CN102432486A - Synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester - Google Patents
Synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester Download PDFInfo
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- CN102432486A CN102432486A CN2011103858148A CN201110385814A CN102432486A CN 102432486 A CN102432486 A CN 102432486A CN 2011103858148 A CN2011103858148 A CN 2011103858148A CN 201110385814 A CN201110385814 A CN 201110385814A CN 102432486 A CN102432486 A CN 102432486A
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- ester
- ammediol
- acid
- nitrobenzoic acid
- propanediol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester. The synthesis method comprises the following steps: a) putting 1,3-propanediol and nitrobenzoic acid at a mol ratio of 1:(1.5-2.5) into a reaction kettle, heating to 130-150 DEG C, reacting for 6-8 hours, then heating to 180-200 DEG C and reacting for 5-8 hours; and b) adding a solvent and a catalyst into materials, introducing hydrogen gas to carry out hydrogenation reducing reaction at the temperature of 80-100 DEG C, filtering and recovering the catalyst immediately after reaction is finished, concentrating, then carrying out cooling crystallization, filtering and drying to obtain the 1,3-propanediol-bis(4-nitrobenzoic acid)ester product. The method disclosed by the invention has the characteristics of easily available raw materials, convenience in operation, high yield, high product purity, low cost and less produced three wastes, and is especially suitable for industrial production and is beneficial to environmental conservation.
Description
Technical field
The present invention relates to a kind of by p-Nitrobenzenecarboxylic acid preparation 1, the compound method of ammediol-two (4-benzaminic acid) ester.
Background technology
1.3 Ucar 35-two (4-benzaminic acid) ester is a kind of colourless, odorless, tasteless crystal, is insoluble in water, be a kind of safely, have the amine curing agent of premium properties, be used for the curing of base polyurethane prepolymer for use as, epoxy resin, can obtain the goods of premium properties.Adopt 1.3 Ucar 35-two (4-benzaminic acid) esters and TDI/ polyethers or the prepared elastomerics of pet reaction, have good physicals; Simultaneously the excellent in chemical performance is also arranged, like water-fast stability of solution, anti-drying/hot, oil resistant/solvent/humidity/ozone etc.
1.3 the existing compound method of Ucar 35-two (4-benzaminic acid) ester mainly contains two kinds.A kind of method is through para-amino benzoic acid first or ethyl ester and 1, and ammediol carries out ester-interchange method in the presence of catalyzer synthetic.Another kind method is to be raw material with the p-Nitrobenzenecarboxylic acid, after chloride, obtains paranitrobenzoyl chloride earlier, and again with 1, ammediol synthesizes 1, and ammediol-two (4-nitrobenzoic acid) ester makes through iron powder reducing or shortening.Though first method technology is fairly simple, exist the shortcoming that yield is low, product purity is not high, cost is high, the suitability for industrialized production difficulty is bigger.The second method synthetic route is long, has a large amount of hydrogenchloride to produce in the production process, and to the production unit seriously corroded, operational condition is complicated, and production cost is high.
The esterification of organic acid and alcohol needs under the catalyzer existence condition such as strong acid usually carries out, and because esterification is a reversible reaction, reaction often is difficult to fully, thereby purifying products difficulty comparatively, especially produces more " three wastes ".
Summary of the invention
The objective of the invention is to overcome the shortcoming that product yield is low, purity is not high, operational condition is complicated, particularly cost is high, environmental pollution is big of prior art; Provide that a kind of product yield is high, purity is high, easy to operate, environmentally friendly 1, the compound method of ammediol-two (4-nitrobenzoic acid) ester.
A kind of 1, the compound method of ammediol-two (4-benzaminic acid) ester is characterized in that, may further comprise the steps:
A) be 1 of 1:1.5-2.5 with mol ratio, ammediol and p-Nitrobenzenecarboxylic acid drop in the reaction kettle, are warming up to 130-150 ℃, react 6-8 hour, are warming up to 180-200 ℃ again, react 5-8 hour;
B) in material, add solvent and catalyzer, under 80-100 ℃ temperature condition, feed hydrogen and carry out hydrogenation reduction, reaction finishes the back filtered while hot and reclaims catalyzer; Concentrate the postcooling crystallization; Filter, oven dry obtains product 1, ammediol-two (4-benzaminic acid) ester.
Further, among the step b, said solvent is selected from benzene,toluene,xylene, N, dinethylformamide, N, a kind of in N-DEF or the DMSO 99.8MIN..
