CN103342654A - Novel method for hydrolyzing nitrile group to acylamino - Google Patents

Novel method for hydrolyzing nitrile group to acylamino Download PDF

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CN103342654A
CN103342654A CN2013102786531A CN201310278653A CN103342654A CN 103342654 A CN103342654 A CN 103342654A CN 2013102786531 A CN2013102786531 A CN 2013102786531A CN 201310278653 A CN201310278653 A CN 201310278653A CN 103342654 A CN103342654 A CN 103342654A
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novel method
hydrolyzed
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amide group
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CN103342654B (en
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景崤壁
谭晓东
丁兆兵
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Yangzhou University
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Abstract

The invention relates to a novel method for hydrolyzing nitrile grouping to acylamino. The method comprises the following steps: adding a nitrile compound, N,N'-Di-n-amyl bromide benzimidazole,1,8-Diazabicyclo[5.4.0]undec-7-ene with a mol ratio of 1:0.05:0.05 into water, uniformly stirring, heating and carrying out heat preservation on reaction liquid until the reaction of the reaction liquid is finished, removing water, and performing thin-layer chromatography separation on residues to obtain amide compounds. According to the method provided by the invention, such original defects as long reaction time, liability to generation of side reactions, harsh reaction conditions and environmental pollution are overcome. The method provided by the invention is moderate in conditions, high in selectivity and short in reaction time, no traditional strong acid or strong alkali is used as a catalyst, the nitrile grouping is completely converted to the acylamino, no further hydrolysis to produce carboxyl by-products is generated and the catalyst is cheap and easy to obtain.

