CN103342655A - New method for synthesizing substituted amide by using substituted ethanedione dianiline Schiff base - Google Patents
New method for synthesizing substituted amide by using substituted ethanedione dianiline Schiff base Download PDFInfo
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- CN103342655A CN103342655A CN2013102790715A CN201310279071A CN103342655A CN 103342655 A CN103342655 A CN 103342655A CN 2013102790715 A CN2013102790715 A CN 2013102790715A CN 201310279071 A CN201310279071 A CN 201310279071A CN 103342655 A CN103342655 A CN 103342655A
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- dianiline
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- schiff bases
- substituted amide
- substituted
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- AJUFKJQPSODDSP-QAVVBOBSSA-N CC1C=CC(/C(/C(/c2ccccc2)=N/c2ccccc2)=N\c2ccccc2)=CC=C1 Chemical compound CC1C=CC(/C(/C(/c2ccccc2)=N/c2ccccc2)=N\c2ccccc2)=CC=C1 AJUFKJQPSODDSP-QAVVBOBSSA-N 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N O=C(c1ccccc1)Nc1ccccc1 Chemical compound O=C(c1ccccc1)Nc1ccccc1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a new method for synthesizing substituted amide by using substituted ethanedione dianiline Schiff base. The new method comprises the following steps: adding 1,2-benzil dianiline Schiff base, a boron trifluoride diethyl ether solution and sodium borohydride according to the molar ratio of 1:1:0.05 into a reaction container in which toluene is placed; stirring uniformly, heating and preserving heat of the reaction liquid until the reaction is finished; removing the toluene by distillation; and performing thin-layer chromatographic separation on the residues to obtain the substituted amid compounds. The new method overcomes the defects of long reaction time, easy generation of side reaction, harsh reaction condition, environmental pollution and the like in the past method. The 1,2-diphenyl dianiline Schiff base is reduced into the substituted amid by a one-step method. The new method is simple to operate and has molecular economy, and the yield of products is highest.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly replace the novel method of the synthetic substituted amide of second diketone dianiline schiff bases.
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 defective such as environment is unfriendly.
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 novel method that replaces the synthetic substituted amide of second diketone dianiline schiff bases.
Technical solution of the present invention is:
The novel method that replaces the synthetic substituted amide of second diketone dianiline schiff bases, its major technique is characterised in that: be 1: 1: 0.05 have substituent 1 with mol ratio earlier, 2-diphenylthanedione dianiline schiff bases, boron trifluoride ether solution and sodium borohydride join and are equipped with in the reaction of toluene container, post-heating and insulation reaction liquid to the reaction that stirs finishes, with toluene steam remove after, residue separated obtaining replacing the substituted amide compounds through thin-layer chromatography.
Reaction expression of the present invention is:
During production, replace 1,2-diphenylthanedione dianiline schiff bases, sodium borohydride, boron trifluoride molar ratio are 1: 1: 0.05, sodium borohydride is as reductive agent, and when charging capacity was less than this proportioning, reaction not exclusively, when charging capacity surpasses this proportioning, cause unnecessary waste, boron trifluoride can reach best catalytic effect as catalyzer under this charging capacity.
The toluene quality that feeds intake is to replace 10～15 times of 1,2-diphenylthanedione dianiline schiff bases quality.When toluene is less than this charging capacity, can cause catalyzer can not bring into play good effect owing to reactant concn is too high.When the toluene amount surpassed this charging capacity, energy consumption was too high in the time of then can too much causing aftertreatment owing to solvent load, and experiment shows that the product productive rate is the highest under this charging capacity.
The described insulation reaction time is 6～7 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 105～110 ℃, 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 8～10: 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.
Advantage of the present invention and effect are with single stage method 1,2-phenylbenzene dianiline schiff bases to be reduced to substituted amide, and this method is simple to operate, has the molecule economy, and the product productive rate is the highest.
