solid (5.76 g) with a yield of 52.74percent.
72%
With trichlorophosphate In N,N-dimethyl-formamide
After the flask was kept under nitrogen atmosphere and cooled to 0 °C, phosphorus oxychloride (POCl3, 3.8 ml, 0.0408 mol) was added dropwise. The temperature inside the flask was kept below 5 °C during the addition of POCl3, After the addition of POCl3 was completed, the solution was allowed to warm up slowly to room temperature. Then a solution of triphenylamine (5 g, 0.0204 mol, from Aldrich, Milwauke, WI) in dry DMF (10 ml) was added dropwise. The reaction mixture was refluxed at 80 °C for 24 hours and then poured into ice water. This solution was neutralized with potassium hydroxide until the pH reached between 6 and 8. The product was extracted with chloroform. The chloroform extract was dried with anhydrous sodium sulfate, filtered, and evaporated off to form the crude product, which was recrystallized from methanol to yield 5.57 g (72percent) of 4-(diphenylamino)benzaldehyde. The melting point was found to be 126.5 °C. The 1H-NMR spectrum (100 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 6.57-7.56 (m, 12H, Ar), 7.60-7.98 (m, 2H, Ar), 10.21 (s, 1H, CHO). The IR spectrum of the product was characterized by the following absorption frequencies (KBr, cm-1): v(C-H) 2743; 2830, v(C-H in Ar) 3037, v(C=O) 1689, v(C=C in Ar) 1585; 1567; 1490, γ(Ar) 825. The mass spectrum of the product was characterized by the following mass peaks (m/z): 274 (100percent, M+1).
Stage #1: at 0℃; for 0.5 h; Stage #2: at 90℃; for 12 h;
A portion of 2.16g (29.5 mmol) of N,N-dimethyl formamide was added dropwiseto a portion of phosphorus oxychloride (4.52 g, 29.5mmol). The reaction mixture was stirred for 30 minutes at 0oC. The mixture was added to a solution of triphenylamine(0.48 g, 1.97 mmol) in 10 mL of dichloroethane. Then thereaction mixture was stirred for 12 h at 90 oC. A portion of100 mL of water was added into the reaction mixture thenextracted three times with 50 mL of methylene chloride(MC). The combined organic layer was washed with aqueoussodium carbonate (10 wt percent) and then dried over anhydrousmagnesium sulfate (MgSO4). The solvent was removedusing a rotary evaporator. The yield of white crystal was0.49 g (92.7percent). mp 135.6 oC. 1H-NMR (400 MHz, CDCl3) 9.80 (s, 1H), 7.69-7.66 (d, J = 11.36 Hz, 2H), 7.35-7.31 (t, J= 7.68 Hz, 4H), 7.18-7.15 (m, 6H), 7.03-7.01 (d, J = 8.8 Hz,3H), 13C-NMR (100 MHz, CDCl3) 190.29, 153.23, 146.05,131.21, 129.65, 129.01, 126.21, 125.02, 119.25. Anal. Calcd.For C19H13NO2: C, 79.43; H, 4.56; N, 4.88; O, 11.14. Found:C, 79.82; H, 4.51; N, 4.782.
92%
at 0 - 45℃; for 2 h;
4-(Diphenylamino)benzaldehyde (2) According to the literature,[27] to a solution of TPA (980 mg,4mmol) and DMF (2mL) was added POCl3 (1.8mL, 4mmol)dropwise at 08C with stirring. During this process, a precipitatewas formed. After addition was completed, the mixture waswarmed to 458C, and was stirred at this temperature for 2 h. The mixture was cooled to room temperature and poured into water(10 mL). A yellow precipitate was then formed by adjustment ofthe pH of the solution to 7 with saturated Na2CO3. Thissuspension was filtered to give a yellow solid. Recrystallisationfrom ethanol afforded a needle-like pale yellow solid (1.00 g,yield 92 percent). dH (400 MHz, CDCl3 TMS) 9.86 (s, 1H), 7.71–7.73(d, J 8.0, 2H), 7.11–7.40 (m, 10H), 7.04–7.06 (d, J 8.2, 2H). Thecharacterisation data were consistent with the literature.
92%
at 50℃; Cooling with ice
A 100 mL round bottom flask was added with 3.00 g (0.04 mol, 3.15 mL) of DMF, during the stirring, 4.90 g (0.02 mol) triphenylamine, an ice-water bath with stirring paddle white After 5min, with stirring under a constant pressure funnel was slowly added dropwise 31.00g (0.2mol, 18mL) phosphine oxychloride, yellow solution, dropping control, about 1h dropwise; the dropwise addition the reaction was warmed to 50 deg.] C 50-60min, to give a red solution, the reaction is tracked until TLC complete, after the reaction, the reaction mixture was poured into 200mL of ice water, adjusted with NaOH solution to pH 8, to give a voluminous yellow precipitate was filtered off with suction, washed three times, and dried in vacuo to give 5.02g of compound 1, 92percent yield.
92%
at 20 - 45℃; for 3.5 h; Cooling with ice
Add 4.0 g of triphenylamine and 17.8 mL of DMF to the flask, stir and dissolve. Slowly add 7.6 mL of phosphorus oxychloride dropwise in an ice bath. Continue to stir for half an hour in an ice bath. After stirring for 1 hour at room temperature, slowly warm up to 45°. C reaction 2h. After the reaction was completed, the reaction solution was poured into ice water, and the unreacted P0C13 was neutralized with NaOH, and the resulting product was allowed to stand and was filtered to give a pale yellow solid, which was compound 2 in 92percent yield
90.4%
With trichlorophosphate In chloroform at 0 - 20℃; for 14 h; Heating / reflux
25.0 g (0.102 mol) triphenylamine and 16 ml (2.0 equivalents, 0.204 mol) of DMF were added to 150 ml of CHCl3 and cooled to 0° C. 16.0 ml (1.5 equivalents, 0.153 mol) of POCl3 were added drop-wise. The flask was allowed to slowly warm to 20° C., stirred for 12 hours, and then refluxed for 2 hours. The solution was cooled and poured into 250 ml cold water (10-15° C.) and then neutralized with aqueous Na2CO3. The solution was extracted with 4.x.75 ml CH2Cl2, washed with 3.x.50 ml H2O, dried with MgSO4, and then concentrated by rotary evaporation. The resulting yellow solid, 4-(diphenylamino)benzaldehyde, was recrystallized from EtOH, giving 20.08 g of bright yellow crystals. A second crop of crystals from the mother liquor gave an additional 5.10 g of 4-(diphenylamino)benzaldehyde. The total yield was 25.18 g or 90.4percent.
89%
Stage #1: at 0℃; for 0.666667 h; Stage #2: at 45℃; for 14 h;
3.00 mL of DMF was cooled to 0 °C in ice bath then 2.95 mL of POCl3 was added dropwise. After stirring for 40 minutes at 0 °C, the solution was warmed up to room temperature then 250 mg of triphenylamine was added and the reaction mixture was heated at 45 °C for 14 hrs. After cooling down to room temperature, the reaction mixture was poured into 15.0 mL of ice and neutralized with a solution of 1.0 M NaOH. Products were extracted with CH2Cl2. Combined organic layers were washed with brine, dried with Na2SO4 and concentrated to give a crude mixture, which was purified by silica gel column chromatography (EtOAc:hexane = 1:30) to give the compound 2 (244.10 mg, 89percent) as a yellowish solid. 1H NMR (300 MHz, DMSO-d6) δ: 9.77 (s, CHO, 1H), 7.72 (d, J = 8.8 Hz, 2H), 7.42 (t, J = 7.9 Hz, 4H), 7.30-7.14 (m, 6H), 6.88 (d, J = 8.8 Hz, 2H); 13C NMR (75 MHz, DMSO-d6) δ 190.54, 145.53, 131.27, 130.01, 128.56, 126.38, 125.45, 118.14, 89.
88%
Stage #1: at 10℃; Inert atmosphere Stage #2: at 35℃; for 24 h; Inert atmosphere Stage #3: With water In N,N-dimethyl-formamideCooling with ice; Inert atmosphere
POCl3 (4.47 mL) was added dropwise to 8.5 mL DMF with stirring under absolutely dry conditions, and the temperature was kept below 10 °C. After adding a mixture of 24.34 mmol (5.97 g) triphenylamine and 2 mL DMF to the reaction vessel at this temperature, the reaction mixture was maintained at 35 °C for 24 h. Subsequently, the reaction solution was poured into ice water and the precipitated mixture was filtered and washed with water. The crude product was purified by column chromatography (silica gel, dichloromethane) to afford 9. Yield 88percent, yellow solid
88.9%
With trichlorophosphate In 1,2-dichloro-ethane at 0 - 90℃; for 12 h;
To a 25 ml round bottomflask was charged with a solution ofDMF (2.01 mol ratio) and 1,2-dichloroethane (3 ml) at 0° C. POCl3(1.25 mol ratio) was slowly added to the mixture. Triphenylamine(5 g, 1 mol ratio) in 1, 2-dichloroethane (3 ml) was added drop wiseto the above mixture. The mixture was stirred for 12 h at 90° C.Next, it was poured into ice water and the compound wasfilteredand dried to give yellow color TA. Yield – 88.9percent, 1H NMR, (400 MHz,CDCl3-d): δ = 9.80 (s, 1H), 7.67 (d, J = 8.8 Hz, 2H), 7.34 (t, J = 7.6 Hz,4H), 7.187.15 (m, 6H), 7.01 (d, J = 8.4 Hz, 2H) ppm. 13C NMR,(100 MHz, CDCl3-d): δ = 190.46, 153.39, 146.18, 131.34, 129.76,129.13, 126.34, 125.15, 119.37 ppm.
88%
Stage #1: for 2 h; Cooling with ice Stage #2: at 95 - 105℃;
step 1, preparation of Triphenylamine monoaldehyde : Under ice-cooling, 1 ml (11.2 mmol) of phosphorus oxychloride was slowly added dropwise to a reaction flask containing 15 ml (194.5 mmol) of N,N-dimethylformamide and stirred for 2 hours to obtain Vilsmeier reagent. 2g (8.2mmol) of triphenylamine was added to Vilsmeier reagent and reacted at 95-105°C for 2.5-8 hours. The product was poured into ice water and the pH was adjusted to neutrality to obtain a precipitate. The crude product was purified by column chromatography to obtain triphenylamine monoaldehyde in a yield of 88.
87%
Stage #1: at 0 - 20℃; Inert atmosphere Stage #2: at 80℃; for 6 h; Inert atmosphere
Synthesis of 4-(diphenylamino)benzaldehyde (2)was adapted from Park et al. (2000) with slight modifications.Dry N,N-dimethylformamide (DMF) (6.0 mL,77.6 mmol) was, under nitrogen atmosphere, added to a 100 mL two-necked flask equipped with a nitrogen inlet, a magnetic stirrer and a condenser. After coolingthe reaction flask to 0C, 2.0 mL of phosphorusoxychloride (3.13 g, 20.4 mmol) were added dropwiseunder stirring. The mixture was allowed to reach roomtemperature then triphenylamine (TPA, 1) (5.0 g,20.4 mmol) and dry DMF (15.0 mL) were added. The mixture was heated at 80C for 6 h under stirring,cooled and poured into chilly water containing 6.0 gof sodium acetate under vigorous stirring. The precipitatedyellow solid was washed with water and purifiedby flash chromatography (silica gel/toluene). The desired product was obtained as a yellow powder (4.87 g,17.8 mmol, 87 percent yield) and its 1H NMR spectrum wasfound in accordance with literature data (Park et al.,2000).
86%
Stage #1: for 2 h; Cooling with ice Stage #2: at 40℃;
The synthesis route is summarized in Scheme 1. POCl3 (11mL) was added to a DMF solution (250mL) with stirring for 2h in ice-water bath. After the color change to nacarat, added triphenylamine (100mmol) to the solution with stirring at 40°C. After the reaction was complete, the reaction mixture was poured into ice water (1000mL) and adjusted pH to 9 with NaOH to separate faint yellow crystals out. The solid obtained by filtered, washed with water and recrystallized in ethanol to give compound B in 86percent as a faint yellow powder. 1H NMR (DMSO-d6, 300MHz): δ (ppm): 9.77 (s, 1H), 7.72 (d, 2H, J=8.7Hz), 7.43 (t, 4H, J=15.6Hz), 7.23 (m, 6H), 6.88 (d, 2H, J=8.7Hz); 13C NMR (DMSO-d6, 75MHz): δ (ppm): 117.7, 125.0, 126.0, 128.1, 129.6, 130.9, 145.1, 152.3, 190.1; Elemental analysis (calcd. percent) for C19H15NO: C, 83.49, H, 5.53, N, 5.12, Found: C, 83.46, H, 5.54, N, 5.14; ESI–MS m/z: [B+H]+ Calcd for C19H16NO 274.12, Found 273.92 (Fig.S1).
83%
Stage #1: at 10 - 35℃; for 24 h; Stage #2: Cooling with ice
POCl3 (4.47 ml, 48.67 mmol) was added dropwise to 8.5 ml DMF with stirring under absolutely dry conditions, and the temperature was kept below 10°C. After adding a mixture of (5.97 g, 24.34 mmol) triphenylamine and 2 ml DMF to the reaction vessel at this temperature, the reaction mixture was maintained at 35°C for 24 h. Subsequently, the reaction solution was poured into ice water and the precipitated mixture was filtered and washed with water. The crude product was purified by column chromatography (silica gel, dichloromethane) to afford a yellow solid (yield: 5.55g, 20.3mmol, 83percent). 1H-NMR (CDCl3, ppm): δ9.81(s, 1H), δ7.68(d, 2H), δ7.36-7.31(m, 4H), δ7.19-7.14(m, 6H), δ7.02(d, 2H).
82%
Stage #1: at 0℃; for 1 h; Stage #2: at 100℃; for 6 h;
Phosphorus oxychloride (1.6mL, 16.8mmol) was added dropwise to DMF (1.3mL, 19.5mmol) at 0°C, and the mixture was stirred at 0°C for 1h. Triphenylamine (3.3g, 13.3mmol) was added and the reaction mixture was stirred at 100°C for 6h. Then, the mixture was cooled to room temperature, poured into ice water and carefully neutralized to pH 7 with 5percent NaOH aqueous solution. The solution was extracted with dichloromethane (3×150mL). Then, the organic phase was washed with water (2×100mL) and dried over anhydrous MgSO4. After filtration, the solvent was removed. The crude product was purified by column chromatography (silica gel, hexane/dichloromethane, 3/1, v/v) to produce white solid.
82%
Stage #1: at 20℃; for 1 h; Stage #2: for 12 h; Reflux
Include in a dry reaction flaskPOCl3 (1.83 mL, 20 mmol) and DMF (3.1 mL, 40 mmol) with chamberThe mixture was stirred at room temperature for 1 h, and 10 mL of 1,2-dichloroethane was added to obtain reaction solution A.The reaction solution A was transferred to a constant pressure dropping funnel,And added dropwise to 100 mL of a 1,2-dichloroethane solution containing triphenylamine (4.91 g, 20 mmol).After completion of the dropwise addition, the reaction mixture was heated under reflux for 12 h.Cooled to room temperature, the reaction solution was slowly poured into 1 L of vigorously stirred deionized water, extracted with dichloromethane, several layers were combined and washed three times with deionized water.The resulting organic phase was dried over anhydrous MgSO4 and dried to remove the solid. The resulting filtrate was concentrated to give the white solid product 4- (diphenylamino) benzaldehyde by ethyl acetate and petroleum ether as eluant. (4.50 g, 16.5 mmol) in 82percent yield.
81%
With trichlorophosphate In ethanol; water
Synthesis of 4-(N,N-diphenylamino)benzaldehyde Into a three-necked flask, 101.4 g of triphenylamine and 35.5 ml of DMF (dimethylformamide) were placed, and 84.4 ml of phosphorus oxychloride was added dropwise thereto with stirring while cooling with ice water, and then the temperature was raised to 95° C. to carry out reaction for 5 hours. The reaction solution obtained was poured into 4 liters of warm water, followed by stirring for 1 hour. Thereafter, the precipitate formed was collected by filtration, and washed with a mixture of ethanol/water (1:1) to obtain 4-(N,N-diphenylamino)benzaldehyde in an amount of 91.5 g (yield: 81.0percent).
77%
at 0 - 50℃; for 5 h;
Triphenylamine (4.0 g, 16.3 mmol) was dissolved in 8.0 mL DMF. POCl3 (7.6 mL, 81.5 mmol) was added drop-wise to the mixture at 0 °C. As the temperature rose to room temperature, the mixture changed to a clear bright red solution. The reaction was heated to 50 °C for an additional 5 h. After being cooled, the mixture was poured into an ice-bath with stirring and later neutralized with sodium carbonate. Pale yellow solids were collected by filtering and recrystallizing in ethanol (3.43 g, 77percent yield). 1H-NMR (400 MHz, CDCl3) δ: 7.01 (d, J = 8.7 Hz, 2H), 7.15–7.18 (m, 6H), 7.34 (t, J = 8 Hz, 4H), 7.68 (d, J = 8.8 Hz, 2H), 9.81 (s, 1H).
77%
Stage #1: at 0℃; for 1 h; Inert atmosphere Stage #2: at 0 - 80℃; Inert atmosphere
Phosphorus oxylchloride (4.47 mL ; 47.9 mmol ; 2 eq.) was added drop-wise to anhydrous DMF (25mL) at 0°C under inert atmosphere and the solution was vigorously stirred for 1 hour. Triphenylamine (5.96 g ; 24.3 mmol ; 1 eq.) was added at 0°C to the mixture which was then allowed to reach room temperature and was stirred at 80°C overnight. The solution was cooled down and slowly poured into iced water (200 mL), The formed yellow sticky precipitate was recovered by filtration, washed with water, and dried overnight in an oven at 65°C under vacuum. The obtained dark solid was dissolved in DCM and purified by chromatography over a silica column gel EP : DCM (gradient 2 : 3 to 1 : 3) and led to 5.17 g of a yellow solid (18,9mmol ; 77percent yield). 1H NMR (400 MHz ; CDCl3): δ 9.79 (s, 1H), 7.66 (d, 2H, J 8.4 Hz), 7.33 (t, 4H, J 8 Hz), 7.16 (m, 6H), 7 (d, 2H, J 8.8 Hz). 13C NMR (101 MHz ; CDCl3): δ 190.6, 146.2, 131.5, 129.8, 129.1, 126.3, 125.2, 119.4, 11 signals obscured or overlapping. ESI MS : 274.1 m/z : [M+H]+ ; 296.1 m/z : [M+Na]+
77%
at 0 - 80℃; Inert atmosphere
Phosphorus oxychloride (4.47 mL; 47.90 mmol.; 2.00 eq.) was added dropwise to anhydrous DMF (25mL) at 0°C under inert atmosphere and the solution was vigorously stirred for 1 hour. Triphenylamine (5.96 g; 24.30 mmol.; 1.00 eq.) was added at 0°C to the mixture which was then allowed to reach room temperature and was stirred at 80°C overnight. The solution was cooled down and slowly poured into iced water (200 mL), The formed yellow sticky precipitate was recovered by filtration, washed with water, and dried overnight in an oven at 65°C under vacuum. The obtained dark solid was dissolved in CH2Cl2 and purified by chromatography over a silica column gel EP : CH2Cl2 (gradient 2 : 3 then 1 : 3) and led to 5.17 g of a yellow solid (18,90 mmol.; 77percent yield). 1H NMR (400 MHz; CDCl3): δ 9.79 (s, 1H), 7.66 (d, 2H, J 8.4 Hz), 7.33 (t, 4H, J 8 Hz), 7.16 (m, 6H), 7 (d, 2H, J 8.8 Hz). 13C NMR (101 MHz; CDCl3): δ 190.6, 146.2, 131.5, 129.8, 129.1, 126.3, 125.2, 119.4, 11 signals obscured or overlapping. ESI MS: 274.1 m/z : [M+H]+ ; 296.1 m/z : [M+Na]+.