Among the step b, said catalyzer is preferably 5% palladium carbon.
The present invention is raw material with the p-Nitrobenzenecarboxylic acid, and with 1, ammediol directly carries out esterification, obtains 1, ammediol-two (4-
NitreYl benzoic acid) ester synthesizes 1, ammediol-two (4-through the method for shortening again
AmmoniaYl benzoic acid) ester.
In the method surprisingly of the present invention; P-Nitrobenzenecarboxylic acid and 1; Esterification directly takes place under the condition that ammediol can not need catalyzer to exist; And side reaction takes place under reaction conditions of the present invention hardly, thereby can obtain 1 of high yield, ammediol-two (4-nitrobenzoic acid) ester intermediates.
In the method for the invention, the direct esterification reaction under the condition that catalyst-free exists of p-Nitrobenzenecarboxylic acid and 1, ammediol obtains 1, produces hardly in the process of ammediol-two (4-nitrobenzoic acid) ester " three wastes ".The method that the technology of employing catalytic hydrogenating reduction nitro replaces traditional iron powder reducing also is a kind of eco-friendly Technology.
The present invention synthesizes 1, and the concrete steps of ammediol-two (4-benzaminic acid) ester are: with 1, the ratio 1:1.5-2.5 that ammediol, p-Nitrobenzenecarboxylic acid are pressed earlier amount of substance drops in the reaction kettle; Be warming up to 130-150 ℃; Reacted 6-8 hour, and be warming up to 180-200 ℃ again, reacted 5-8 hour; In material, add solvent and catalyzer, feed hydrogen under 80-100 ℃ temperature condition, under catalyst action, carry out the shortening building-up reactions, condensing crystal obtains 1 behind the filtering recovering catalyst, ammediol-two (4-benzaminic acid) ester product.Perhaps after esterification, add solvent and carry out crystallization, filter, obtain 1, ammediol-two (4-
NitreYl benzoic acid) ester solid carries out the catalytic hydrogenating reduction reaction with solvent, catalyzer and hydrogen again with this solid under 80-100 ℃ temperature condition, condensing crystal obtains 1 behind the filtering recovering catalyst, ammediol-two (4-
AmmoniaYl benzoic acid) ester product.
The inventive method has that raw material is easy to get, easy to operate, yield is high, product purity is high and cost is low characteristics, be specially adapted to suitability for industrialized production, and " three wastes " that produce is few, help environment protection.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage of the present invention and characteristics will be more clear along with description.But these embodiment only are exemplary, scope of the present invention are not constituted any restriction.It will be understood by those skilled in the art that and down can make amendment with form and replace without departing from the spirit and scope of the present invention the details of technical scheme of the present invention, but these modifications and replace and all list in protection scope of the present invention.
Embodiment 1
In the 2000ml four-hole boiling flask of stirring, TM, water distilling apparatus is housed, add 228g 1, ammediol and 1025g p-Nitrobenzenecarboxylic acid are warming up to 130-150 ℃ gradually; Reaction is 8 hours under this temperature, is warming up to 180-200 ℃ of reaction 6 hours again, is cooled to about 100 ℃, adds 2500ml toluene; Transfer in the autoclave of 5000ml, add 20 grams, 5% palladium carbon catalyst, feed hydrogen down at 80-90 ℃, the pressure of 1000KPa and react till no longer absorb hydrogen filtered while hot recovery catalyzer; Cool to room temperature, filter, solid is with 300ml toluene wash three times; Oven dry gets 1, ammediol-two (4-benzaminic acid) ester solid: 830.8g; Yield (with 1, the ammediol meter): 88.2%, HPLC content: 97.86%.
Embodiment 2
In the 3000ml four-hole boiling flask of stirring, TM, water distilling apparatus is housed, add 228g 1, ammediol and 1025g p-Nitrobenzenecarboxylic acid are warming up to 130-150 ℃ gradually; Reaction is 8 hours under this temperature, is warming up to 180-200 ℃ of reaction 6 hours again, is cooled to about 100 ℃; Add 1500ml toluene, cool to room temperature filters; Solid is with 300ml toluene wash three times, dry 1, ammediol-two (4-nitrobenzoic acid) ester solid: 1033.4 grams; Yield (with 1, the ammediol meter): 92.1%, HPLC content: 97.53%
Embodiment 3
In the 3000ml four-hole boiling flask of stirring, TM, water distilling apparatus is housed, add the toluene solution in the instance 2, distillation adds 228g 1, ammediol and 1025g p-Nitrobenzenecarboxylic acid after reclaiming toluene again; Be warming up to 140-150 ℃ gradually, reaction is 7 hours under this temperature, is warming up to 180-190 ℃ of reaction 6 hours again, is cooled to about 100 ℃; Add 1500ml toluene, cool to room temperature filters; Solid is with 300ml toluene wash three times, dry 1, ammediol-two (4-nitrobenzoic acid) ester solid: 1090.6 grams; Yield (with 1, the ammediol meter): 97.2%, HPLC content: 97.76%
Embodiment 4
In the autoclave of 1000ml, add obtain in the instance 31, ammediol-two (4-nitrobenzoic acid) ester solid 100 grams, 500ml YLENE, 5 restrain 5% palladium carbon catalyst; Under 90 ℃, the pressure of 1000KPa, feed hydrogen and react till no longer absorb hydrogen, filtered while hot reclaims catalyzer, is concentrated to about 300ml; Cool to room temperature, filter, solid is with 50ml YLENE washing three times; Oven dry gets 1, ammediol-two (4-benzaminic acid) ester solid: 79.2g; Yield: 94.3%, HPLC content: 98.52%.
Claims (3)
1. one kind 1, the compound method of ammediol-two (4-benzaminic acid) ester is characterized in that, may further comprise the steps:
A) be 1 of 1:1.5-2.5 with mol ratio, ammediol and p-Nitrobenzenecarboxylic acid drop in the reaction kettle, are warming up to 130-150 ℃, react 6-8 hour, are warming up to 180-200 ℃ again, react 5-8 hour;
B) in material, add solvent and catalyzer, under 80-100 ℃ temperature condition, feed hydrogen and carry out hydrogenation reduction, reaction finishes the back filtered while hot and reclaims catalyzer; Concentrate the postcooling crystallization; Filter, oven dry obtains product 1, ammediol-two (4-benzaminic acid) ester.
2. compound method as claimed in claim 1 is characterized in that, among the step b, said solvent is selected from benzene,toluene,xylene, N, dinethylformamide, N, a kind of in N-DEF or the DMSO 99.8MIN..
3. compound method as claimed in claim 1 is characterized in that, among the step b, said catalyzer is 5% palladium carbon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103858148A CN102432486A (en) | 2011-11-29 | 2011-11-29 | Synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester |
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| CN2011103858148A CN102432486A (en) | 2011-11-29 | 2011-11-29 | Synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester |
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| CN102432486A true CN102432486A (en) | 2012-05-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478444A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of method that use chlorination sodium reduction produces 2- acetylaminohydroxyphenylarsonic acid 6- nitrobenzoic acid |
| CN110452366A (en) * | 2019-08-20 | 2019-11-15 | 西安近代化学研究所 | Polyadipate 2- ethyl -2- nitro propylene glycol ester and its preparation method and application |
| CN115073296A (en) * | 2022-08-23 | 2022-09-20 | 深圳市易瑞生物技术股份有限公司 | Method and device for rapidly detecting propylene glycol in food |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0013956A1 (en) * | 1979-01-25 | 1980-08-06 | Hoechst Aktiengesellschaft | Process for the preparation of alcanediol-bis-aminobenzoic acid esters |
| US4283549A (en) * | 1977-12-12 | 1981-08-11 | Aktiebolaget Bofors | Method of producing alkandiol-diaminobenzoates |
-
2011
- 2011-11-29 CN CN2011103858148A patent/CN102432486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283549A (en) * | 1977-12-12 | 1981-08-11 | Aktiebolaget Bofors | Method of producing alkandiol-diaminobenzoates |
| EP0013956A1 (en) * | 1979-01-25 | 1980-08-06 | Hoechst Aktiengesellschaft | Process for the preparation of alcanediol-bis-aminobenzoic acid esters |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478444A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of method that use chlorination sodium reduction produces 2- acetylaminohydroxyphenylarsonic acid 6- nitrobenzoic acid |
| CN110452366A (en) * | 2019-08-20 | 2019-11-15 | 西安近代化学研究所 | Polyadipate 2- ethyl -2- nitro propylene glycol ester and its preparation method and application |
| CN115073296A (en) * | 2022-08-23 | 2022-09-20 | 深圳市易瑞生物技术股份有限公司 | Method and device for rapidly detecting propylene glycol in food |
| CN115073296B (en) * | 2022-08-23 | 2022-11-01 | 深圳市易瑞生物技术股份有限公司 | Method and device for rapidly detecting propylene glycol in food |
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Application publication date: 20120502 |