2-isocyanato-1,3,5-trimethylbenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,4,6-Trimethylphenyl isocyanate (Lancaster Co., 20.5 g, 0.127 mol) and 2,4,6-trimethylaniline (17.2 g, 0.127 mol) were reacted in a procedure analogous to that described in Example 1, giving a brown solution. A thick, white flaky precipitate was observed to form about 2 hours after aniline addition. This material was collected by filtration, rinsed with hexanes, and dried in vacuo (crop 1). The CHCl3 reaction filtrate (also containing rinse hexanes) was set aside and was observed to produce additional white precipitate overnight. It was concentrated somewhat using a rotary evaporator and insolubles were similarly collected by filtration, rinsed with hexanes until a pinkish impurity was removed, and dried (crop 2). Three additional crops of material were collected in this fashion. Crop 3 was collected by removal of volatiles from the filtrate of crop 2, crushing the resultant solid, slurrying it in hexanes overnight, and collecting insolubles by filtration and rinsing them with hexanes. Crop 4 was collected by removal of volatiles from the filtrate of crop 3, slurrying with petroleum ether, and collecting insolubles by filtration and rinsing them with petroleum ether. Crop 5 was collected identically by treatment of the filtrate from Crop 4, using smaller slurry and rinse volumes of petroleum ether. The weights of crops 1 to 5 were 11.1 g, 8.32 g, 5.96 g, 2.30 g, and 4.19 g, respectively (total 31.9 g, 84.6%). 1H NMR (solid state CRAMPS, 500 MHz): δ 7.5 (br, aryl), 6.1 and 5.1 (NH), 1.4, 0.9 (sh), and 0.5 (sh) (overlapping, CH3). 13C{1H} NMR (solid state CPMAS, 50 MHz): δ 157.9 and 154.9 (br, C=0, 1 C), 135.0, 129.6, 128.7, and 127.6 (aryl, 12 C), 22.8, 20.0, 19.4, and 17.9 (CH3, 6 C). IR (KBr pellet): 3286 (vs), 3003 (w), 2972 (m), 2918 (s), 2855 (w), 1640 (vs), 1609 (s), 1553 (vs), 1485 (m), 1470 (sh), 1446 (sh), 1377 (w), 1308 (w), 1285 (w), 1252 (sh), 1223 (s), 1065 (w), 1032 (w), 1013 (w), 882 (w), 849 (m), 760 (w), 748 (w), 721 (sh), 696 (m), 580 (w) cm−1. FD-MS m/z (%): 296.7 (MH+, 100). Exact mass calculated for C19H24N2O: 296.19. Melting point (DSC): onset (extrapolated) 236° C., max. 240° C. giving a brown solution to form about 2 hours This material was collected by filtration rinsed with hexanes dried in vacuo (crop 1) The CHCl3 reaction filtrate ( also containing rinse hexanes) to produce additional white precipitate overnight It was concentrated somewhat a rotary evaporator and insolubles were similarly collected by filtration rinsed with hexanes until a pinkish impurity was removed dried (crop 2) Three additional crops of material were collected in this fashion Crop 3 was collected by removal of volatiles from the filtrate of crop 2 crushing the resultant solid overnight collecting insolubles by filtration rinsing them with hexanes Crop 4 was collected by removal of volatiles from the filtrate of crop 3 collecting insolubles by filtration rinsing them with petroleum ether Crop 5 was collected identically by treatment of the filtrate from Crop 4 rinse volumes of petroleum ether onset (extrapolated) 236° C., max 240° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,4,6-Trimethylphenyl isocyanate (Lancaster Co., 20.5 g, 0.127 mol) and 2,4,6-trimethylaniline (17.2 g, 0.127 mol) were reacted in a procedure analogous to that described in Example 1, giving a brown solution. A thick, white flaky precipitate was observed to form about 2 hours after aniline addition. This material was collected by filtration, rinsed with hexanes, and dried in vacuo (crop 1). The CHCl3 reaction filtrate (also containing rinse hexanes) was set aside and was observed to produce additional white precipitate