Embodiment
One, reactions steps (the N-phenylbenzamaide is example):
In being housed, the 100ml round-bottomed flask of reflux condensing tube adds 1mmol, 2-diphenylthanedione dianiline schiff bases, 1mmol NaBH
4, 10ml toluene, 0.05mmol BF
3. (OCH
2CH
3)
2, the post-heating that stirs is reacted to 105～110 ℃ of insulation 6h, revolves except toluene after reaction is finished, and thin-layer chromatography is told 1,2-phenylbenzene-2 hydroxy ethylamine 0.15g.
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 8: 1.
As replace with difference 1,2-diphenylthanedione dianiline schiff bases replace 1,2-diphenylthanedione dianiline schiff bases also adopt more than roughly the same technology, then can obtain the different amidess that replace.
Reaction expression of the present invention is:
Two, product is identified:
It is as follows to adopt different concrete functional groups to carry out the experimental data of the amide derivatives that difference that explained hereafter of the present invention goes out replaces
The N-phenylbenzamaide, white solid, fusing point: 165-168 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm): 8.15 (brs, 1H), 7.83 (m, 2H), 7.65 (m, 2H), 7.52 (m, 2H), 7.36 (m, 2H), 7.16 (m, 1H);
13CNMR (150MHz, CDCl
3) δ (ppm): 165.8,137.5,134.7,132.0,129.1,127.0,124.3,120.2; IR (KBr) v:3357,3067,1674,1587,1536,1457,1425,1326,1287,1183,1102,927,877,786,721cm
-1.
The N-phenyl is to chlorobenzamide, yellow solid, fusing point: 195-197 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm): 8.57 (bs, 1H), 7.42 (m, 7H), 6.81 (d, J=9Hz, 2H);
13CNMR (150MHz, CDCl
3) δ (ppm): 165.5,153.4,137.0,131.3,129.9,127.8,127.3,122.4; IR (KBr) v:3343,3015,1679,1603,1523,1501,1431,1402,1327,1264,1153,1109,907,823,763,703cm
-1.
The adjacent chlorobenzamide of N-phenyl, yellow solid, fusing point: 195-197 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm): 10.49 (s, 1H), 7.70 (m, 2H), 7.57 (m, 3H), 7.46 (m, 2H), 7.10 (m, 1H);
13CNMR (150MHz, CDCl
3) δ (ppm): 164.7,138.6,137.0,131.1,129.8,129.6,128.7,128.6,127.2,123.7,119.4; IR (KBr) v:3267,2926,1657,1597,1549,1443,1329,1265,895,752cm
-1.
The N-phenyl is to brombenzamide, yellow solid, fusing point: 202-205 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm): 10.05 (s, 1H), 7.91 (d, J=16.8,2H), 7.73 (d, J=12.8Hz, 3H), 7.42 (m, 2H), 7.15 (m, 1H);
13CNMR (150MHz, CDCl
3) δ (ppm): 164.2,138.6,136.7,131.1,129.4,128.4,125.0,123.6,120.2; IR (KBr) v:3335,2927,1654,1598,1534,1467,1440,846,757cm
-1.
The N-phenyl is to methyl benzamide, white solid, fusing point: 149-150 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm): 7.80 (d, J=9Hz, 2H), 7.66 (d, J=7.2Hz, 2H), 7.40 (m, 2H), 7.31 (m, 3H), 2.38 (s, 3H);
13CNMR (150MHz, CDCl
3) δ (ppm): 165.5,142.0,137.9,132.4,129.7,129.6,127.3,127.0,123.8,120.5,21.7; IR (KBr) v:3348,3025,1651,1601,1545,1499,1405,1317,1271,1056,818,736cm
-1.
The N-phenyl is to methoxy benzamide, white solid, fusing point: 173-174 ℃;
1HNMR (600MHz, CDCl
3) δ (ppm) 7.91 (d, J=9Hz, 2H), 7.81 (s, 1H), 7.69 (d, J=9.6Hz, 2H), 7.43 (m, 2H), 7.21 (m, 1H), 7.03 (d, J=8.4Hz, 2H), 3.87 (s, 3H);
13CNMR (150MHz, CDCl
3) δ (ppm): 163.2,162.1,139.2,129.8,128.9,127.3,123.8,114.0,55.8; IR (KBr) v:3337,2913,1655,1605,1534,1509,1421,1315,1203,1121,1056,813,771,725cm
-1
Claims (5)
1. the novel method that replaces the synthetic substituted amide of second diketone dianiline schiff bases, it is characterized in that: be 1: 1: 0.05 have substituent 1 with mol ratio earlier, 2-diphenylthanedione dianiline schiff bases, boron trifluoride ether solution and sodium borohydride join and are equipped with in the reaction of toluene container, post-heating and insulation reaction liquid to the reaction that stirs finishes, with toluene steam remove after, residue separated obtaining replacing the substituted amide compounds through thin-layer chromatography.
2. the novel method of the synthetic substituted amide of replacement second diketone dianiline schiff bases according to claim 1, the quality that it is characterized in that the described toluene that drops into is substituent 1 for having, 10～15 times of 2-diphenylthanedione dianiline schiff bases quality.
3. the novel method of the synthetic substituted amide of replacement second diketone dianiline schiff bases according to claim 1 is characterized in that the described insulation reaction time is 6～7 hours.
4. the novel method of the synthetic substituted amide of replacement second diketone dianiline schiff bases according to claim 1 is characterized in that reacting by heating liquid to 105～110 ℃.
5. replacement second diketone dianiline schiff bases according to claim 1 is synthesized the novel method of substituted amide, it is characterized in that described thin-layer chromatography makees eluent with hexanaphthene and ethyl acetate mixture, wherein, the mixed volume of hexanaphthene and ethyl acetate ratio is 8～10: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0999207A2 (en) * | 1998-11-05 | 2000-05-10 | Nalco/Exxon Energy Chemicals L.P. | Method for removal of aldehydes from chemical manufacturing production streams during distillative purification |
| CN1989102A (en) * | 2004-10-02 | 2007-06-27 | 舒沃茨药物股份公司 | Improved synthesis scheme for lacosamide |
| WO2013060011A1 (en) * | 2011-10-27 | 2013-05-02 | Givaudan Sa | Novel process |
| CN103168027A (en) * | 2010-02-18 | 2013-06-19 | 阿斯利康(瑞典)有限公司 | Processes for making cyclopropyl amide derivatives and intermediates associated therewith |
-
2013
- 2013-07-02 CN CN2013102790715A patent/CN103342655A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0999207A2 (en) * | 1998-11-05 | 2000-05-10 | Nalco/Exxon Energy Chemicals L.P. | Method for removal of aldehydes from chemical manufacturing production streams during distillative purification |
| CN1989102A (en) * | 2004-10-02 | 2007-06-27 | 舒沃茨药物股份公司 | Improved synthesis scheme for lacosamide |
| CN103168027A (en) * | 2010-02-18 | 2013-06-19 | 阿斯利康(瑞典)有限公司 | Processes for making cyclopropyl amide derivatives and intermediates associated therewith |
| WO2013060011A1 (en) * | 2011-10-27 | 2013-05-02 | Givaudan Sa | Novel process |
Non-Patent Citations (4)
| Title |
|---|
| JACQUES SIMONET等: "DEGRADATION CATHODIQUE DES α DI-IHINES EN PRESENCE D’OXYGENE.ELECTROSYNTHESE D’AMIDES.", 《TETRAHEDRON LETTERS》 * |
| KLAUS GOLLNICK等: "Photooxygenation of 1,4-Diaza-l,3-butadiene(α-Diimines): Formation of Isonitriles", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 邓芹英等: "《波谱分析教程》", 31 December 2003, article "各类化合物的红外特征管普", pages: 54 - 2-10 * |
| 邓芹英等: "《精细有机合成与设计》", 31 December 2003 * |
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Application publication date: 20131009 |