CN104230739A - Process for producing N,N',N''-tricyclohexyl-1,3,5-benzamide by using trimesic acid - Google Patents
Process for producing N,N',N''-tricyclohexyl-1,3,5-benzamide by using trimesic acid Download PDFInfo
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- CN104230739A CN104230739A CN201410417195.XA CN201410417195A CN104230739A CN 104230739 A CN104230739 A CN 104230739A CN 201410417195 A CN201410417195 A CN 201410417195A CN 104230739 A CN104230739 A CN 104230739A
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- benzamide
- ethyl acetate
- trimesic acid
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Abstract
The invention discloses a process for producing N,N',N''-tricyclohexyl-1,3,5-benzamide by using a trimesic acid. The process comprises the following steps: firstly, in the presence of an initiator, synthesizing the trimesic acid and triphosgene into trimesoyl chloride in an ethyl acetate medium; then, dropwise adding the obtained product not required to be treated and a solvent into a cyclohexylamine and ethyl acetate medium-containing reaction kettle, wherein in the process of dropwise adding, the temperature is strictly controlled, so that the system temperature is lower than 40 DEG C; after the process of dropwise adding is completed, raising the temperature to 78 DEG C, reacting for 6-10 hours, stopping heating, cooling to below 60 DEG C, carrying out suction filtration on the obtained product, and pulverizing the obtained filter cake, so that a crude product is obtained; washing the crude product by using boiling water, carrying out suction filtration, and washing the obtained filter cake by using a NaOH solution; and washing the obtained filter cake by using clean water, carrying out suction filtration, and drying the obtained product, so that white powder N,N',N''-tricyclohexyl-1,3,5-benzamide is obtained. Raw materials used in the production process disclosed by the invention are easily obtained, the process is simple in operation, and obtained products are high in purity, good in color, and easily industrialized.
Description
Technical field
The present invention relates to and produce N, N ˊ, N ˊ ˊ-three substituting group-1,3,5-benzamide preparation method technical field, particularly one trimesic acid produces N, the technique of N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide.
Background technology
N, N ˊ, N ˊ ˊ-three substituting group-1,3,5-benzamide meets
Logical formula I:
Comprise (II):
Wherein R is alkyl or aromatic substituents.Mainly be used as the nucleator of the polymkeric substance such as poly(lactic acid).
Current trimesic acid produces N, and the technological reaction condition of N ˊ, N ˊ ˊ-three substituting group-1,3,5-benzamide is harsh, and yield is not high.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides one trimesic acid and producing N, the technique of N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide.
The technical solution adopted in the present invention is: one produces N by trimesic acid, and the technique of N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, comprises the following steps:
A: the trimesic acid being first 1:3 by amount of substance ratio and triphosgene are blended in ethyl acetate medium, water bath heat preservation 25 DEG C, pre-configured N is dripped wherein in 60 ~ 120 minutes, the ethyl acetate solution of dinethylformamide, DMF is 1.28 with trimesic acid amount of substance ratio;
B: after dropwising, removes water-bath, is warming up to 60 DEG C ~ 65 DEG C, is incubated 6 ~ 10 hours, synthesis pyromellitic trimethylsilyl chloride;
C: after reaction terminates, drop in another reactor by hexahydroaniline and ethyl acetate successively, hexahydroaniline is 15.76 with trimesic acid amount of substance ratio, ice bath, stir, ice bath controls below 40 DEG C, drips pyromellitic trimethylsilyl chloride solution obtained in step B lentamente wherein;
D: after dropwising, is warming up to 78 DEG C, insulation reaction 6 ~ 10 hours;
E: be cooled to less than 60 DEG C, suction filtration, pulverize gained filter cake and obtain thick product, boiling water washs thick product, suction filtration, again with NaOH solution washing gained filter cake, suction filtration, then use clear water washing leaching cake, suction filtration, dry, both white powder N, N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide was obtained.
As preferably, the solvent in described steps A is ethyl acetate, and wherein ethyl acetate is 7.52 with trimesic acid amount of substance ratio.
As preferably, the ethyl acetate solution of the DMF of the dropping in described steps A, ethyl acetate is 7.52 with trimesic acid amount of substance ratio.。
As preferably, the time for adding in described steps A is 60 minutes.
As preferably, the temperature of reaction in described step B is 8 hours.
As preferably, be slowly added dropwise in the mixed solution of hexahydroaniline and ethyl acetate in described step C by pyromellitic trimethylsilyl chloride solution obtained in steps A, in described mixing solutions, ethyl acetate is 22.55 with trimesic acid amount of substance ratio.
As preferably, in described step D, the reaction times is 7.5 hours.
As preferably, in described step e, wash the pH=14 of thick product NaOH solution used for the second time.
Compared with prior art, the invention has the beneficial effects as follows: producing and manufacturing technique raw material is easy to get, technological operation simple, products obtained therefrom purity is high, color good, be easy to industrialization.
Embodiment
In order to more clearly understand technical scheme of the present invention, below the present invention is further described.
Embodiment 1
In the 500 ml reaction flasks with stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant pressure addition device, add 15.8g trimesic acid, 66.8g triphosgene and 55ml ethyl acetate, open and stir, water bath heat preservation 25 DEG C, in 60 minutes, drip the mixed solution of 7.0g DMF and 55ml ethyl acetate, remove water-bath, in 10 minutes to 20 minutes, be slowly warming up to 60 DEG C ~ 65 DEG C after stirring, react 8 hours.
Aforesaid liquid is poured in constant pressure addition device.In the 500ml reaction flask with stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant pressure addition device, add 117.0g hexahydroaniline and 165ml ethyl acetate, open and stir, ice bath is incubated less than 40 DEG C, drips above-mentioned midbody solution, after dropwising, remove ice bath, be warming up to reflux temperature (about 78 DEG C) reaction 7.5 hours, stop heating, be cooled to less than 60 DEG C, thick product is poured in funnel, suction filtration, gained filtrate collection is for subsequent use, and gained filter cake pulverizes.Solid is leached with the washing of 1000ml boiling water, suction filtration, soak gained filter cake, suction filtration by the NaOH solution of 1000ml pH=14 again, then use 1000ml clear water washing leaching cake at twice, suction filtration, drying, obtains target product white powder 32.3g, and yield is that 94.8%(carries out gauge calculation by trimesic acid), fusing point is 360.0 ~ 368.7 DEG C, and efficient liquid phase chromatographic analysis purity is 95.55%.
Embodiment 2
In the 5L reaction flask with stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant pressure addition device, add 505.6g trimesic acid, 1635.2g triphosgene and 1760ml ethyl acetate, open and stir, water bath heat preservation 25 DEG C, in 60 minutes, drip the mixed solution of 240.0g DMF and 1440ml ethyl acetate, remove water-bath, in 10 minutes to 20 minutes, be slowly warming up to 60 DEG C ~ 65 DEG C after stirring, react 8 hours.
Aforesaid liquid is poured in constant pressure addition device.In the 30L reactor with stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant pressure addition device, add 2860.0g hexahydroaniline and 7300ml ethyl acetate, open and stir, ice bath is incubated less than 40 DEG C, drips above-mentioned midbody solution, after dropwising, remove ice bath, be warming up to reflux temperature (about 78 DEG C) reaction 7.5 hours, stop heating, be cooled to less than 60 DEG C, thick product is poured in funnel, suction filtration, gained filtrate collection is for subsequent use, and gained filter cake pulverizes.Solid is leached with the washing of 16L boiling water, suction filtration, soak gained filter cake, suction filtration by the NaOH solution of 16L pH=14 again, then use 32L clear water washing leaching cake at twice, suction filtration, drying, get final product target product white powder 1038.3g, yield is that 95.2%(carries out gauge calculation by trimesic acid), fusing point is 366.0 ~ 374.4 DEG C, and efficient liquid phase chromatographic analysis purity is 96.42%.
The said products all determines structure through infrared spectra, nuclear-magnetism and efficient liquid phase chromatographic analysis, tries out in poly(lactic acid) nucleation, obtains good effect.
The above is only better embodiment of the present invention, therefore all equivalences done according to structure, feature and the principle described in patent claim of the present invention change or modify, and are included in patent claim of the present invention.
Claims (8)
1. produce a N with trimesic acid, the technique of N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that:
Comprise the following steps:
A: the trimesic acid being first 1:3 by amount of substance ratio and triphosgene are blended in ethyl acetate medium, water bath heat preservation 25 DEG C, pre-configured N is dripped wherein in 60 ~ 120 minutes, the ethyl acetate solution of dinethylformamide, DMF is 1.28 with trimesic acid amount of substance ratio;
B: after dropwising, removes water-bath, is warming up to 60 DEG C ~ 65 DEG C, is incubated 6 ~ 10 hours, synthesis pyromellitic trimethylsilyl chloride;
C: after reaction terminates, drop in another reactor by hexahydroaniline and ethyl acetate successively, hexahydroaniline is 15.76 with trimesic acid amount of substance ratio, ice bath, stir, ice bath controls below 40 DEG C, drips pyromellitic trimethylsilyl chloride solution obtained in step B lentamente wherein;
D: after dropwising, is warming up to 78 DEG C, insulation reaction 6 ~ 10 hours;
E: be cooled to less than 60 DEG C, suction filtration, pulverize gained filter cake and obtain thick product, boiling water washs thick product, suction filtration, again with NaOH solution washing gained filter cake, suction filtration, then use clear water washing leaching cake, suction filtration, dry, both white powder N, N ˊ, N ˊ ˊ-thricyclohexyl-1,3,5-benzamide was obtained.
2. production N, N ˊ according to claim 1, the technique of N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that: the solvent in described steps A is ethyl acetate, and wherein ethyl acetate is 7.52 with trimesic acid amount of substance ratio.
3. production N, N ˊ according to claim 1, N ˊ ˊ-thricyclohexyl-1, the technique of 3,5-benzamide, is characterized in that: the N dripped in described steps A, the ethyl acetate solution of dinethylformamide, ethyl acetate is 7.52 with trimesic acid amount of substance ratio.
4. production N, N ˊ according to claim 1, the technique of N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that: the time for adding in described steps A is 60 minutes.
5. production N, N ˊ according to claim 1, the technique of N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that: the reaction times in described step B is 8 hours.
6. production N according to claim 1, N ˊ, N ˊ ˊ-thricyclohexyl-1,3, the technique of 5-benzamide, it is characterized in that: be slowly added dropwise in the mixed solution of hexahydroaniline and ethyl acetate by pyromellitic trimethylsilyl chloride solution obtained in step B in described step C, in described mixing solutions, ethyl acetate is 22.55 with trimesic acid amount of substance ratio.
7. production N, N ˊ according to claim 1, the technique of N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that: in described step D, the reaction times is 7.5 hours.
8. production N, N ˊ according to claim 1, the technique of N ˊ ˊ-thricyclohexyl-1,3,5-benzamide, is characterized in that: the second time in described step e washs the pH=14 of thick product NaOH solution used.
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| CN201410417195.XA CN104230739B (en) | 2014-08-23 | 2014-08-23 | N, the technique of N, N-thricyclohexyl-1,3,5-benzamide is produced with trimesic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501605A (en) * | 2017-10-25 | 2017-12-22 | 山西省化工研究所（有限公司） | A kind of new application of benzene trimethamide class compound |
| CN113429768A (en) * | 2021-07-16 | 2021-09-24 | 湖南工业大学 | Polylactic acid composition containing amide nucleating agent and preparation method thereof |
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| CN101155776A (en) * | 2005-04-07 | 2008-04-02 | 新日本理化株式会社 | Process for producing tricarboxylic acid tris(alkyl-substituted cyclohexylamide) |
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| JP2008274126A (en) * | 2007-04-27 | 2008-11-13 | New Japan Chem Co Ltd | Nucleating agent composition for polyolefin, polyolefin resin composition containing the nucleating agent composition and its molded product |
| JP2009155489A (en) * | 2007-12-27 | 2009-07-16 | Toray Ind Inc | Molding and manufacturing method therefor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501605A (en) * | 2017-10-25 | 2017-12-22 | 山西省化工研究所（有限公司） | A kind of new application of benzene trimethamide class compound |
| CN113429768A (en) * | 2021-07-16 | 2021-09-24 | 湖南工业大学 | Polylactic acid composition containing amide nucleating agent and preparation method thereof |
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| CN104230739B (en) | 2016-07-20 |
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