CN104230739B - N, the technique of N, N-thricyclohexyl-1,3,5-benzamide is produced with trimesic acid - Google Patents
N, the technique of N, N-thricyclohexyl-1,3,5-benzamide is produced with trimesic acid Download PDFInfo
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- CN104230739B CN104230739B CN201410417195.XA CN201410417195A CN104230739B CN 104230739 B CN104230739 B CN 104230739B CN 201410417195 A CN201410417195 A CN 201410417195A CN 104230739 B CN104230739 B CN 104230739B
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- thricyclohexyl
- ethyl acetate
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Abstract
The invention discloses one trimesic acid and produce N, N, N thricyclohexyl 1, 3, the technique of 5 benzamides, first use trimesic acid and triphosgene in the presence of initiator, ethyl acetate medium synthesizes pyromellitic trimethylsilyl chloride, it is not required to afterwards process be added dropwise in the reactor containing cyclohexylamine and ethyl acetate medium together with product and solvent, strict temperature control during dropping is so that system temperature is less than 40 DEG C, 78 DEG C it are warming up to after dropping, react 6 10 hours, stop heating, it is cooled to less than 60 DEG C, sucking filtration, pulverize gained filter cake and obtain thick product, boiling water washs thick product, sucking filtration, gained filter cake is washed again by NaOH solution, sucking filtration, filter cake is washed again with clear water, sucking filtration, it is dried, both white powder N had been obtained, N, N thricyclohexyl 1, 3, 5 benzamides.Manufacturing technique method raw material of the present invention is easy to get, technological operation simple, products obtained therefrom purity is high, color is good, be prone to industrialization.
Description
Technical field
The present invention relates to produce N, N, N-three substituent group-1,3,5-benzamide preparation method technical fields, produce N, N, N-thricyclohexyl-1, the technique of 3,5-benzamides particularly to one trimesic acid.
Background technology
N, N, N-three substituent group-1,3,5-benzamide meet
Logical formula I:
Including (II):
Wherein R is alkyl or aromatic substituents.Mainly it is used as the nucleator of the polymer such as polylactic acid.
Current trimesic acid produces N, and N, N-three substituent group-1, the technological reaction condition of 3,5-benzamides is harsh, and yield is the highest.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides one trimesic acid and produce N, N, N-thricyclohexyl-1, the technique of 3,5-benzamides.
The technical solution adopted in the present invention is: one is produced N, N, N-thricyclohexyl-1, the technique of 3,5-benzamides by trimesic acid, comprises the following steps:
A: first the amount of material is blended in ethyl acetate medium than trimesic acid and the triphosgene for 1:3, 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 the amount ratio of trimesic acid material；
B: after dropping, removes water-bath, is warming up to 60 DEG C ~ 65 DEG C, is incubated 6 ~ 10 hours, synthesizes pyromellitic trimethylsilyl chloride；
C: after reaction terminates, putting in another reactor by cyclohexylamine and ethyl acetate successively, cyclohexylamine is 15.76 with the amount ratio of trimesic acid material, ice bath, stirring, ice bath controls below 40 DEG C, the pyromellitic trimethylsilyl chloride solution prepared in dropping step B the most lentamente；
D: after dropping, is warming up to 78 DEG C, insulation reaction 6 ~ 10 hours；
E: be cooled to less than 60 DEG C, sucking filtration, pulverize gained filter cake and obtain thick product, boiling water washs thick product, sucking filtration, wash gained filter cake, sucking filtration by NaOH solution again, then wash filter cake, sucking filtration with clear water, be dried, both white powder N, N, N-thricyclohexyl-1,3,5-benzamides had been obtained.
As preferably, the described solvent in step A is ethyl acetate, and wherein ethyl acetate is 7.52 with the amount ratio of trimesic acid material.
As preferably, the ethyl acetate solution of the DMF of the described dropping in step A, ethyl acetate is 7.52 with the amount ratio of trimesic acid material..
As preferably, the described time for adding in step A is 60 minutes.
As preferably, the described reaction temperature in step B is 8 hours.
As preferably, being slowly added dropwise in the mixed liquor of cyclohexylamine and ethyl acetate by pyromellitic trimethylsilyl chloride solution obtained in step A in described step C, in described mixed solution, ethyl acetate is 22.55 with the amount ratio of trimesic acid material.
As preferably, in described step D, the response time is 7.5 hours.
As preferably, in described step E, second time washs the pH=14 of NaOH solution used by thick product.
Compared with prior art, the invention has the beneficial effects as follows: manufacturing technique method raw material is easy to get, technological operation simple, products obtained therefrom purity is high, color is good, be prone to industrialization.
Detailed description of the invention
In order to be able to be more clearly understood that technical scheme, below the present invention is further described.
Embodiment 1
In the 500 ml reaction bulbs 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 stirring, water bath heat preservation 25 DEG C, in 60 minutes, drip 7.0g DMF and the mixed liquor of 55ml ethyl acetate, remove water-bath, in 10 minutes to 20 minutes, it is slowly ramped to 60 DEG C ~ 65 DEG C after stirring, reacts 8 hours.