overnight. It was concentrated somewhat using a rotary evaporator and insolubles were similarly collected by filtration, rinsed with hexanes until a pinkish impurity was removed, and dried (crop 2). Three additional crops of material were collected in this fashion. Crop 3 was collected by removal of volatiles from the filtrate of crop 2, crushing the resultant solid, slurrying it in hexanes overnight, and collecting insolubles by filtration and rinsing them with hexanes. Crop 4 was collected by removal of volatiles from the filtrate of crop 3, slurrying with petroleum ether, and collecting insolubles by filtration and rinsing them with petroleum ether. Crop 5 was collected identically by treatment of the filtrate from Crop 4, using smaller slurry and rinse volumes of petroleum ether. The weights of crops 1 to 5 were 11.1 g, 8.32 g, 5.96 g, 2.30 g, and 4.19 g, respectively (total 31.9 g, 84.6%). 1H NMR (solid state CRAMPS, 500 MHz): δ 7.5 (br, aryl), 6.1 and 5.1 (NH), 1.4, 0.9 (sh), and 0.5 (sh) (overlapping, CH3). 13C{1H} NMR (solid state CPMAS, 50 MHz): δ 157.9 and 154.9 (br, C=0, 1 C), 135.0, 129.6, 128.7, and 127.6 (aryl, 12 C), 22.8, 20.0, 19.4, and 17.9 (CH3, 6 C). IR (KBr pellet): 3286 (vs), 3003 (w), 2972 (m), 2918 (s), 2855 (w), 1640 (vs), 1609 (s), 1553 (vs), 1485 (m), 1470 (sh), 1446 (sh), 1377 (w), 1308 (w), 1285 (w), 1252 (sh), 1223 (s), 1065 (w), 1032 (w), 1013 (w), 882 (w), 849 (m), 760 (w), 748 (w), 721 (sh), 696 (m), 580 (w) cm−1. FD-MS m/z (%): 296.7 (MH+, 100). Exact mass calculated for C19H24N2O: 296.19. Melting point (DSC): onset (extrapolated) 236° C., max. 240° C. giving a brown solution to form about 2 hours This material was collected by filtration rinsed with hexanes dried in vacuo (crop 1) The CHCl3 reaction filtrate ( also containing rinse hexanes) to produce additional white precipitate overnight It was concentrated somewhat a rotary evaporator and insolubles were similarly collected by filtration rinsed with hexanes until a pinkish impurity was removed dried (crop 2) Three additional crops of material were collected in this fashion Crop 3 was collected by removal of volatiles from the filtrate of crop 2 crushing the resultant solid overnight collecting insolubles by filtration rinsing them with hexanes Crop 4 was collected by removal of volatiles from the filtrate of crop 3 collecting insolubles by filtration rinsing them with petroleum ether Crop 5 was collected identically by treatment of the filtrate from Crop 4 rinse volumes of petroleum ether onset (extrapolated) 236° C., max 240° C.

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The hydrochoride salt of 2-imino-1-methylpyrrolidine (6.73 g.; 0.05 L mole) is converted to free base (4.0 g.; 0.05 mole) by adding 10 ml. of 50% NaOH to an aqueous slurry (minimal amount of water) of the salt and benzene extraction. After drying over K2CO3, the benzene solution is stirred at room temperature and 8.06 g. (0.05 mole) of 2,4,6-trimethylphenylisocyanate [made according to the method of K. Inukai and Y. Maki, Kogyo Kagaku Zasshi, 70 (4), 491-4 (1967)] dissolved in anhydrous benzene is added. The reaction mixture is stirred at room temperature for 11/2 hours and then the solvent is evaporated in vacuo leaving an oily residue, which crystallizes on cooling. Recrystallizaton from acetone yields the pure product, 1-mesityl-3-(1-methyl-2-pyrrolidylidene)urea, m.p. = 121°-123° C. by adding 10 ml of 50% NaOH to an aqueous slurry (minimal amount of water) of the salt and benzene extraction After drying over K2CO3 is added The reaction mixture is stirred at room temperature for 11/2 hours the solvent is evaporated in vacuo leaving an oily residue, which crystallizes on cooling

