CN103342654B - Novel method for hydrolyzing nitrile group to acylamino - Google Patents
Novel method for hydrolyzing nitrile group to acylamino Download PDFInfo
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- CN103342654B CN103342654B CN201310278653.1A CN201310278653A CN103342654B CN 103342654 B CN103342654 B CN 103342654B CN 201310278653 A CN201310278653 A CN 201310278653A CN 103342654 B CN103342654 B CN 103342654B
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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
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, it to have in fields such as organic synthesis, pharmaceutical synthesis, agricultural chemicals, papermaking and functional materialss as intermediate or final product applies extremely widely, especially in the production of fine chemical product, is seized of very important low level.The synthesis of amides is an important reaction in organic chemistry.
Before making the present invention, common synthetic method is first converted into the carboxylic acid derivative such as acyl chlorides, ester or acid anhydrides by carboxylic acid, then generate corresponding amides by these carboxylic acid derivative generation ammonolysis reactions.Also report is had by microwave method or enzymatic method synthesizing amide.But these methods all also exist long reaction time, easily side reaction occur, severe reaction conditions, wait deficiency to environment is unfriendly.
Summary of the invention
Object of the present invention is just the above-mentioned defect overcoming 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 technical characteristics is: be first nitrile compounds, the N of 1: 0.05: 0.05 by mol ratio, N '-two n-pentyl benzoglyoxaline bromine salt, 1, B-diazabicylo [5.4.0] 11 carbon-7-alkene is added to the water, stir post-heating insulation reaction liquid to reacting end, water is steamed after removing, residue is separated through thin-layer chromatography and obtains amides.
Reaction expression of the present invention is:
The present invention is with N, N '-two n-pentyl benzoglyoxaline 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, the method is simple to operate, has high selectivity, nitrile compounds, N during production, the molar ratio of N '-two n-pentyl benzoglyoxaline bromine salt and 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) is 1: 0.05: 0.05.Wherein N, N '-two n-pentyl benzoglyoxaline 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, or speed of response is too low, when charging capacity exceedes this proportioning, cause unnecessary waste, best catalytic effect can be reached under this charging capacity.
The feed ratio of nitrile compounds and water is 1mol: 5L.When the amount of water is less than this charging capacity, whole solubilize effect is bad, and not exclusively, when then can cause aftertreatment when whose consumption exceedes this charging capacity, energy consumption is too high, and experiment shows that products collection efficiency is the highest under this charging capacity in reaction.
The described insulation reaction time is 2 ~ 3 hours.During deficiency of time, reaction is not thorough, and experiment shows that products collection efficiency is the highest within this time.
Described temperature of reaction is 70 ~ 85 DEG C, and during lower than this temperature, this speed of response is slower.Experiment shows that this temperature is optimal reaction temperature.
Described thin-layer chromatography makees 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 too low, then washing and dehydrating integrated machine polarity becomes large, can not separating-purifying product completely.
Described nitrile compounds, N, N '-two n-pentyl benzoglyoxaline bromine salt and deionized water, stir lower instillation 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene.
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 completely, and the by-product not being hydrolyzed to carboxyl further occurs.
3. the reaction times of the present invention is short, and catalyzer is cheap and easy to get.
Embodiment
One, reactions steps (cyanobenzene is converted into benzamide be example be example):
The cyanobenzene of 2g is added respectively in the round-bottomed flask of 25mL, the N of 0.3g, N '-two n-pentyl benzoglyoxaline bromine salt and 100ml deionized water, stir the DBU (1 of lower instillation 0.1g, 8-diazabicylo [5.4.0] 11 carbon-7-alkene), be heated to 80 DEG C, insulation backflow 2.5h, after reaction terminates, boil off most of water thin-layer chromatography and separate benzamide amine 1.9g.
Make eluent with hexanaphthene and ethyl acetate mixture in the thin-layer chromatography adopted, the mixed volume ratio of hexanaphthene and ethyl acetate is 10: 1.
Replace cyanobenzene then can obtain dissimilar amides as replaced nitrile compounds with difference.
Reaction expression of the present invention is:
Two, Product Identification:
The experimental data of the acid amides that adopt different concrete functional groups to carry out difference that present invention process produces replaces is as follows
Benzamide, white solid, fusing point: 122 ~ 124 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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 DEG C.
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.
P-nitrophenyl methane amide, white solid, fusing point: 201 ~ 203 DEG C.
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 method for amide group, it is characterized in that: be first cyanobenzene, the N of 1: 0.05: 0.05 by mol ratio, N '-two n-pentyl benzoglyoxaline bromine salt, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene is added to the water, stir post-heating insulation reaction liquid to reacting end, water is steamed after removing, residue is separated through thin-layer chromatography and obtains amides.
2. itrile group according to claim 1 is hydrolyzed to the method for amide group, it is characterized in that the feed ratio of described cyanobenzene and water is 1mol: 5L.
3. itrile group according to claim 1 is hydrolyzed to the method for 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 method for amide group, it is characterized in that reacting by heating liquid to 70 ~ 85 DEG C
5. itrile group according to claim 1 is hydrolyzed to the method for amide group, it is characterized in that described thin-layer chromatography makees eluent with hexanaphthene and ethyl acetate mixture, and wherein, the mixed volume ratio of hexanaphthene and ethyl acetate is 10 ~ 12: 1.
6. itrile group according to claim 1 is hydrolyzed to the method for amide group, it is characterized in that cyanobenzene, N, N '-two n-pentyl benzoglyoxaline bromine salt and deionized water, stirs lower instillation 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene.
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TW200529812A (en) * | 2003-12-26 | 2005-09-16 | Chugai Pharmaceutical Co Ltd | Benzamide derivatives |
CA2658675A1 (en) * | 2006-07-24 | 2008-01-31 | Jubilant Organosys Limited | Process for producing 10-oxo-10, 11-dihydr0-5h-dibenz [b, f] azepine-5-carboxamide starting from 5-cyanoiminostilbene |
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TW201102365A (en) * | 2009-07-03 | 2011-01-16 | China Petrochemical Dev Corp | Method for producing organic carboxylic acid amide |
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