Aforesaid liquid is poured in constant pressure addition device.In the 500ml reaction bulb with stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant pressure addition device, add 117.0g cyclohexylamine and 165ml ethyl acetate, open stirring, ice bath is incubated less than 40 DEG C, drips above-mentioned midbody solution, after dropping, remove ice bath, it is warming up to reflux temperature (about 78 DEG C) react 7.5 hours, stops heating, be cooled to less than 60 DEG C, thick product is poured in funnel, sucking filtration, gained filtrate collection is standby, and gained filter cake pulverizes.Solid is leached with the washing of 1000ml boiled water, sucking filtration, soak gained filter cake, sucking filtration by the NaOH solution of 1000ml pH=14 again, then wash filter cake at twice with 1000ml clear water, sucking filtration, being dried, obtain target product white powder 32.3g, yield is that 94.8%(is by the trimesic acid amount of carrying out calculating), 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 bulb 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 stirring, water bath heat preservation 25 DEG C, in 60 minutes, drip 240.0g DMF and the mixed liquor of 1440ml ethyl acetate, remove water-bath, in 10 minutes to 20 minutes, it is slowly ramped to 60 DEG C ~ 65 DEG C after stirring, reacts 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 cyclohexylamine and 7300ml ethyl acetate, open stirring, ice bath is incubated less than 40 DEG C, drips above-mentioned midbody solution, after dropping, remove ice bath, it is warming up to reflux temperature (about 78 DEG C) react 7.5 hours, stops heating, be cooled to less than 60 DEG C, thick product is poured in funnel, sucking filtration, gained filtrate collection is standby, and gained filter cake pulverizes.Solid is leached with the washing of 16L boiled water, sucking filtration, soak gained filter cake, sucking filtration by the NaOH solution of 16L pH=14 again, then wash filter cake at twice with 32L clear water, sucking filtration, being dried, get final product target product white powder 1038.3g, yield is that 95.2%(is by the trimesic acid amount of carrying out calculating), fusing point is 366.0～374.4 DEG C, and efficient liquid phase chromatographic analysis purity is 96.42%.
The said goods all determines structure through infrared spectrum, nuclear-magnetism and efficient liquid phase chromatographic analysis, tries out in polylactic acid nucleation, obtains preferable effect.
The above is only the better embodiment of the present invention, therefore all equivalence changes done according to structure, feature and the principle described in present patent application scope or modification, in the range of being all included in present patent application.
Claims (8)
1. produce a N, N, N-thricyclohexyl-1, the technique of 3,5-benzamides with trimesic acid, it is characterised in that:
Comprise the following steps:
A: first the amount of material is blended in ethyl acetate medium than trimesic acid and the triphosgene for 1:3, 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 the amount ratio of trimesic acid material；
B: after dropping, removes water-bath, is warming up to 60 DEG C ~ 65 DEG C, is incubated 6 ~ 10 hours, synthesizes pyromellitic trimethylsilyl chloride；
C: after reaction terminates, putting in another reactor by cyclohexylamine and ethyl acetate successively, cyclohexylamine is 15.76 with the amount ratio of trimesic acid material, ice bath, stirring, ice bath controls below 40 DEG C, the pyromellitic trimethylsilyl chloride solution prepared in dropping step B the most lentamente；
D: after dropping, is warming up to 78 DEG C, insulation reaction 6 ~ 10 hours；
E: be cooled to less than 60 DEG C, sucking filtration, pulverize gained filter cake and obtain thick product, boiling water washs thick product, sucking filtration, wash gained filter cake, sucking filtration by NaOH solution again, then wash filter cake, sucking filtration with clear water, be dried, both white powder N, N, N-thricyclohexyl-1,3,5-benzamides had been obtained.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: the described solvent in step A is ethyl acetate, and wherein ethyl acetate is 7.52 with the amount ratio of trimesic acid material.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: the N of dropping in described step A, the ethyl acetate solution of dinethylformamide, ethyl acetate is 7.52 with the amount ratio of trimesic acid material.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: the described time for adding in step A is 60 minutes.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: the described response time in step B is 8 hours.
Production N the most according to claim 1, N, N-thricyclohexyl-1,3, the technique of 5-benzamide, it is characterized in that: being slowly added dropwise in the mixed liquor of cyclohexylamine and ethyl acetate by pyromellitic trimethylsilyl chloride solution obtained in step B in described step C, in described mixed solution, ethyl acetate is 22.55 with the amount ratio of trimesic acid material.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: in described step D, the response time is 7.5 hours.
Production N the most according to claim 1, N, N-thricyclohexyl-1, the technique of 3,5-benzamides, it is characterised in that: the second time in described step E washs the pH=14 of NaOH solution used by thick product.
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| CN107501605B (en) * | 2017-10-25 | 2019-03-08 | 山西省化工研究所（有限公司） | A kind of purposes of equal benzene trimethamide class compound |
| CN113429768B (en) * | 2021-07-16 | 2022-08-02 | 湖南玥昇杰科技有限责任公司 | Polylactic acid composition containing amide nucleating agent and preparation method thereof |
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