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The hydrochloride salt of 2-imino-1-methylpyrrolidine (6.73 g.; 0.05 mole) is converted to free base (4.0 g.; 0.05 mole) by adding 10 ml. of 50% NaOH to an aqueous slurry (minimal amount of water) of the salt and benzene extraction. After drying over K2CO3, the benzene solution is stirred at room temperature and 8.06 g. (0.05 mole) of 2,4,6-trimethylphenylisocyanate [made according to the method of K. Inukai and Y. Maki, Kogyo Kagaku Zasshi, 70 (4), 491-4 (1967)] dissolved in anhydrous benzene is added. The reaction mixture is stirred at room temperature for 11/2 hours and then the solvent is evaporated in vacuo leaving an oily residue, which crystallizes on cooling. Recrystallization from acetone yields the pure product, 1-mesityl-3-(1-methyl-2-pyrrolidylidene)urea, m.p. = 121°-123° C. by adding 10 ml of 50% NaOH to an aqueous slurry (minimal amount of water) of the salt and benzene extraction After drying over K2CO3 is added The reaction mixture is stirred at room temperature for 11/2 hours the solvent is evaporated in vacuo leaving an oily residue, which crystallizes on cooling Recrystallization from acetone

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,4,6-Trimethylphenyl isocyanate (Lancaster Co., 20.5 g, 0.127 mol) and 2,4,6-trimethylaniline (17.2 g, 0.127 mol) were reacted in a procedure analogous to that described in Example 1, giving a brown solution. A thick, white flaky precipitate was observed to form about 2 hours after aniline addition. This material was collected by filtration, rinsed with hexanes, and dried in vacuo (crop 1). The CHCl3 reaction filtrate (also containing rinse hexanes) was set aside and was observed to produce additional white precipitate overnight. It was concentrated somewhat using a rotary evaporator and insolubles were similarly collected by filtration, rinsed with hexanes until a pinkish impurity was removed, and dried (crop 2). Three additional crops of material were collected in this fashion. Crop 3 was collected by removal of volatiles from the filtrate of crop 2, crushing the resultant solid, slurrying it in hexanes overnight, and collecting insolubles by filtration and rinsing them with hexanes. Crop 4 was collected by removal of volatiles from the filtrate of crop 3, slurrying with petroleum ether, and collecting insolubles by filtration and rinsing them with petroleum ether. Crop 5 was collected identically by treatment of the filtrate from Crop 4, using smaller slurry and rinse volumes of petroleum ether. The weights of crops 1 to 5 were 11.1 g, 8.32 g, 5.96 g, 2.30 g, and 4.19 g, respectively (total 31.9 g, 84.6%). 1H NMR (solid state CRAMPS, 500 MHz): δ 7.5 (br, aryl), 6.1 and 5.1 (NH), 1.4, 0.9 (sh), and 0.5 (sh) (overlapping, CH3). 13C{1H} NMR (solid state CPMAS, 50 MHz): δ 157.9 and 154.9 (br, C═O, 1 C), 135.0, 129.6, 128.7, and 127.6 (aryl, 12 C), 22.8, 20.0, 19.4, and 17.9 (CH3, 6 C). IR (KBr pellet): 3286 (vs), 3003 (w), 2972 (m), 2918 (s), 2855 (w), 1640 (vs), 1609 (s), 1553 (vs), 1485 (m), 1470 (sh), 1446 (sh), 1377 (w), 1308 (w), 1285 (w), 1252 (sh), 1223 (s), 1065 (w), 1032 (w), 1013 (w), 882 (w), 849 (m), 760 (w), 748 (w), 721 (sh), 696 (m), 580 (w) cm−1. FD-MS m/z (%): 296.7 (MH+, 100). Exact mass calculated for C19H24N2O: 296.19. Melting point (DSC): onset (extrapolated) 236° C., max. 240° C. giving a brown solution to form about 2 hours This material was collected by filtration rinsed with hexanes dried in vacuo (crop 1) The CHCl3 reaction filtrate ( also containing rinse hexanes) to produce additional white precipitate overnight It was concentrated somewhat a rotary evaporator and insolubles were similarly collected by filtration rinsed with hexanes until a pinkish