Description

Itrile group is hydrolyzed to the novel method of amide group
Technical field
The invention belongs to chemosynthesis technical field, particularly relate to the novel method that itrile group is hydrolyzed to amide group.
Background technology
Amides is the important organic compound of a class, fields such as it is synthetic in organic synthesis, medicine as intermediate or final product, agricultural chemicals, papermaking and functional materials have uses extremely widely, especially is seized of very important low level in the production of fine chemical product.Amides synthetic is an important reaction in the organic chemistry.
Before the present invention, common synthetic method is at first to be converted into carboxylic acid derivative such as acyl chlorides, ester or acid anhydrides by carboxylic acid, generates corresponding amides by these carboxylic acid derivative generation ammonolysis reactions again.Report is also arranged by microwave method or enzymatic method synthesizing amide.But these methods all exist long reaction time, and side reaction easily takes place, and severe reaction conditions is to the unfriendly deficiency that waits of environment.
Summary of the invention
Purpose of the present invention just is to overcome the above-mentioned defective of existing production technology, develops a kind of synthetic method of the molecule of amides easily.
Technical solution of the present invention is:
Itrile group is hydrolyzed to the novel method of amide group, its major technique is characterised in that: the nitrile compounds, the N that with mol ratio are 1: 0.05: 0.05 earlier, N '-two n-pentyl benzo imidazoles bromine salt, 1, B-diazabicylo [5.4.0] 11 carbon-7-alkene is added to the water, post-heating and insulation reaction liquid to the reaction that stirs finishes, with water steam remove after, residue separated obtaining amides through thin-layer chromatography.
Reaction expression of the present invention is:
Figure BSA00000920919500011
The present invention is with N, N '-two n-pentyl benzo imidazoles bromine salt and 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) acting in conjunction in water, itrile group is hydrolyzed to amides, this method is simple to operate, has high selectivity, nitrile compounds, N during production, the molar ratio of N '-two n-pentyl benzo imidazoles bromine salt and 1,8-diazabicylo [5.4.0], 11 carbon-7-alkene (DBU) is 1: 0.05: 0.05.N wherein, N '-two n-pentyl benzo imidazoles bromine salt and 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) occurs as catalyzer, when two kinds of catalyzer charging capacitys are less than this proportioning, reaction is incomplete, and perhaps speed of response is low excessively, when charging capacity surpasses this proportioning, cause unnecessary waste, under this charging capacity, can reach best catalytic effect.
The feed ratio of nitrile compounds and water is 1mol: 5L.When the amount of water was less than this charging capacity, whole solution solute effect was bad, and reaction is incomplete, and energy consumption was too high when whose consumption then can cause aftertreatment when surpassing this charging capacity, and experiment shows that the product productive rate is the highest under this charging capacity.
The described insulation reaction time is 2～3 hours.During deficiency of time, react not thorough, experiment shows that the product productive rate is the highest in this time.
Described temperature of reaction is 70～85 ℃, and when being lower than this temperature, this speed of response is slower.Experiment shows that this temperature is optimal reaction temperature.
Described thin-layer chromatography is made eluent with hexanaphthene and ethyl acetate mixture, wherein, the mixed volume ratio of hexanaphthene and ethyl acetate is 10～12: 1, if this ratio is too high, then washing and dehydrating integrated machine polarity diminishes, and product retention time on chromatoplate is long, hangover is serious, if this ratio is low excessively, then washing and dehydrating integrated machine polarity becomes big, can not separate purified product fully.
Described nitrile compounds, N, N '-two n-pentyl benzo imidazoles bromine salt and deionized water splash into 1,8-diazabicylo [5.4.0], 11 carbon-7-alkene under stirring.
Advantage of the present invention and effect are:
1. mild condition of the present invention does not need traditional strong acid or highly basic as catalyzer.
2. selectivity of the present invention is very high, and itrile group is converted into amide group fully, and the by-product that further is not hydrolyzed to carboxyl occurs.
3. the reaction times of the present invention lacks, and catalyzer is cheap and easy to get.
Embodiment
One, reactions steps (it is that example is example that cyanobenzene is converted into benzamide):
The cyanobenzene that in the round-bottomed flask of 25mL, adds 2g respectively, 0.3g N, N '-two n-pentyl benzo imidazoles bromine salt and 100ml deionized water, stir the DBU (1 that splashes into 0.1g down, 8-diazabicylo [5.4.0] 11 carbon-7-alkene), be heated to 80 ℃, insulation backflow 2.5h, reaction boils off most of water thin-layer chromatography and tells benzamide amine 1.9g after finishing.
Make eluent with hexanaphthene and ethyl acetate mixture in the thin-layer chromatography that adopts, the mixed volume ratio of hexanaphthene and ethyl acetate is 10: 1.
Replace cyanobenzene then can obtain dissimilar amidess as replace nitrile compounds with difference.
Reaction expression of the present invention is:
Figure BSA00000920919500031
Two, product is identified:
It is as follows to adopt different concrete functional groups to carry out the experimental data of the acid amides that difference that explained hereafter of the present invention goes out replaces
Benzamide, white solid, fusing point: 122～124 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.82 (d, J=7.2Hz, 2H, PhH), 7.53 (t, J=7.8Hz, 1H, PhH), 7.44 (d, J=7.2Hz, 2H, PhH), 6.09 (brs, 1H, NH), 5.97 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 169.4,133.4,132.0,128.6,127.3; IR (KBr) v:3368 (vs), 3172 (vs), 1657 (vs), 1623 (s), 1575 (s), 1448 (m), 1403 (m), 1296 (w), 1179 (m), 1142 (m), 1121 (m), 1024 (m), 1000 (w), 918 (w), 811 (m), 792 (m), 770 (m), 703 (m) cm -1.
To toluamide, white solid, fusing point: 153～155 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.72 (d, J=7.8Hz, 2H, PhH), 7.24 (d, J=7.8Hz, 2H, PhH), 6.13 (brs, 2H, NH 2), 2.40 (s, 3H, CH 3); 13C NMR (600MHz, CDCl 3) δ (ppm): 169.8,142.9,130.4,129.5,127.6,21.7; IR (KBr) v:3343 (s), 3165 (s), 1671 (s), 1616 (s), 1568 (m), 1412 (m), 1188 (m), 1145 (m), 1119 (m), 840 (m), 793 (w), 730 (w) cm -1.
Anthranilamide, white solid, fusing point: 102～104 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.36 (d, J=7.8Hz, 1H, PhH), 7.23 (t, J=7.8Hz, 1H, PhH), 6.68 (d, J=7.8Hz, 1H, PhH), 6.64 (t, J=7.8Hz, 1H, PhH), 5.83 (brs, 2H, NH 2), 5.67 (s, 2H, NH 2); 13C NMR (600MHz, CDCl 3) δ (ppm): 171.6,149.5,133.0,128.0,117.5,116.4,114.0; IR (KBr) v:3411 (vs), 3321 (vs), 3202 (s), 1660 (vs), 1628 (s), 1586 (s), 1544 (m), 1491 (w), 1452 (w), 1401 (m), 1315 (m), 1257 (m), 1150 (w), 855 (w), 746 (m), 627 (m) cm -1.
Para Amino Benzamide, white solid, fusing point: 177～179 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.41 (d, J=8.4Hz, 2H, PhH), 6.84 (d, J=8.4Hz, 2H, PhH), 5.74 (brs, 2H, NH 2), 4.15 (s, 2H, NH 2); 13C NMR (600MHz, CDCl 3) δ (ppm): 170.4,146.8,131.6,127.8,114.3,113.1; IR (KBr) v:3470 (vs), 3328 (vs), 3210 (s), 1616 (s), 1600 (s), 1568 (m), 1514 (m), 1397 (w), 1289 (m), 1174 (m), 1095 (m), 838 (m), 778 (m), 693 (w), 545 (m) cm -1.
Adjacent fluorobenzamide, white solid, fusing point: 149～151 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 8.10 (t, J=7.8Hz, 1H, PhH), 7.46～7.49 (m, 1H, PhH), 7.24～7.25 (m, 1H, PhH), 7.10～7.13 (m, 1H, PhH), 6.67 (brs, 1H, NH), 6.21 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 164.9,161.8,160.1,133.9,132.3,124.8,120.2,116.1; IR (KBr) v:3392 (vs), 3197 (vs), 1646 (vs), 1460 (s), 1403 (m), 1215 (m), 1144 (m), 1118 (m), 957 (w), 836 (m), 767 (s), 628 (m), 537 (w) cm -1.
Between fluorobenzamide, white solid, fusing point: 150～152 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.53～7.57 (m, 2H, PhH), 7.40～7.44 (m, 1H, PhH), 7.21～7.26 (m, 1H, PhH), 6.13 (brs, 2H, NH 2); 13C NMR (600MHz, CDCl 3) δ (ppm): 168.2,163.6,161.9,135.6,130.3,122.8,119.0,114.7; IR (KBr) v:3368 (vs), 3178 (vs), 1661 (s), 1584 (s), 1451 (m), 1397 (m), 1271 (w), 1229 (m), 915 (m), 880 (w), 791 (m), 741 (m), 672 (w) cm -1.
To fluorobenzamide, white solid, fusing point: 154～156 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.84 (d, J=8.4Hz, 2H, PhH), 7.13 (d, J=8.4Hz, 2H, PhH), 5.95 (brs, 2H, NH 2); 13C NMR (600MHz, CDCl 3) δ (ppm): 167.3,137.8,132.4,127.6,127.9; IR (KBr) v:3330 (vs), 3154 (vs), 1674 (s), 1625 (s), 1511 (m), 1418 (s), 1294 (w), 1228 (m), 1155 (m), 1122 (m), 1012 (w), 849 (s), 801 (w), 674 (m), 625 (w), 587 (m) cm -1.
2,6-difluorobenzamide, white solid, fusing point: 143～144 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.36～7.41 (m, 1H, PhH), 6.94～6.97 (m, 2H, PhH), 6.37 (brs, 1H, NH), 6.09 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 162.3,161.1,159.4,132.1,112.1; IR (KBr) v:3402 (vs), 3198 (vs), 1654 (vs), 1606 (s), 1467 (m), 1405 (m), 1237 (m), 1102 (m), 1005 (m), 799 (m), 753 (m), 695 (m), 636 (w), 584 (m) cm -1.
To chlorobenzamide, white solid, fusing point: 175～176 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.76 (d, J=8.4Hz, 2H, PhH), 7.43 (d, J=8.4Hz, 2H, PhH), 6.09 (brs, 1H, NH), 5.95 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 168.2,138.4,131.6,128.9,128.8; IR (KBr) v:3368 (vs), 3176 (vs), 1668 (vs), 1620 (s), 1565 (m), 1490 (m), 1407 (m), 1147 (m), 1123 (m), 1087 (s), 1009 (m), 845 (m), 788 (m), 750 (m), 646 (m), 617 (w) cm -1.
To brombenzamide, white solid, fusing point: 187～188 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 7.69 (d, J=8.4Hz, 2H, PhH), 7.59 (d, J=8.4Hz, 2H, PhH), 6.06 (brs, 1H, NH), 5.70 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 167.8,136.9,130.1,126.5,126.3; IR (KBr) v:3361 (vs), 3178 (vs), 1660 (vs), 1622 (s), 1563 (w), 1485 (w), 1408 (s), 1067 (m), 1009 (m), 843 (m), 783 (w), 650 (w), 530 (m) cm -1.
The p-nitrophenyl methane amide, white solid, fusing point: 201～203 ℃. 1H NMR (600MHz, CDCl 3) δ (ppm): 8.32 (d, J=8.4Hz, 2H, PhH), 7.99 (t, J=8.4Hz, 2H, PhH), 6.14 (brs, 1H, NH), 5.79 (brs, 1H, NH); 13C NMR (600MHz, CDCl 3) δ (ppm): 169.1,149.6,140.8,128.6,123.9; IR (KBr) v:3418 (vs), 3313 (vs), 1664 (vs), 1614 (s), 1513 (m), 1407 (s), 1340 (m), 1118 (m), 1103 (m), 1014 (w), 866 (s), 788 (m), 762 (w) cm -1

Claims (6)

1. itrile group is hydrolyzed to the novel method of amide group, it is characterized in that: the nitrile compounds, the N that with mol ratio are 1: 0.05: 0.05 earlier, N '-two n-pentyl benzo imidazoles bromine salt, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene is added to the water, post-heating and insulation reaction liquid to the reaction that stirs finishes, with water steam remove after, residue separated obtaining amides through thin-layer chromatography.
2. itrile group according to claim 1 is hydrolyzed to the novel method of amide group, and the feed ratio that it is characterized in that described nitrile compounds and water is 1mol: 5L.
3. itrile group according to claim 1 is hydrolyzed to the novel method of amide group, it is characterized in that the described insulation reaction time is 2～3 hours.
4. itrile group according to claim 1 is hydrolyzed to the novel method of amide group, it is characterized in that reacting by heating liquid to 70～85 ℃.
5. itrile group according to claim 1 is hydrolyzed to the novel method of amide group, it is characterized in that described thin-layer chromatography makees eluent with hexanaphthene and ethyl acetate mixture, and wherein, the mixed volume of hexanaphthene and ethyl acetate ratio is 10～12: 1.
6. itrile group according to claim 1 is hydrolyzed to the novel method of amide group, it is characterized in that nitrile compounds, N, and N '-two n-pentyl benzo imidazoles bromine salt and deionized water splash into 1,8-diazabicylo [5.4.0], 11 carbon-7-alkene under stirring.
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CN104744288A (en) * 2013-12-31 2015-07-01 南京理工大学 Method for synthesizing amide through nitrile hydrolysis
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