76%
Stage #1: at 0 - 25℃; for 1 h; Inert atmosphere Stage #2: at 90℃; for 3 h; Inert atmosphere
General procedure: Aldehyde derivatives were synthesized by a revised method ofthe literature [48]. Phosphorous oxychloride (POCl3) (10 mL, 107mmoL,1.0 equiv.) was added dropwise to DMF (8 mL,107 mmoL,1.0equiv.) at 0 °C. The mixture was stirred at 25 °C for 1 h. Triphenylamineor its derivatives (Ar) (107 mmol, 1.0 equiv.) was addedand the reaction mixture was stirred and heated at 90 °C for 3 h.After cooling down to room temperature, the mixture was pouredinto 50 mL cold distilled H2O and extracted with dichloromethane (3 x 20 mL). The combined organic layer was dried with anhydrousNa2SO4 and then filtered. The filtrates were concentrated by rotaryevaporation. The target compounds were purified by columnchromatography on silica gel using petroleum:ethyl aceate(v:v = 4:1) as the eluent.2.4.1.1. 4-formyltriphenylamine(2a). Yield 76percent as orange solid,Rf = 0.44, m.p. =132 °C; ESI-MS: m/z = 273.3(M)+. 1H NMR (CDCl3,500 MHz) δ:9.81 (s, 1H, -CHO), 7.68 (d, J = 8.8 Hz, 2H), 7.34 (t,J = 9.0 Hz, 4H), 7.17 (d, J = 9.0 Hz, 4H), 7.15 (d, J = 9.0 Hz, 2H),7.12-6.98 (m, 2H), 13C NMR (CDCl3, 500 MHz) δ: 190.29, 153.30,146.10, 131.26, 129.68, 129.10, 126.27, 125.10, 119.32.
76%
at -5 - 85℃; for 1 h; Inert atmosphere
To a 100 mL four-necked flask was added a solution of triphenylamine in DMF (previously prepared by dissolving 3 g of triphenylamine in 40 mL of DMF), nitrogen-protected, magnetically stirred, and cooled to -5 ° C.Slowly add 9.3 g of POCl3 to the reaction solution using a constant pressure dropping funnel.After the completion of the dropwise addition, the reaction conditions were maintained for 1 h. The temperature was raised to 85 ° C to react.After the reaction is completed, the reaction mixture is poured into ice water and quenched.Extracted with dichloromethane, washed 5 times with deionized water, dried over anhydrous magnesium sulfate and filtered.The solvent was concentrated under reduced pressure and the crude material was purified eluteSeparation and purification to give a white solid in a yield of 76percent.
71.5%
Stage #1: for 0.25 h; Cooling with ice Stage #2: at 65℃; for 16 h;
Was added to a 250 mL flask7.4 mL (0.1 mol) of DMF, stirred in an ice-water bath followed by dropwise addition of 9.2 mL(0. lmol)Phosphorus oxychloride, continue to stir, 15min bottle in the liquid becomes sticky,And finally get white slightly red solid frozen salt.100 ml of a solution containing 24.5 g (0. lmol)Triphenylamine in chloroform was added to the flask and the temperature was raised to about 50 ° C for about 30 minutes.65 ° C under reflux reaction 16h, thin layer chromatography to determine the reaction completely after the steaming finished chloroform,The residue into the 1000mL cold water to potassium carbonate to adjust the pH value of the solution to the weak alkaline, a large number of yellow-green solid precipitation, pumping, spin dry solvent, the residue by column separation and purification, eluent is pure petroleum ether,7.81 g of product was obtained in a yield of 71.5percent
71.5%
Stage #1: for 0.5 h; Cooling with ice Stage #2: at 50 - 65℃; for 3 h;
Add 7.4 mL (0.1 mol) of DMF to a 250 mL flask.Stir in the ice water bath,Then 9.2 mL (0.1 mol) of phosphorus oxychloride was added dropwise.Stirring was continued and the liquid became viscous after 30 min, and finally a whiteish yellow solid frozen salt was obtained.Then 24.5 g (0.1 mol) of triphenylamine was added to the above flask.Warm up to 50 ° C for about 30 min until the frozen salt is completely dissolved,Reflow reaction at 65 ° C for 2.5 h,TLC was used to determine the completion of the reaction (TLC). The reaction solution was added dropwise to a 1000 mL ice water flask, and the solution was adjusted to pH=9 with sodium hydroxide. A large amount of yellow-green solid was precipitated, suction filtered, dried, and separated by chromatography. Purification (eluent is n-hexane),7.81 g of product were obtained in a yield of 71.5percent.
69.6%
Stage #1: for 0.25 h; Cooling with ice Stage #2: at 40 - 50℃; for 18 h;
Under ice cooling, was added to 250mL flask 0.1mol N, N-dimethylformamide, followed by dropwise addition of phosphorus oxychloride 0.1mol, stirring was continued, after 15min becomes viscous liquid in the bottle, and finally to give a white slightly reddish solid frozen salt; 0.1mol containing the triphenylamine 100ml chloroform was added to the flask, the temperature rose to 50°C , about 30min to freeze all dissolved salts, the reaction was refluxed for 18h at 40 °C, the reaction was judged complete by thin layer chromatography, after rotary evaporation and then chloroform, the residue was poured into 1000mL of cold water, the pH adjusted with potassium carbonate to be weakly basic, a large yellow-green solid was precipitated, after filtration, rotary evaporation, the residue was purified by column chromatography (eluent pure petroleum ether) separation and purification, to give the product as a light yellow solid 7.60g, intermediate i.e., a yield of 69.6percent.
67%
at 0 - 90℃;
To a solution of triphenylamine(4.9 g, 20 mmol) in N,N-dimethyl formamide (DMF) (50 ml) was added POCl3 (1.2 mL), the solution was stirred under ice-bath condition for 10 min. The reaction mixture was heated to 90 °C and stirred for 4 h. After cooling down to room temperature, the mixture was extracted with ethyl acetate three times. After evaporating the solvent, the mixture was added sodium borohydride in absolute ethanol (50 mL) and reacted for 2 h. After removing the solvent, the residue was added triphenyl phosphorus hydrobromide (6.86 g, 20 mmol) in CHCl3. The solution was heated to reflux for 2 h. After removing the solvent, the residual solid was recrystallized in anhydrous ethyl ether to give the light green solid (7.2 g, 60percent yield). Mp=249 °C. 1H NMR (CDCl3) δ: 5.36-5.38(d, J=14 Hz, 2H, CH2), 6.79-6.81(d, J=8 Hz, 2H, Ph), 6.90-6.93(m, J=8.5 Hz, 2H, Ph), 6.99-7.03(m, J=8.5 Hz, 6H, Ph), 7.21-7.24(t, 4H, J=8.5, 7.5 Hz, Ph), 7.62-7.66(t, J=7.5 Hz, 6H, Ph), 7.75-7.79(t, 9H, J=7.5 Hz, Ph). 13C NMR (125 MHz, CDCl3, TMS): δ (ppm) 149.75, 145.91, 137.43, 136.26, 129.94, 129.65, 128.88, 128.71, 127.93, 126.98, 125.74, 50.14.
63%
Stage #1: at 0 - 20℃; Stage #2: at 80℃; for 2 h;
4-Diphenylamino-benzaldehyde was synthesized according to the previously described method [Wijesinghe, Channa A.; El-Khouly, Mohamed E.; Zandler, Melvin E.; Fukuzumi, Shunichi; D'Souza, Francis; - Chemistry - A European Journal, 2013, vol. 19, 29, p. 9629 - 9638]: phosphorus oxychloride (22 mL) was added dropwise to anhydrous DMF (25 mL) and cooled at 0 °C in a two necked 250 mL round-bottomed flask over a period of 30 min. After completing the addition, the mixture was allowed to warm to room temperature. Then triphenylamine (6 g, 24.5 mmol) was added and the mixture was heated to 80 °C for 2 h. After cooling to room temperature, the reaction mixture was quenched by pouring into ice cold water. Ammonium hydroxide was added for neutralization, a yellow solid precipitated out. The solid was filtered and washed with water, recrystallized from ethanol. Yield 4.2 g (63percent) 1H NMR (300 MHz, CDCl3) δ 9.83 (s, 1H), 7.70 (d, J = 8.7 Hz, 2H), 7.42 – 7.31 (m, 4H), 7.24 – 7.14 (m, 6H), 7.04 (d, J = 8.7 Hz, 2H).
62.3%
at 5 - 60℃; for 15.5 h;
The triphenylamine (110.0g, 0.45mol) was added to the mixture of Phosphoryl chloride (83.0mL, 0.90mol) in N,N-Dimethylformamide (550.0mL) at 5 and then further stirred for 30mins., followed by further stirred for 15hrs at 60. After triphenylamine was consumed, the reaction temperature was allowed to room temperature and then, added 200mL of ethyl acetate and 100 mL of water followed by stirred for 30 mins. Separated and extracted the aqueous layer by ethyl acetate. After combined the organic layers, washed with water and brine and then dried over anhydrous Na2SO4. Filtered and concentrated under the pressure followed by purified by recrystallized with methanol (300mL) to give 76.4g of pale yellowish solids. (yield: 62.3percent)
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3
[ 68-12-2 ]
[ 603-35-0 ]
[ 4181-05-9 ]
Yield
Reaction Conditions
Operation in experiment
95%
Stage #1: for 0.5 h; Cooling with ice Stage #2: at 55℃; for 1 h;
(1) in ice bath was added purified DMF (N,N-dimethylformamide) (5.85g, 80mmol) in 100mL round bottom flask was added dropwise with stirring POCl3 Solution (15.33g, 100mmol), after about 0.5h dropwise, forming a white slurry; warmed to 55°C, triphenylamine was added (2.45g, 10mmol), TLC trace reaction, the reaction solution turned deep red after 1h, the reaction solution was poured into a large number of ice water, sodium carbonate solution was added to adjust the pH to 8 to obtain a large amount of yellow precipitate was suction filtration the crude product was obtained as a pale yellow crude product obtained was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate acrylate = 25/1 (V / V )) to give 2.59g of the formula the compound 1, compound 1 in a yield of 95percent.
With sodium acetate trihydrate; magnesium sulfate; trichlorophosphate In methanol
EXAMPLE 1-1 Synthesis of 4-(diphenylamino)benzaldehyde 30 mL of dimethylformaldehyde (DMF) was put into a 250 mL flask, cooled to 0° C. and 3.8 mL of POCl3 was slowly added thereto. Then, 10 g of triphenylamine was added to the resultant mixture and heated to 70° C. for 5 hours. The reaction container was cooled to room temperature and then a reactant solution was poured into ice water. Subsequently, 40 g of sodium acetate trihydrate was put for neutralization and then an organic layer was separated with methylenechloride. The obtained organic layer was dried using magnesium sulfate and methylenechloride was removed under reduced pressure, yielding a product. The product was recrystallized using methanol and a light yellow solid was finally obtained, yielding 73percent of a desired product. Data of NMR spectra confirmed that the product had the same structure as 4-(diphenylamino)benzaldehyde, that is, the compound (1) in the reaction scheme 2.
Reference：
[1] Patent: US2003/87127, 2003, A1,
5
[ 20441-00-3 ]
[ 4181-05-9 ]
Reference：
[1] Angewandte Chemie (International Edition in English), 2000, vol. 39, # 3, p. X517-521
6
[ 603-34-9 ]
[ 190334-72-6 ]
[ 4181-05-9 ]
Reference：
[1] Patent: US5688961, 1997, A,
7
[ 1122-91-4 ]
[ 122-39-4 ]
[ 4181-05-9 ]
Reference：
[1] Dyes and Pigments, 2012, vol. 95, # 2, p. 229 - 235
Reference：
[1] Organic Process Research and Development, 2012, vol. 16, # 5, p. 934 - 938
24
[ 4181-05-9 ]
[ 1034-49-7 ]
[ 205877-26-5 ]
Yield
Reaction Conditions
Operation in experiment
77%
Stage #1: With potassium <i>tert</i>-butylate In tetrahydrofuran at -78℃; for 2 h; Inert atmosphere Stage #2: at -78 - 20℃; for 21 h; Inert atmosphere
t-BuOK (4 equiv) was allowed to dissolve in dried THF (2 ml/mmol) under argon and the solution was cooled to 78 C. After 20 min, 1.6 equiv of (bromomethyl)triphenylphosphonium bromide was added portionwise and stirring under argon continued for 2 h. Then a solution of aldehyde 8 (2.47 mmol) or 9 (0.74 mmol) in dried THF (2 ml/mmol) was slowly added dropwise and stirring continued for 1 h at 78 C and 20 h at rt. The solution was mixed with the same volume of NH4Cl (aq), acidified with 2 M HCl (aq) and extracted with ethyl acetate (350 ml). The organic layer was dried over Na2SO4, filtered and the solvent was evaporated in vacuo. Purification of the residue by chromatography on a SiO2 column (20percent CHCl3 in hexanes) gave the title compound 7a (510 mg), 77percent, (yellow solid) or 7b (80 mg, 41percent, light-yellow crystalline solid; after chromatography the semi-solid oil was dissolved in hot hexanes, the solution was allowed to reach RT, filtered and concentrated under vacuum).
Reference：
[1] Tetrahedron, 2016, vol. 72, # 44, p. 7081 - 7092
[2] Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 3053 - 3068
[3] Journal of Organic Chemistry, 2011, vol. 76, # 21, p. 8726 - 8736
25
[ 4181-05-9 ]
[ 90965-06-3 ]
[ 205877-26-5 ]
Reference：
[1] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9700 - 9713
[2] Synlett, 2009, # 18, p. 2977 - 2981
26
[ 558-13-4 ]
[ 4181-05-9 ]
[ 205877-26-5 ]
Reference：
[1] Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 3053 - 3068
27
[ 4181-05-9 ]
[ 205877-26-5 ]
Reference：
[1] European Journal of Inorganic Chemistry, 2012, # 1, p. 65 - 75
28
[ 4181-05-9 ]
[ 808758-81-8 ]
Yield
Reaction Conditions
Operation in experiment
96%
With potassium iodate; potassium iodide In water; acetic acid at 80℃; for 5 h; Inert atmosphere
4-(Bis(4-iodophenyl)amino)benzaldehyde (3) wassynthesized by contacting 4-(diphenylamino)benzaldehyde(2) (3.8 g, 13.9 mmol), potassium iodide (3.0 g,18.1 mmol), acetic acid (45.0 mL) and deionized water(5.0 mL) in a 100 mL two-neck flask equipped witha nitrogen inlet, a magnetic stirrer, and a condenser.After heating the reaction mixture to 80C, potassiumiodate (2.98 g, 13.9 mmol) was added in one portionand the resulting mixture was kept at 80C understirring for 5 h. The solution was allowed to cool toroom temperature and it was poured into ice-waterunder stirring. Yellow precipitate was collected by filtrationand treated with a 5 mass percent NaHSO3 solution(40.0 mL). Upon filtration, the desired aldehyde wasobtained as a yellow solid (3) (7.0 g, 13.4 mmol, 96 percentyield), the 1H NMR spectrum of which was found inaccordance with literature data (Ning et al., 2007).
93%
With potassium iodate; potassium iodide In water at 80℃; for 6 h;
250 mL three-necked flask was added 100 mL of acetic acid and 10 mL of water,2.0 g of compound 2 and 1.8 g of KI were added under stirring, and the temperature was raised to 80 ° C, and 1.7 g of KIO3 was added thereto, and the reaction was carried out at 80 ° C for 6 hours.After completion of the reaction, the reaction solution was poured into water, filtered, and the precipitate was washed several times with distilled water and recrystallized from ethanol to give a yellow solid, compound 3, 93percent
93%
With potassium iodate; acetic acid; potassium iodide In water at 80℃; for 6 h;
In a 250 mL three-necked flask, 100 mL of acetic acid and 10 mL of water were added, 2.0 g of compound 2 and 1.8 g of KI were added under stirring, and the temperature was raised to 80° C., 1.7 g of KI03 was added, and the reaction was carried out at 80° C. for 6 h. After the reaction was completed, the reaction solution was poured into water and filtered. The precipitate was washed several times with distilled water and recrystallized from ethanol to give a yellow solid, which was compound 3 in 93percent yield, mp 140-142°C
87%
With potassium iodate; potassium iodide In water; acetic acid at 80℃; for 3 h;
To an acetic acid (20ml) – water (2ml) solution of 4-(diphenylamino)benzaldehyde 1.0 g (3.7mmol) was added potassium iodide 0.85 g (5.1 mmol) and the solution was heated to 80 °C.Potassium iodate 0.79 g (3.7 mmol) was added to the solution at a time, and the mixture wascontinuously stirred at 80 °C for 3 h. After the solvent was evaporated, the product was extractedwith ethyl acetate. The extracts were washed with water and brine, and dried over anhydrousmagnesium sulfate. The solvent was evaporated, and the obtained product was chromatographedon silica gel (eluent; hexane and chloroform 1:1) to give 2 (1.70 g, 87 percent).IR (KBr) ν: 1694 (C=O), 511 (C-I) cm-1; 1H-NMR (CDCl3) δ: 6.96 (4H, d, J=8.5 Hz), 7.00 (2H, d,J=8.5 Hz), 7.73 (4H, d, J=8.5 Hz), 7.76 (4H, d, J=8.5 Hz), 9.83 (1H, s).
76%
With potassium iodate; acetic acid; potassium iodide In water at 85℃; for 3 h;
To begin, acetic acid (20 mL) and DI water (2 mL) were added to a mixture of 4-(diphenylamino)benzaldehyde (1.40 g, 5.12 mmol), potassium iodide (1.14 g,6.88 mmol) and potassium iodate (1.10 g, 5.12 mmol). After the mixture was heated at 85° C for 3 h, the mixture was cooled to room temperature and filtered.The crude products were recrystallized from ethanol to give a yellow solid of 2.04 g (yield: 76.0 percent; m.p.: 142.5–143.6° C). 1H NMR (400 MHz, CDCl3): d 9.84 (1H, s),7.70 (2H, d, J = 8.80 Hz), 7.61–7.63 (4H, m), 7.05 (2H, d, J = 8.40 Hz), 6.87–6.90(4H, m).
75%
Stage #1: With potassium iodide In water; acetic acid at 80℃; for 1 h; Stage #2: With potassium metaperiodate In water; acetic acid at 80℃; for 4 h;
A modified version of a previously reported method was used. In a 500 mL three-necked round-bottom flask, 4-(N,Ndiphenyl- amino)benzaldehyde (14.00 g, 51.28 mmol), potassium iodide (11.43 g, 68.85 mmol), acetic acid (210 mL) and water (20 mL) were heated to 80℃ . After stirring for 1 h, potassium iodate (10.97 g, 51.26 mmol) was added and the reaction was stirred at 80℃ for 4 h. The solution was allowed to cool and the solid was collected, washed withwater and recrystallised from DCM–ethanol (1: 5) giving the product as a yellow powder (20.05 g, yield: 75percent)
72%
at 110℃; for 18 h;
An AcOH solution (100 mL) of 4-(N,N-diphenylamino)benzaldehyde (6.00 g, 21.95 mmol), potassiumiodide (8.02 g, 48.31 mmol) and potassium iodate(5.17 g, 24.15 mmol) was stirred at 110 C for 18 h. Aftercooling to room temperature, the precipitate was filteredand washed with water. The crude solid was dissolved inmethylene chloride and washed with aqueous solution ofsodium sulfite and sodium hydrogen carbonate, consecutively.The organic layer was dried in vacuo and purifiedby column chromatography on silica gel using methylenechloride and n-hexane as an eluent. Yield (8.31 g, 72percent).Mp 139–140 C. 1H NMR (400 MHz, DMSO-d6) 6.89(d, J = 88 Hz, 4 H, –N–Ph–I), 7.05 (d, J = 8.4 Hz,2 H, CHO–Ph–N–), 7.62 (d, J = 8.8 Hz, 4 H, –N–Ph–I),7.70 (d, J = 84 Hz, 2 H, CHO–Ph–N–), 9.84 (s, 1 H,–Ph–CHO); 13C NMR (100.64 MHz, DMSO-d6) 89.63,121.83, 126.51, 128.88, 134.01, 135.78, 144.58, 145.35,190.40.
61%
With potassium iodate; acetic acid; potassium iodide In water at 80℃;
To a stirred mixture of 4-formyl triphenylamine(4.96 g, 18.2 mmol), potassium iodide (1.95 g, 12 mol), acetic acid (60 mL), and water (6 mL) at 80 °C was added potassium iodate (1.92 g, 9.1 mmol) in one portion, and the resulting mixture was stirred and heated for 4 h. After the reaction, most of the acetic acid was removed by rotary evaporation. The black residue was dissolved in ethyl acetate and washed several times with water and sodium bicarbonate solution. The organic layer was dried over MgSO4, filtered, and concentrated, and the crude material was purified by column chromatography to give the product as a yellow solid. Yield 4.43 g (61 percent). 1H-NMR (CDCl3, ppm) δ9.85(s, 1H), δ7.72(d, 2H), δ7.63(d, 4H), δ7.06(d, 2H), δ6.90(d, 4H).
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29
[ 4181-05-9 ]
[ 1206731-57-8 ]
Reference：
[1] Proceedings of the National Academy of Sciences of the United States of America, 2016, vol. 113, # 46, p. 13162 - 13167
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