impurity was removed dried (crop 2) Three additional crops of material were collected in this fashion Crop 3 was collected by removal of volatiles from the filtrate of crop 2 crushing the resultant solid overnight collecting insolubles by filtration rinsing them with hexanes Crop 4 was collected by removal of volatiles from the filtrate of crop 3 collecting insolubles by filtration rinsing them with petroleum ether Crop 5 was collected identically by treatment of the filtrate from Crop 4 rinse volumes of petroleum ether onset (extrapolated) 236° C., max 240° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,4,6-Trimethylphenyl isocyanate (Lancaster Co., 20.5 g, 0.127 mol) and 2,4,6-trimethylaniline (17.2 g, 0.127 mol) were reacted in a procedure analogous to that described in Example 1, giving a brown solution. A thick, white flaky precipitate was observed to form about 2 hours after aniline addition. This material was collected by filtration, rinsed with hexanes, and dried in vacuo (crop 1). The CHCl3 reaction filtrate (also containing rinse hexanes) was set aside and was observed to produce additional white precipitate overnight. It was concentrated somewhat using a rotary evaporator and insolubles were similarly collected by filtration, rinsed with hexanes until a pinkish impurity was removed, and dried (crop 2). Three additional crops of material were collected in this fashion. Crop 3 was collected by removal of volatiles from the filtrate of crop 2, crushing the resultant solid, slurrying it in hexanes overnight, and collecting insolubles by filtration and rinsing them with hexanes. Crop 4 was collected by removal of volatiles from the filtrate of crop 3, slurrying with petroleum ether, and collecting insolubles by filtration and rinsing them with petroleum ether. Crop 5 was collected identically by treatment of the filtrate from Crop 4, using smaller slurry and rinse volumes of petroleum ether. The weights of crops 1 to 5 were 11.1 g, 8.32 g, 5.96 g, 2.30 g, and 4.19 g, respectively (total 31.9 g, 84.6%). 1H NMR (solid state CRAMPS, 500 MHz): δ 7.5 (br, aryl), 6.1 and 5.1 (NH), 1.4, 0.9 (sh), and 0.5 (sh) (overlapping, CH3). 13C{1H} NMR (solid state CPMAS, 50 MHz): δ 157.9 and 154.9 (br, C=0, 1 C), 135.0, 129.6, 128.7, and 127.6 (aryl, 12 C), 22.8, 20.0, 19.4, and 17.9 (CH3, 6 C). IR (KBr pellet): 3286 (vs), 3003 (w), 2972 (m), 2918 (s), 2855 (w), 1640 (vs), 1609 (s), 1553 (vs), 1485 (m), 1470 (sh), 1446 (sh), 1377 (w), 1308 (w), 1285 (w), 1252 (sh), 1223 (s), 1065 (w), 1032 (w), 1013 (w), 882 (w), 849 (m), 760 (w), 748 (w), 721 (sh), 696 (m), 580 (w) cm−1. FD-MS m/z (%): 296.7 (MH+, 100). Exact mass calculated for C19H24N2O: 296.19. Melting point (DSC): onset (extrapolated) 236° C., max. 240° C. giving a brown solution to form about 2 hours This material was collected by filtration rinsed with hexanes dried in vacuo (crop 1) The CHCl3 reaction filtrate ( also containing rinse hexanes) to produce additional white precipitate overnight It was concentrated somewhat a rotary evaporator and insolubles were similarly collected by filtration rinsed with hexanes until a pinkish impurity was removed dried (crop 2) Three additional crops of material were collected in this fashion Crop 3 was collected by removal of volatiles from the filtrate of crop 2 crushing the resultant solid overnight collecting insolubles by filtration rinsing them with hexanes Crop 4 was collected by removal of volatiles from the filtrate of crop 3 collecting insolubles by filtration rinsing them with petroleum ether Crop 5 was collected identically by treatment of the filtrate from Crop 4 rinse volumes of petroleum ether onset (extrapolated) 236° C., max 240° C.

反応条件: temp:0.00; pressure:0.00; stir: