* 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.
Example 37 Terephthalonitrile (12.8 g), 95percent sulfuric acid (10.3 g), and ethanol (72.5 g) were placed in a glass autoclave, and the mixture was allowed to react at 130° C. for six hours. The reaction mixture was cooled, and water (9 g) was added thereto. Gas chromatographic analysis revealed that ethyl p-cyanobenzoate had been produced at a yield of 33percent and a selectivity of 83percent.
30%
With hydrogenchloride In ethanol; water
Example 38 Terephthalonitrile (12.8 g), hydrogen chloride gas (2.24 NL), and ethanol (72.5 g) were placed in a glass autoclave, and the mixture was allowed to react at 130° C. for six hours. The reaction mixture was cooled, and water (9 g) was added thereto. Gas chromatographic analysis revealed that ethyl p-cyanobenzoate had been produced at a yield of 30percent and a selectivity of 96percent.
General procedure: To the stirred suspension of dinitrile 1 (0.300 g,2.34 mmol) in liquid NH3 (30-40 mL) in the atmosphere of evaporating NH3, at temperature –(33-50)°C sodium metal (2.15-2.20 eq) was added by portions. The obtained black-brown suspension of the disodium salt of dianion [1]2– was stirred foradditional 5 min. Then ω-X-alkyl bromide 5a-d (1.3 eq in respectto dinitrile 1) was added dropwise and the stirring was continued for1-1.5 h at –33°C in the atmosphere of evaporating NH3. Then thereaction mixture was allowed to contact with air, Et2O (20-30mL) was added and the stirring was continued until complete evaporation of NH3. Water (30 ml) was added to the residue and the organic products were extracted with Et2O (3×25 mL). The combined ether extract was washed till neutral with water, then with saturated solution of NaCl, dried over MgSO4, and the solvent was evaporated. The compositions of mixtures and yields of products were determined according to 1 NMR (dimethyl terephthalate asstandard) and GLC/MS. Individual compounds were separated by preparative thin layer chromatography (L) using fixed layer of absorbent (silica gel 60 PF254 with addition of gypsum, Merck), the eluent was hexane-Et2O. The result of separation was controlled visually by exposure of dried plate to UV light. The fractions of products were washed from the adsorbent by Et2O.
Reference:
[1] Russian Chemical Bulletin, 2016, vol. 65, # 10, p. 2430 - 2436[2] Izv. Akad. Nauk, Ser. Khim., 2016, vol. 10, p. 2430 - 2436,6
3
[ 623-26-7 ]
[ 35963-33-8 ]
[ 83-41-0 ]
[ 623-26-7 ]
Reference:
[1] Journal of the American Chemical Society, 1986, vol. 108, # 18, p. 5453 - 5459
4
[ 623-26-7 ]
[ 109-65-9 ]
[ 100-47-0 ]
[ 1591-30-6 ]
[ 104-51-8 ]
[ 52709-83-8 ]
[ 20651-73-4 ]
Reference:
[1] European Journal of Organic Chemistry, 2005, # 12, p. 2558 - 2565
5
[ 623-26-7 ]
[ 109-65-9 ]
[ 100-47-0 ]
[ 1591-30-6 ]
[ 52709-83-8 ]
[ 20651-73-4 ]
[ 134785-03-8 ]
Reference:
[1] European Journal of Organic Chemistry, 2005, # 12, p. 2558 - 2565
6
[ 623-26-7 ]
[ 10406-25-4 ]
[ 539-48-0 ]
Yield
Reaction Conditions
Operation in experiment
92.1%
With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃;
EXAMPLE 5 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 molpercent, the yield of 4-cyanobenzylamine was 88.8 molpercent and the yield of p-xylynenediamine was 5.8 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of the catalyst A. The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 molpercent, the yield of 4-cyanobenzylamine was 0.2 molpercent and the yield of p-xylynenediamine was 92.1 molpercent.
87.7%
With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃;
EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 molpercent, the yield of 4-cyanobenzylamine was 88.8 molpercent and the yield of p-xylynenediamine was 5.8 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of Ni-diatomaceous earth pellets (manufactured by Nikki Chemical Co., Ltd.; Ni supported amount = 46percent by weight). The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 molpercent, the yield of 4-cyanobenzylamine was 0.5 molpercent and the yield of p-xylynenediamine was 87.7 molpercent.
With hydrogen In 1,2,4-Trimethylbenzene; ammonia at 80℃; for 24 h;
The procedure of Example 1 was repeated except for using terephthalonitrile in place of isophthalonitrile and changing the amount of Catalyst A to 0.6 g, the pretreatment gas to a mixed gas (methanol:nitrogen=4:96 by volume), and the pretreatment conditions to atmospheric pressure, 250° C., a flow rate of 0.18 NL/h, and 3 h. After 24 h of the hydrogenation, the conversion of terephthalonitrile was 100 mol percent, the yield of p-xylylenediamine was 98.7 mol percent, and the yield of high-boiling condensation products was 1.3 mol percent.
92.4%
With hydrogen In 1,2,4-Trimethylbenzene; ammonia at 80℃; for 24 h;
The procedure of Example 12 was repeated except for omitting the pretreatment. After 24 h of the hydrogenation, the conversion of terephthalonitrile was 100 mol percent, the yield of p-xylylenediamine was 92.4 mol percent, and the yield of high-boiling condensation products was 7.6 mol percent.
92%
With hydrogen In ethanol at 95℃; for 1 h;
(1) 100g of terephthalonitrile and 3g of Raney-Ni and 400mL of ethanol were added into a 1L hydrogenation kettle, H2 was continuously charged, The reaction pressure during the system is always maintained at 7MPa. The reaction temperature 95 for 1h, cooling. When the temperature in the reaction vessel was lowered to room temperature, the solution was vented to give p-xylylenediamine (purity of 99percent or more) by filtration and recrystallization in a yield of 92percent
35.6%
With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃;
COMPARATIVE EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of the catalyst A, and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.4 molpercent and the yield of p-xylynenediamine was 35.6 molpercent.
Reference:
[1] ChemCatChem, 2014, vol. 6, # 2, p. 538 - 546
[2] Russian Journal of Applied Chemistry, 2003, vol. 76, # 8, p. 1304 - 1309
[3] Patent: US2008/39658, 2008, A1, . Location in patent: Page/Page column 5
[4] Patent: US2008/39658, 2008, A1, . Location in patent: Page/Page column 5
[5] Patent: CN105016939, 2017, B, . Location in patent: Paragraph 0144; 0145
[6] ChemSusChem, 2017, vol. 10, # 5, p. 842 - 846
[7] Angewandte Chemie - International Edition, 2016, vol. 55, # 47, p. 14653 - 14657[8] Angew. Chem., 2016, vol. 128, # 47, p. 14873 - 14877,5
[9] Patent: EP1449825, 2004, A1, . Location in patent: Page 6
[10] Vestnik Akad.Kazachsk.S.S.R., 1959, vol. 15, # 6, p. 92[11] Chem.Abstr., 1960, p. 10944
[12] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 880[13] Doklady Chemistry, 112-117<1957>141,
[14] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 880[15] Doklady Chemistry, 112-117<1957>141,
[16] Vestnik Akad.Kazachsk.S.S.R., 1959, vol. 15, # 6, p. 92[17] Chem.Abstr., 1960, p. 10944
[18] Journal of the American Chemical Society, 2016, vol. 138, # 28, p. 8781 - 8788
[19] Patent: CN105001032, 2018, B, . Location in patent: Paragraph 0146; 0147
[20] Patent: CN105016940, 2018, B, . Location in patent: Paragraph 0143; 0144
8
[ 623-26-7 ]
[ 10406-25-4 ]
[ 539-48-0 ]
Yield
Reaction Conditions
Operation in experiment
88.8%
With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃;
EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 molpercent, the yield of 4-cyanobenzylamine was 88.8 molpercent and the yield of p-xylynenediamine was 5.8 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of Ni-diatomaceous earth pellets (manufactured by Nikki Chemical Co., Ltd.; Ni supported amount = 46percent by weight). The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 molpercent, the yield of 4-cyanobenzylamine was 0.5 molpercent and the yield of p-xylynenediamine was 87.7 molpercent. EXAMPLE 5 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 molpercent, the yield of 4-cyanobenzylamine was 88.8 molpercent and the yield of p-xylynenediamine was 5.8 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of the catalyst A. The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 molpercent, the yield of 4-cyanobenzylamine was 0.2 molpercent and the yield of p-xylynenediamine was 92.1 molpercent.
With hydrogen;Ni(NO3)2, Cu(NO3)2, Cr(NO3)3, Na2CO3; calcined at 380 deg C for 18 h; pretreatment is given in full text; In 1,2,4-Trimethylbenzene; ammonia; at 80℃; for 24h;Product distribution / selectivity;
The procedure of Example 1 was repeated except for using terephthalonitrile in place of isophthalonitrile and changing the amount of Catalyst A to 0.6 g, the pretreatment gas to a mixed gas (methanol:nitrogen=4:96 by volume), and the pretreatment conditions to atmospheric pressure, 250 C., a flow rate of 0.18 NL/h, and 3 h. After 24 h of the hydrogenation, the conversion of terephthalonitrile was 100 mol %, the yield of p-xylylenediamine was 98.7 mol %, and the yield of high-boiling condensation products was 1.3 mol %.
92.4%
With hydrogen;Ni(NO3)2, Cu(NO3)2, Cr(NO3)3, Na2CO3; calcined at 380 deg C for 18 h; In 1,2,4-Trimethylbenzene; ammonia; at 80℃; for 24h;Product distribution / selectivity;
The procedure of Example 12 was repeated except for omitting the pretreatment. After 24 h of the hydrogenation, the conversion of terephthalonitrile was 100 mol %, the yield of p-xylylenediamine was 92.4 mol %, and the yield of high-boiling condensation products was 7.6 mol %.
