CN109651254A - A method of preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids - Google Patents
A method of preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids Download PDFInfo
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- CN109651254A CN109651254A CN201910091115.9A CN201910091115A CN109651254A CN 109651254 A CN109651254 A CN 109651254A CN 201910091115 A CN201910091115 A CN 201910091115A CN 109651254 A CN109651254 A CN 109651254A
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- Prior art keywords
- reaction
- dibenzyl
- ketone
- dicarboxylic acids
- dimethyl carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
Abstract
The present invention relates to the present invention relates to chemical industry synthesis fields, and in particular to a kind of to prepare 1,3- dibenzyl imidazole -2- ketone -4, the method of 5- dicarboxylic acids, its key step are as follows: with cis- 2,3- dibenzyl amido succinic acid and dimethyl carbonate for raw material, prepared under the catalytic action of zinc acetate.The present invention can effectively avoid environmental hazard brought by phosgene, and have transforming degree high, and reaction condition is mild, and side reaction is few, isolates and purifies the advantages such as easy, reduces the cost of production, be more conducive to industrial production.
Description
Technical field
The present invention relates to chemical industry synthesis fields, and in particular to a kind of to prepare 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids
Method.
Background technique
1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids is that biotin synthesizes very important intermediate, and industry is commonly called as ring
Acid.The technique of traditional industrial production naphthenic acid is to use phosgene as carbonylation agent, but phosgene causes very environment
Big harm, at the same it is larger to personal safety threat in production process, and dimethyl carbonate is a kind of free of contamination green of low toxicity
Chemicals, because its chemical structure is similar with property with naphthenic acid, replacing phosgene with dimethyl carbonate will be a kind of green
The research direction of chemicals technique, this technology provide a kind of new technology with dimethyl carbonate substitution optical self-encoding naphthenic acid.
Summary of the invention
The object of the present invention is to provide the preparation method of one kind 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, steps
Are as follows:
With cis- 2,3- dibenzyl amido succinic acid and dimethyl carbonate for raw material, made under the catalytic action of zinc acetate
It is standby.
The present invention substitutes toxic raw material phosgene with dimethyl carbonate, is paid no attention to very much using catalytic effect when other catalyst
Think, by multiple experiment and exploration, discovery can just obtain preferable reaction effect in the case where zinc acetate is as catalyst.
Preferably, the mass ratio of cis- 2, the 3- dibenzyl amido succinic acid and dimethyl carbonate is 0.5~3:1.It is above-mentioned anti-
Application amount is conducive to increase the reaction yield for succinic acid.
Preferably, the mass ratio of the zinc acetate and dimethyl carbonate is 0.05~0.3:1.Above-mentioned dosage is controllable appropriate
Reaction rate.
Preferably, the temperature of reaction is 100~200 DEG C.
Preferably, the pressure of reaction is 0.5~3Mpa.By-product can be reduced under above-mentioned temperature and pressure reaction condition
It generates.
Preferably, the time reacted in the step 1) is 4~10h.More preferably 5~10h.
Preferably, purifying is further included the steps that after the completion of preparation；Specifically, the mixed solution after reaction is filtered,
Washing and drying.
Preferably, it is secondary to be first that 3~5%HCl aqueous solution washs with 0~5 DEG C of concentration for the filter cake of the filtering, then with 0
DEG C ice water washed once, and vacuum drying is after washing to get 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids.
As a preferred option, the method for the present invention includes following steps:
With cis- 2,3- dibenzyl amido succinic acid and dimethyl carbonate for raw material, made under the catalytic action of zinc acetate
It is standby；
The mass ratio of the cis- 2,3- dibenzyl amido succinic acid and dimethyl carbonate is 1~1.25:1.
The mass ratio of the zinc acetate and dimethyl carbonate is 0.1~0.125:1, and the temperature of reaction is 120 DEG C~150
DEG C, the pressure of reaction is 2Mpa, and the time of reaction is 7~8h.
The structural formula of cis- 2,3- dibenzyl amido succinic acid of the present invention are as follows:
The invention has the following beneficial effects:
1) method of the present invention can stablize the yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids
92% or more, conversion ratio is conducive to industrialized production 90% or more, with the effect of conventional method quite and its prepare raw material without
Poison ring is protected.
2) present invention can effectively avoid environmental hazard brought by phosgene, and have transforming degree height, reaction condition
Mildly, side reaction is few, isolates and purifies the advantages such as easy, reduces the cost of production, be more conducive to industrial production.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment provides a kind of methods for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, including following step
It is rapid:
Cis- 2, the 3- dibenzyl amido succinic acid of 25kg is added in the dimethyl carbonate of 20kg parts by weight, adds 3kg's
Zinc acetate reacts 6h at 130 DEG C of temperature and 2Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield for 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids that the present embodiment the method is prepared is 91%,
Purity is 98%.
Embodiment 2
The present embodiment provides a kind of methods for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, including following step
It is rapid:
Cis- 2, the 3- dibenzyl amido succinic acid of 20kg is added in the dimethyl carbonate of 25kg, adds the acetic acid of 2kg
Zinc reacts 7h at 140 DEG C of temperature and 3Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of the 1 of the present embodiment the method, 3 dibenzyl imidazole -2- ketone -4,5 dicarboxylic acids is 89%, and purity is
98.5%.
Embodiment 3
The present embodiment provides a kind of methods for preparing 1,3 dibenzyl imidazole -2- ketone -4,5 dicarboxylic acids, comprising the following steps:
Cis- 2, the 3- dibenzyl amido succinic acid of 30kg is added in the dimethyl carbonate of 30kg, adds the acetic acid of 3kg
Zinc reacts 7h at 150 DEG C of temperature and 2Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids of the present embodiment the method is 94%, purity
It is 99%.
Embodiment 4
The present embodiment provides a kind of methods for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, including following step
It is rapid:
Cis- 2, the 3- dibenzyl amido succinic acid of 35kg is added in the dimethyl carbonate of 20kg, adds 3kg parts by weight
Zinc acetate reacts 6h at 160 DEG C of temperature and 3Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids of the present embodiment the method is 90%, purity
It is 99.1%.
Embodiment 5
The present embodiment provides a kind of methods for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, including following step
It is rapid:
Cis- 2, the 3- dibenzyl amido succinic acid of 25kg is added in the dimethyl carbonate of 20kg, adds the acetic acid of 2.5kg
Zinc reacts 8h at 120 DEG C of temperature and 2Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids of the present embodiment the method is 92%, purity
It is 99.5%.
Comparative example 1
The present embodiment is related to a kind of method for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, with 1 phase of embodiment
Than difference is to change the temperature of reaction and the dosage of catalyst, specifically, by cis- 2, the 3- dibenzyl amido fourth of 25kg
Diacid is added in the dimethyl carbonate of 20kg, adds the zinc acetate of 2.5kg, reacts at 80 DEG C of temperature and 2Mpa pressure
8h。
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids of the present embodiment the method is 20%, purity
It is 30%.
Comparative example 2
The present embodiment is related to a kind of method for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, with 1 phase of embodiment
Than dosage that, difference is to change the pressure of reaction, temperature and catalyst by cis- 2, the 3- dibenzyl amido succinic acid of 25kg
It is added in the dimethyl carbonate of 20kg, adds the zinc acetate of 2.5kg, react 8h at 150 DEG C of temperature and 0.5Mpa pressure.
After reaction, mixed solution is filtered at normal temperatures and pressures, it is 3% that filtered filter cake, which first uses 0 DEG C of concentration,
HCL aqueous solution washing is secondary, then washed once with 0 DEG C of ice water, and filter cake is dried in vacuo to get 1,3- dibenzyl miaow after washing
Azoles -2- ketone -4,5- dicarboxylic acids.
The yield of 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids of the present embodiment the method is 30%, purity
It is 40%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of method for preparing 1,3- dibenzyl imidazole -2- ketone -4,5- dicarboxylic acids, which is characterized in that with cis- 2,3- dibenzylamine
Base succinic acid and dimethyl carbonate are raw material, are prepared under the catalytic action of zinc acetate.
2. the method according to claim 1, wherein cis- 2, the 3- dibenzyl amido succinic acid and carbonic acid diformazan
The mass ratio of ester is 0.5~3:1.
3. method according to claim 1 or 2, which is characterized in that the mass ratio of the zinc acetate and dimethyl carbonate is
0.05~0.3:1.
4. described in any item methods according to claim 1~3, which is characterized in that the temperature of reaction is 100-200 DEG C.
5. method according to any one of claims 1 to 4, which is characterized in that the pressure of reaction is 0.5~3Mpa.
6. described in any item methods according to claim 1~5, which is characterized in that the time of reaction be 4~10h, preferably 5
~10h.
7. described in any item methods according to claim 1~6, which is characterized in that further include the steps that purifying after the completion of preparation.
8. the method according to the description of claim 7 is characterized in that the purifying is specially to carry out the mixed solution after reaction
Filtering, washing and drying.
9. according to the method described in claim 8, it is characterized in that, filter cake specifically, is first used 0~5 DEG C dense by the washing
Degree is that the washing of 3~5%HCl aqueous solution is secondary, then washed once with 0 DEG C of ice water, and vacuum drying is after washing to get 1, the 3- bis-
Benzyl imidazole -2- ketone -4,5- dicarboxylic acids.
10. described in any item methods according to claim 1~9, which is characterized in that cis- 2, the 3- dibenzyl amido succinic acid
Mass ratio with dimethyl carbonate is 1~1.25:1；The mass ratio of the zinc acetate and dimethyl carbonate is 0.1~0.125:1,
The temperature of reaction is 120 DEG C~150 DEG C, and the pressure of reaction is 2Mpa, and the time of reaction is 7~8h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996038421A1 (en) * | 1995-06-02 | 1996-12-05 | Berlex Laboratories, Inc. | N,n-di(arylmethyl)cyclic urea derivatives as anti-coagulants |
| CN1488623A (en) * | 2003-08-26 | 2004-04-14 | 河北工业大学 | Method for preparing 2,4-toluene diamino menthyl formate |
| CN104628602A (en) * | 2015-02-05 | 2015-05-20 | 宋和璇 | Tetramethyl diethylenetriamine formate compound as well as preparation method and application thereof |
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2019
- 2019-01-30 CN CN201910091115.9A patent/CN109651254A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996038421A1 (en) * | 1995-06-02 | 1996-12-05 | Berlex Laboratories, Inc. | N,n-di(arylmethyl)cyclic urea derivatives as anti-coagulants |
| CN1488623A (en) * | 2003-08-26 | 2004-04-14 | 河北工业大学 | Method for preparing 2,4-toluene diamino menthyl formate |
| CN104628602A (en) * | 2015-02-05 | 2015-05-20 | 宋和璇 | Tetramethyl diethylenetriamine formate compound as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 岳红杉等: "反应条件对合成苯氨基甲酸甲酯乙酸锌催化剂结构的影响", 《河北工业大学学报》 * |
| 范素兵等: "乙酸锌催化一步法合成吡咯甲酸甲酯", 《石油化工》 * |
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Application publication date: 20190419 |