92%
With hydrogen; In ethanol; at 95℃; under 52505.3 Torr; for 1h;
(1) 100g of terephthalonitrile and 3g of Raney-Ni and 400mL of ethanol were added into a 1L hydrogenation kettle, H2 was continuously charged, The reaction pressure during the system is always maintained at 7MPa. The reaction temperature 95 for 1h, cooling. When the temperature in the reaction vessel was lowered to room temperature, the solution was vented to give p-xylylenediamine (purity of 99% or more) by filtration and recrystallization in a yield of 92%
80%
With sodium tetrahydroborate; copper ferrite; In water; for 0.25h;Reflux; Green chemistry;
General procedure: As a representative example, in a round-bottom flask (15 mL) equipped with a magnetic stirrer, benzonitrile (1 mmol, 0.103 g) was dissolved in H2O (2 mL). Afterward, CuFe2O4 (0.2 mmol, 0.048 g) was added and the mixture was stirred. Then, NaBH4 (2 mmol, 0.076 g) was also added, and the resulting mixture continued to stir at reflux for 5 min. Upon completion of the reaction (monitored by TLC), the mixture was cooled to room temperature, and the catalyst was separated by an external magnet. The reaction mixture was extracted with ethyl acetate (EtOAc) (2 x 4 mL). The organic layers were combined together and dried over anhydrous sodium sulfate (Na2SO4). The solvent was evaporated under reduced pressure. The pure colorless liquid benzylamine was obtained in 95% yield.
35.6%
With hydrogen;catalyst A; In ammonia; 1,3,5-trimethyl-benzene; at 50℃; under 36753.7 Torr;
COMPARATIVE EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of the catalyst A, and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.4 mol% and the yield of p-xylynenediamine was 35.6 mol%.
With hydrogen; In ethanol; at 95℃; under 52505.3 Torr; for 1h;
(1) Add 100g of terephthalonitrile and 3g of Raney-Ni to a 1L hydrogenation tank,400 mL of ethanol was continuously charged with H2 so that the pressure of the system was always maintained at 7 MPa during the reaction. After the reaction was performed at a reaction temperature of 95C for 1 hour, the temperature was lowered. Until the reactorWhen the temperature was lowered to room temperature, the gas was released, and p-xylylenediamine (having a purity of 99% or more) was obtained by filtration and recrystallization. The yield was 92% by weight.
With hydrogen; In ethanol; at 95℃; under 52505.3 Torr; for 1h;
(1) 100 g of terephthalonitrile and 3 g of Raney-Ni, 400 mL of ethanol are charged in a 1L hydrogenation reactor, and H2 is continuously charged, so that the pressure of the system is always maintained at 7 MPa during the reaction. After the reaction was performed at a reaction temperature of 95C for 1 hour, the temperature was lowered. When the temperature in the reaction vessel was lowered to room temperature, the mixture was degassed, and p-xylylenediamine (with a purity of 99% or more) was obtained by filtration and recrystallization. The yield was 92% by weight.
(Z,Z)-α,α'-bis[3,3-diphenyl-2-(trimethylsilyloxy)-2-propenylidene]-N,N'-bis(trimethylsilyl)-1,4-benzenedimethanamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
Stage #1: 1,1-diphenylacetone With potassium hydride In tetrahydrofuran at 20℃; for 1h;
Stage #2: terephthalonitrile With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 2h;
Stage #3: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; for 12h;
Into a solution of 3-bromobenzaldehyde (7.40 g, 40 mmol) and 3?-bromoacetophenone (7.96 g, 40 mmol) in methanol (80 mL), sodium hydroxide (0.16 g, 4 mmol) was added, and the resultant solution was stirred for 8 h at room temperature. The precipitated chalcone intermediate C3 was collected by filtration and dried. Into a solution of terephthalonitrile (2.56 g, 20 mmol) in 200 mL of dry methanol, 2 mL of a 1 N methanol solution of sodium methoxide was added, and the resultant solution was stirred for 2 h at room temperature. After adding ammonium chloride (1.18 g, 22 mmol), the solution was further stirred for 4 h at room temperature. The solvent was evaporated off under reduced pressure to obtain the benzamidine hydrochloride intermediate D-3, which was dissolved in ethanol (120 mL). After adding the chalcone intermediate C-3 synthesized above and sodium hydroxide (1.60 g, 40 mmol) to the obtained solution, the reaction was allowed to proceed for 8 h while refluxing under heating. The generated white powder was collected by filtration, washed with ethanol until the filtrate became colorless, further washed with water and then ethanol, and vacuum-dried to obtain the aimed pyrimidine intermediate B-3 (7.37 g, yield: 75%).
With hydrogen;Pd-alumina; In ammonia; 1,3,5-trimethyl-benzene; at 50℃; under 36753.7 Torr;
EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5% by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 mol%, the yield of 4-cyanobenzylamine was 88.8 mol% and the yield of p-xylynenediamine was 5.8 mol%. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of Ni-diatomaceous earth pellets (manufactured by Nikki Chemical Co., Ltd.; Ni supported amount = 46% by weight). The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 mol%, the yield of 4-cyanobenzylamine was 0.5 mol% and the yield of p-xylynenediamine was 87.7 mol%. EXAMPLE 5 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5% by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 mol%, the yield of 4-cyanobenzylamine was 88.8 mol% and the yield of p-xylynenediamine was 5.8 mol%. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of the catalyst A. The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 mol%, the yield of 4-cyanobenzylamine was 0.2 mol% and the yield of p-xylynenediamine was 92.1 mol%.
With hydrogen;sponge nickel (R-2400, product of W.R. Grace & Co.); In methanol; at 150℃; under 750.075 - 3750.38 Torr; for 1h;
Crude p-cyanobenzylamine was synthesized in accordance with the process described in Japanese Unexamined Patent Publication (kokai) No. 9-40630 as follows. Into a 100 ml autoclave, methanol (30 ml) and sponge nickel (R-2400, product of W.R. Grace & Co.) (1.0 g) were placed, and the internal pressure of the autoclave was elevated to 1.0 MPa by introducing hydrogen. The mixture contained in the autoclave was stirred while heating at 150 C. for one hour. Terephthalonitrile (5.0 g) and sodium hydroxide (0.1 g) were introduced into the reactor, and the internal pressure was elevated to 0.5 MPa at ambient temperature while introducing hydrogen. Under monitoring of the hydrogen absorbing rate, when the hydrogen pressure was dropped to 0.1 MPa, the pressure was elevated again to 0.5 MPa. This pressure control operation was repeated. Reaction was terminated when the hydrogen absorption ratio reached 115% of the theoretical value. From the thus-obtained reaction mixture, methanol was removed through distillation. The resultant mixture was subjected to a further distillation at a high temperature under a reduced pressure, thereby removing crude p-cyanobenzylamine. Through high-performance liquid chromatographic analysis of the distillate, the p-cyanobenzylamine content and the p-xylylenediamine content were found to be 93 mass % and 7 mass %, respectively.
With ammonia; hydrogen;nickel; In methanol; m-xylylene; at 80 - 120℃; under 60006 Torr; for 4.5 - 6h;Conversion of starting material;
EXAMPLE 3; Hydrogenation; Into a 1-L autoclave equipped with an electromagnetic stirrer, 4 g of Raney nickel catalyst ("NDHT" manufactured by Kawaken Fine Chemicals Co., Ltd.) was charged. Then, 60 g of terephthalonitrile, 60 g of MX and 120 g of methanol were charged into the autoclave and the inner atmosphere thereof was replaced with nitrogen. After introducing 120 g of NH3, the autoclave was heated to 80C. Then, hydrogen gas was introduced into the autoclave to perform the hydrogenation under 8 MPaG at 80C. After initiating the hydrogenation, the reaction liquids were sampled at regular time intervals and analyzed by gas chromatography. After three hours from the initiation, the nitrile conversion reached 97.9 mol%. At this time, the residue of terephthalonitrile was 0.0 mol%, the yield of p-xylylenediamine was 79.0 mol%, and the yield of 4-cyanobenzylamine was 4.3 mol%. After three hours from the initiation, the reaction temperature was raised to 120C to continue the hydrogenation for 1.5 h (overall reaction time = 4.5 h). The results of gas chromatographic analysis showed that the nitrile conversion was 99.99 mol%, the residue of terephthalonitrile was 0.0 mol%, the yield of p-xylylenediamine was 83.9 mol%, and the yield of 4-cyanobenzylamine was 0.015 mol%. Purification of Xylylenediamine After releasing the pressure, MX and methanol were removed from the recovered reaction liquid in a rotary evaporator. By distilling the resultant solution under 0.5 kPa, p-xylylenediamine was obtained as the major distillate. The purity was 99.9% by weight or more and the content of 4-cyanobenzylamine was 0.016% by weight. COMPARATIVE EXAMPLE 3; Hydrogenation; The procedure of Example 3 was repeated except for performing the hydrogenation for 6 h at a constant reaction temperature of 80C. After 6 h of the initiation of hydrogenation, the reaction liquid was analyzed by gas chromatography. The residue of terephthalonitrile was 0.0 mol%, the yield of p-xylylenediamine was 82.2 mol%, and the yield of 4-cyanobenzylamine was 0.4 mol%. Although the hydrogenation was continued longer than in Example 3, a larger amount of the intermediate 4-cyanobenzylamine remained.Purification of Xylylenediamine After releasing the pressure, MX and methanol were removed from the recovered reaction liquid in a rotary evaporator. By distilling the resultant solution under 0.5 kPa, p-xylylenediamine was obtained as the major distillate. The obtained p-xylylenediamine contained 0.4% by weight of 4-cyanobenzylamine. COMPARATIVE EXAMPLE 4; The procedure of Example 3 was repeated except for performing the hydrogenation for 4.5 h at a constant reaction temperature of 120C. The results of gas chromatographic analysis showed that the residue of terephthalonitrile was 0.0 mol%, the yield of p-xylylenediamine was 74.2 mol%, and the yield of 4-cyanobenzylamine was 0.01 mol%.
With hydrogen;catalyst A; In ammonia; 1,3,5-trimethyl-benzene; at 50℃; under 36753.7 Torr;
EXAMPLE 5 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5% by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 mol%, the yield of 4-cyanobenzylamine was 88.8 mol% and the yield of p-xylynenediamine was 5.8 mol%. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of the catalyst A. The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 mol%, the yield of 4-cyanobenzylamine was 0.2 mol% and the yield of p-xylynenediamine was 92.1 mol%.
87.7%
With hydrogen;Ni-diatomaceous earth; In ammonia; 1,3,5-trimethyl-benzene; at 50℃; under 36753.7 Torr;
EXAMPLE 2 Hydrogenation of Terephthalonitrile Into a 100-ml autoclave, were charged 3.2 g of terephthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5% by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 94.8 mol%, the yield of 4-cyanobenzylamine was 88.8 mol% and the yield of p-xylynenediamine was 5.8 mol%. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of Ni-diatomaceous earth pellets (manufactured by Nikki Chemical Co., Ltd.; Ni supported amount = 46% by weight). The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of terephthalonitrile was 100 mol%, the yield of 4-cyanobenzylamine was 0.5 mol% and the yield of p-xylynenediamine was 87.7 mol%.
rac.-4-[5-(2-methoxy-phenoxy)-4,6-dioxo-1,4,5,6-tetrahydro-pyrimidin-2-yl]-benzo-nitrile[ No CAS ]
[ 117837-77-1 ]
Yield
Reaction Conditions
Operation in experiment
With ammonium chloride; sodium methylate; In methanol;
Preparation of the starting material: From 1,4-dicyanobenzene and sodium methylate in methanol followed by ammonium chloride there is obtained 4-cyano-benzamidine hydrochloride, which is used in the next step without further purification, and therefrom with diethyl (2-methoxy-phenoxy)-malonate there is obtained rac.-4-[5-(2-methoxy-phenoxy)-4,6-dioxo-1,4,5,6-tetrahydro-pyrimidin-2-yl]-benzo-nitrile as a yellow product with a melting point >250 C.
Thiophene-2,5-dicarboximidic acid-diethyl ester-dihydrochloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95.5%
With hydrogenchloride; In 1,4-dioxane; ethanol; 2-methoxy-ethanol; acetone;
Thiophene-2,5-dicarboximidic acid-diethyl ester-dihydrochloride= TDD (Formula III) 30 g of thiophene-2,5-dicarboxylic acid nitrile are dissolved in 160 ml of dioxane. After the addition of 30 ml of ethanol, gaseous hydrochloric acid is introduced till saturation, while maintaining the temperature of the solution below 20 C. The suspension formed is stirred with ether for 24 hours, filtered off with suction, washed with ether and dried over KOH in a desiccator. Yield: 64 g (corresponding to 95.5% of the theoretical yield) Melting point above 300 C. In analogous manner is prepared: Furane-2,5-dicarboximidic acid diethyl ester-dihydrochloride= FDD (formula III), Melting point 126-127 C., decomposition, from <strong>[58491-62-6]furane-2,5-dicarboxylic acid nitrile</strong>. Terephthalimidic acid-bis(2-methoxyethyl)-ester-dihydrochloride= TIB (Formula III) 50 g of terephthalic acid dinitrile are dissolved in 500 ml of 2-methoxyethanol. Gaseous hydrochloric acid is introduced till saturation, while maintaining the temperature of the solution below 20 C. The suspension formed is agitated with ether, filtered off with suction, washed with ether and dried over KOH in a desiccator. Yield: 135 g (97.9% theor. yield), Melting point above 300 C. In analogous manner is prepared: Isophthalimidic acid-bis-(2-methoxyethyl-ester-dihydrochloride= IIB (Formula III) Melting point 141 C. with decomposition, from isophthalic acid dinitrile. 4,4'-bis-(2-methoxyethoxycarbonimidoyl)-diphenylether-dihydro-chloride= BMD (Formula III) 50 g of 4,4'-dicyanodiphenylether are suspended in 500 ml of 2-methoxyethanol. Gaseous hydrochloric acid is introduced, the temperature is allowed to rise to 70 C., and this temperature is maintained by cooling until it decreases by itself. The solution is allowed to stand overnight, it is then concentrated in vacuo at max. 45 C. and acetone is added. The precipitate is filtered off with suction, washed with acetone and dried over KOH in a desiccator. Yield: 88 g (87.1% of theor. yield), Melting point 101-103 C.
{(η5-C5H5)(dppm)Ru-(1,4-dicyanobenzene)-Ru(dppm)(η5-C5H5)}(PF6)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
40%
In methanol heating of a suspn. of Ru-complex in dry CH3OH containing the suitable anion salt and DCB under reflux for ca 2 h; filtration, evapn. to dryness, extn. of residue with CH2Cl2, pptn. by addn. of petroleum ether to the extract, filtration, washing several times with petroleum ether, drying in vac.; elem. anal.;
{(η5-C5H5)(dppm)Ru-(1,4-dicyanobenzene)-Ru(dppm)(η5-C5H5)}(BF4)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
40%
In methanol heating of a suspn. of Ru-complex in dry CH3OH containing the suitable anion salt and DCB under reflux for ca 2 h; filtration, evapn. to dryness, extn. of residue with CH2Cl2, pptn. by addn. of petroleum ether to the extract, filtration, washing several times with petroleum ether, drying in vac.; elem. anal.;
With 1-methyl-1H-imidazole; oxygen; copper(ll) bromide; In dimethyl sulfoxide; at 100℃; for 24h;
General procedure: To a 100 mL eggplant type Schlenk flask were added CuBr2 (67.0 mg, 0.3 mmol), corresponding amine (3 mmol) and a solution of NMI (73.8 mg, 0.9 mmol) in DMSO (6 mL). The flask was evacuated and purged with oxygen for three times before the flask was attached to a balloon filled with oxygen. Then the flask was heated at 100 C for 24 h. After the flask was cooled down and the reaction mixture turned into green color, water (15 mL) and dichloromethane (15 mL) was added into the mixture. The water layer was extracted with dichloromethane (5 mL x 3) and the organic layers were combined. After removing the solvent, residue was purified by column chromatography (PE/EA = 100:1) to give the product.
With cupric indole-3-acetate; at 80℃; for 0.333333h;Neat (no solvent); Microwave irradiation;
The typical reaction procedure under MW irradiation. A mixture of nitrile (10 mmol), EDA (40 mmol) and Cu(II)-(IAA)2 (2.0 mmol) was irradiated with microwave (1000 W) for 5-20 min by pulsed irradiation. At the end of the reaction (monitored by TLC, eluent: EtOAc/MeOH, 3:1), the mixture was cooled to room temperature, CH2Cl2 was then added and the catalyst was filtered. Evaporation of the solvent gave the almost pure product. Further purification was performed as for the procedure used in the synthesis of imidazolines under reflux condition. The identities of products were confirmed by mp, 1H NMR, MS and IR data.
With cupric indole-3-acetate; at 80℃; for 0.0833333h;Neat (no solvent); Microwave irradiation;
The typical reaction procedure under MW irradiation. A mixture of nitrile (10 mmol), EDA (40 mmol) and Cu(II)-(IAA)2 (2.0 mmol) was irradiated with microwave (1000 W) for 5-20 min by pulsed irradiation. At the end of the reaction (monitored by TLC, eluent: EtOAc/MeOH, 3:1), the mixture was cooled to room temperature, CH2Cl2 was then added and the catalyst was filtered. Evaporation of the solvent gave the almost pure product. Further purification was performed as for the procedure used in the synthesis of imidazolines under reflux condition. The identities of products were confirmed by mp, 1H NMR, MS and IR data.
With potassium carbonate In butan-1-ol at 150℃; for 0.5h; Microwave irradiation;
21
Terephthalonitrile (115 mg, 0.90 mmol), 4-trifluoromethylbenzoic acid hydrazide (92 mg, 0.450 mmol), K2CO3 (31 mg, 0.225 mmol), and n-butyl alcohol (~2 mL) were combined in a 10 mL CEM Microwave reaction vial fitted with magnetic stir bar and subjected to microwave irradiation at 150 0C for 30 min. The contents were then filtered and concentrated to dryness. Chromatography (3:1 hexanes/EtOAc) afforded the 1,2,4-triazole nitrile (72 mg, 0.230 mmol, 51%). Reduction with DIBAL then generated the corresponding aldehyde.
51%
With potassium carbonate In butan-1-ol at 150℃; for 0.5h; Microwave irradiation;
23
Example 23: Preparation of 4-[5-(4-trifluoromethylphenyl)-lH-[l,2,4]triazol-3-yl]- benzonitrile.Terephthalonitrile (115 mg, 0.90 mmol), 4-trifluoromethylbenzoic acid hydrazide (92 mg, 0.450 mmol), K2Cθ3 (31 mg, 0.225 mmol), and n-butyl alcohol (~2 mL) were combined in a 10 mL CEM Microwave reaction vial fitted with magnetic stir bar and subjected to microwave irradiation at 150 0C for 30 min. The contents were then filtered and concentrated to dryness. Chromatography (3:1 hexanes/EtOAc) afforded the 1,2,4-triazole nitrile (72 mg,
With 1,4-diaza-bicyclo[2.2.2]octane; hexamethylene imine; 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; tris[2-phenylpyridinato-C2,N]iridium(III); acetic acid In water at 23℃; Irradiation;
60%
With 1,4-diaza-bicyclo[2.2.2]octane; hexamethylene imine; perixanthenoxanthene; acetic acid In water at 23℃; for 64h; Inert atmosphere; Irradiation; Schlenk technique; Sealed tube;
tert-butyl (1-(4-cyanophenyl)-2-methylpropyl)carbamate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With phenanthrene; sodium hydroxide In water; acetonitrile at 20 - 40℃; for 8h; Inert atmosphere; Irradiation; regioselective reaction;
General Procedure for thePhotoreaction of 1a with 2a
General procedure: An aqueous CH3CN solution (CH3CN54 ml, H2O 6 ml) of N-Boc Val-OMe1a (0.6 mmol, 10 mM), phenanthrene(0.6 mmol, 10 mM), 1,4-dicyanobenzene (0.6 mmol, 10 mM) and NaOH (3 mmol, 50 mM)in three Pyrex vessels (18 mm x 180 mm) was purged with argon for 10 min andadded by acrylonitrile 2a (0.6 mmol,10 mM) under argon atmosphere. The mixture was heated by water bath at 40 for 2h and irradiated with a 100-W high-pressure mercury lamp for 3 h at roomtemperature. Then the mixture was evaporated, and the resulting residue wasdissolved in EtOAc and washed with water, dried over Na2SO4,and concentrated under reduced pressure. The product was purified by silica gelcolumn chromatography using hexane and EtOAc as eluents to give adduct 3a
4-(1,3-dihydroxy-2,2-dimethyl-propyl)-benzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
Stage #1: pantolactone With potassium hydroxide In water; acetonitrile for 2h; Reflux;
Stage #2: terephthalonitrile With phenanthrene In water; acetonitrile at 20℃; for 6h; Inert atmosphere; Irradiation;
General Procedure for the Photoreactionof 6 with 2a
General procedure: An aqueous CH3CN solution (CH3CN54 ml, H2O 6 ml) of 6(0.6 mmol, 10 mM) and KOH (3 mmol, 50 mM) was refluxed for 2 h. The resulting mixture was transferredto three Pyrex Vessels (18 mm x 180 mm), and was added by phenanthrene(0.6 mmol, 10 mM), 1,4-dicyanobenzene (0.6 mmol, 10 mM). The mixture was purgedwith argon for 10 min, and addition of acrylonitrile 2a (0.6 mmol, 10 mM) under argon atmosphere and irradiation with a 100-Whigh-pressure mercury lamp for 6 h at room temperature gave 7 after the above mentioned workup
4-([4-(trifluoromethoxy)phenyl]carbonyl)benzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
With n-butyllithium; In tetrahydrofuran; at -70℃; for 2h;
4-([4-(Truoromethoxy)phenylJ carbonyl}benzonitrile (6i). To a solution of n-butyllithium(8.87 ml, 12.5 mmol) in THF (30 ml) at -70C 4-bromotrifluoromethoxybenzene (3.00 g, 12.5mmol) in THF (10 ml) was added without allowing the temperature to exceed -70C. To thegrey-brown solution 1,4-dicyanobenzene (1.60 g, 12.5 mmol) was added as a suspension inTHF (10 ml). After 2 h at -70C the red suspension was quenched with aq. 2NHC1 (75 ml)and ice (about 25 g) and TBME (150 ml) was added. After separation of the organic layer theinorganic phase was extracted with TBME (2 x 30 ml). The organic phases were combined,dried over Na2SO4 and concentrated at reduced pressure. The crude product (2 g) was purifiedby silica gel flash chromatography (TBME/hept 1:8) to afford a white solid 6i (1.2 g, 33%).?H-NMR (400 MHz, CDC13): 7.35 (m, 2 H), 7.78-7.9 1 (m, 6 H).HPLC retention time: 4.95 mm
With tert.-butylhydroperoxide; copper(l) iodide; In N,N-dimethyl-formamide; at 130℃; for 48h;
General procedure: To a 25 mL round flask was added the mixture of boronic acid (1) (0.3 mmol), ethyl2-cyano-3-ethoxyacrylate (2a, 0.6 mmol), CuI (0.3 mmol), t-BuOOH (0.6 mmol) in DMF (2 mL)successively. The mixture was stirred at 130 C for 24 h under air. After the reaction was completed, themixture was cooled to room temperature, diluted with water (15 mL) and then extracted withdichloromethane (5 mL × 3). The organic extract was washed with H2O (10 mL × 3) and dried overanhydrous Na2SO4. After removal of the CH2Cl2 in vacuum, the crude product thus obtained was purified bycolumn chromatography on silica gel using petroleum ether/ethyl acetate as eluent to give the desired product3
General procedure: To the stirred suspension of dinitrile 1 (0.300 g,2.34 mmol) in liquid NH3 (30-40 mL) in the atmosphere of evaporating NH3, at temperature -(33-50)C sodium metal (2.15-2.20 eq) was added by portions. The obtained black-brown suspension of the disodium salt of dianion [1]2- was stirred foradditional 5 min. Then omega-X-alkyl bromide 5a-d (1.3 eq in respectto dinitrile 1) was added dropwise and the stirring was continued for1-1.5 h at -33C in the atmosphere of evaporating NH3. Then thereaction mixture was allowed to contact with air, Et2O (20-30mL) was added and the stirring was continued until complete evaporation of NH3. Water (30 ml) was added to the residue and the organic products were extracted with Et2O (3×25 mL). The combined ether extract was washed till neutral with water, then with saturated solution of NaCl, dried over MgSO4, and the solvent was evaporated. The compositions of mixtures and yields of products were determined according to 1 NMR (dimethyl terephthalate asstandard) and GLC/MS. Individual compounds were separated by preparative thin layer chromatography (L) using fixed layer of absorbent (silica gel 60 PF254 with addition of gypsum, Merck), the eluent was hexane-Et2O. The result of separation was controlled visually by exposure of dried plate to UV light. The fractions of products were washed from the adsorbent by Et2O.
4-(cyclobutyl(hydroxy)(phenyl)methyl)benzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
29%
With methanol; (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; triethylamine at -78 - 20℃; for 72h; Irradiation; Inert atmosphere;
With thiobenzoic acid; dipotassium hydrogenphosphate; fac-tris(2-phenylpyridinato-N,C2')iridium(III) In N,N-dimethyl acetamide at 20℃; for 2h; Irradiation; regioselective reaction;
With thiobenzoic acid; dipotassium hydrogenphosphate; fac-tris(2-phenylpyridinato-N,C2')iridium(III) In N,N-dimethyl acetamide at 20℃; for 2h; Irradiation; regioselective reaction;
58%
With thiobenzoic acid; potassium phosphate In N,N-dimethyl acetamide at 20℃; for 6h; Irradiation;
With sodium acetate In N,N-dimethyl acetamide at 20℃; for 24h; Inert atmosphere; Irradiation;
89%
With caesium carbonate In N,N-dimethyl acetamide at 20℃; for 16h; Irradiation;
1-1; 1-2; 1-3; 1-4; 2-1; 2-2; 2-3; 2-4; 3-1; 3-2; 3-3; 3-4
In the 20mL reaction tube, add magnets,1-Phenylpyrrolidine (x mmol),Terephthalonitrile (0.5mmol), Cs2CO3 (y mmol), different solvents (5mL),React for 16 hours under normal temperature and blue light irradiation.The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, rotary evaporated to remove the solvent, and dried by a vacuum oil pump to obtain the target product. The yield of each product is calculated by weighing, as shown in Table 3.
78%
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrabutylammonium perchlorate In N,N-dimethyl acetamide at 25℃; Sealed tube; Inert atmosphere; Electrochemical reaction;
With lithium acetate; tetrabutylammonium tetrafluoroborate In dimethyl sulfoxide Inert atmosphere; Electrolysis;
With sodium acetate; C33H24N4*3Cd(2+)*2C21H12NO6(3-) In N,N-dimethyl acetamide at -78 - 20℃; for 12h; Inert atmosphere; Irradiation; regioselective reaction;
88 %Spectr.
With fac-tris(2-phenylpyridinato-N,C2')iridium(III); sodium acetate In N,N-dimethyl acetamide at 23℃; for 12h; Irradiation; Inert atmosphere;
With 2,4,5,6‐tetra‐9H‐carbazol‐9‐yl‐1,3‐benzenedicarbonitrile; caesium carbonate In dimethyl sulfoxide at 20℃; for 24h; Inert atmosphere; Irradiation;
2.2 General procedure for the synthesis of acetalation-pyridylation of alkenes
General procedure: In a 10 mL reaction vial with a stirring bar, 4-cyanopyridine 1 (0.2 mmol), Cs2CO3 (2.0 equiv.), and 1,2,3,5-tetrakis(carbazol- 9-yl)-4,6-dicyanobenzene (4CzIPN) (3 mol%) were added. The vial was then evacuated and backfilled three times with N2, followed by adding DMSO (2 mL), styrene 2 (2.5 equiv.), and 2,2-diethoxyacetic acid 3 (2.5 equiv.). The mixture was stirred at room temperature with 10 W blue LED irradiation for 24 h under a nitrogen atmosphere. After the reaction was completed, it was quenched with water (5 mL), and then the ethyl acetate (15 mL) was added three times for extraction. The combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum. The residue was purified by silica gel chromatography (petroleum ether/ethyl acetate = 5/1) to afford the desired product 4 or 5.
With ammonium bicarbonate; copper(II) nitrate In dimethyl sulfoxide at 140℃; for 40h; Autoclave;
Representative Procedure for Conversion of Various Arylethenesto Aromatic Nitriles
General procedure: To a stainless steel autoclave lined with Teflon, 0.5 mmol substrate,0.075 mmol Cu(NO3)2, 1 mmol (NH4)2CO3, and 2 mLDMSO were added. Then the reactor was filled with 2 MPaoxygen and was heated under magnetic stirring at 140 °C for 30h or 40 h (Caution: the use of the high-pressure oxygen ispotentially hazardous. Thus, experiments using the high-pressureoxygen must only be carried out under rigorous safety precautions,and it is required to use the appropriate high-pressurereactor to avoid the potential leakage or explosion of the gas).Once the reaction time was reached, the mixture was cooled toroom temperature, diluted with 30 mL diethyl ether, and filteredvia a Celite pad. The organic mixture was washed withwater (3 × 5 mL), dried with anhydrous sodium sulfate, and concentratedin vacuum. GC analysis provided the GC yields of theproduct with an internal standard. In addition, the combinedcrude product from another 1-5 parallel experiments was purifiedby column chromatography and identified by 1H NMR and13C NMR spectroscopy. All the products are the known compounds,and the analytical data of several typical compoundsare as follows: