CN100463900C - Prepn process of 3-amino-4-cetyl chlorobenzoate - Google Patents
Prepn process of 3-amino-4-cetyl chlorobenzoate Download PDFInfo
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- CN100463900C CN100463900C CNB2006100983592A CN200610098359A CN100463900C CN 100463900 C CN100463900 C CN 100463900C CN B2006100983592 A CNB2006100983592 A CN B2006100983592A CN 200610098359 A CN200610098359 A CN 200610098359A CN 100463900 C CN100463900 C CN 100463900C
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Abstract
The present invention relates to the preparation process of 3-amino-4-cetyl chlorobenzoate. Compound 3-amino-4-cetyl chlorobenzoate is prepared with 3-amino-4- chlorobenzoic acid and cetanol as main material, and tin tetrachloride, stannous chloride or butyl titanate as catalyst, and through solvent reflux dewatering and esterification. The preparation process includes the following steps: setting 3-amino-4- chlorobenzoic acid and cetanol into organic solvent, heating to dissolve and adding catalyst via stirring, reflux dewatering, recovering solvent after reaction and adding refined organic solvent, filtering to obtain solid, re-crystallizing in refined organic solvent and stoving to obtain 3-amino-4-cetyl chlorobenzoate product. The present invention has great production capacity and high product purity, and is suitable for industrial production.
Description
Technical field
The present invention relates to 3-amino-4-cetyl chlorobenzoate, relate in particular to the preparation method of 3-amino-4-cetyl chlorobenzoate, belong to the organic acid acetic synthesis technical field.
Background technology
3-amino-4-cetyl chlorobenzoate is a kind of important sensitive materials intermediate, is that raw material synthetic sensitive materials has the reactive behavior height with this product, and oil soluble is good, to characteristics such as light, thermostability height.
At present, the preparation method of 3-amino-4-cetyl chlorobenzoate has: be starting raw material with 3-amino-4-chloro-benzoic acid and bromohexadecane 1., prepare under alkaline condition; 2. be starting raw material with 3-amino-4-chloro-benzoic acid and hexadecanol, under acidic conditions, prepare.
Characteristics of 1. planting method are the reaction conditions gentlenesses, be swift in response, the yield height, can be referring to European patent EP 853077; But the bromohexadecane price is high, makes the production cost of this method higher, is difficult to have market competition advantage.Yet, method 2. adopt cheap hexadecanol come alternative method 1. in expensive bromohexadecane, prepare 3-amino-4-cetyl chlorobenzoate by esterification at sulfuric acid under as the condition of catalyzer, can be referring to Japanese Patent JP9286766; Though cost of material is cheap, because the activity of hexadecanol is lower than bromohexadecane, therefore reaction is difficult to carry out, the vitriol oil has strong oxidizing property, be unfavorable for high temperature esterification reaction, it is excessive 300% that the consumption of raw material hexadecanol is wanted, and is unfavorable for reclaiming the purification with product.Big excessive hexadecanol has not only weakened the suitability for industrialized production ability, numerously increases the aftertreatment recovery process, and 3-amino-4-cetyl chlorobenzoate separates quite difficulty from a large amount of hexadecanols, and purification of products exists technological deficiency; Be difficult to realize large-scale industrial production.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of 3-amino-4-cetyl chlorobenzoate, adopt new catalyzer and reaction solvent, on the basis that keeps original operational path advantage, overcome all deficiencies of prior art, make easier the carrying out of preparation process of 3-amino-4-cetyl chlorobenzoate, product purity is higher, and cost is lower, can realize large-scale industrial production.
Technical solution of the present invention is: the preparation method of 3-amino-4-cetyl chlorobenzoate is a raw material with 3-amino-4-chloro-benzoic acid and hexadecanol, comprises following processing step---
1. 3-amino-4-chloro-benzoic acid and hexadecanol are joined in the organic solvent;
2. rising temperature for dissolving adds tin tetrachloride or tin protochloride or tetrabutyl titanate as catalyzer under stirring, and carries out esterification;
3. reflux dewatering goes out to no longer including moisture;
4. after reaction finishes, reclaim solvent, add refining organic solvent crystallization then;
5. filter out solid, with refining organic solvent recrystallization, oven dry gets 3-amino-4-cetyl chlorobenzoate finished product.
The further technical solution that realizes the object of the invention is:
The preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, the mol ratio of the 1. middle 3-amino of step-4-chloro-benzoic acid and hexadecanol is 1:1.0～1.5.
Further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, the mol ratio of the 1. middle 3-amino of step-4-chloro-benzoic acid and hexadecanol is 1:1.2.
Further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, the organic solvent that 1. step is adopted is toluene or dimethylbenzene or chlorobenzene.
Further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, step 1. in the consumption of organic solvent be 1～3 times of 3-amino-4-chloro-benzoic acid weight.
Further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, the step 2. add-on of middle catalyzer is that the mol ratio of catalyzer and 3-amino-4-chloro-benzoic acid is 0.02～0.4:1.
Further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, 4. step is methyl alcohol, ethanol, Virahol, normal hexane or sherwood oil with the refining organic solvent that 5. step is adopted.
Again further, the preparation method of aforesaid 3-amino-4-cetyl chlorobenzoate, wherein, the weight ratio of the 4. middle 3-amino of step-4-chloro-benzoic acid and refining organic solvent is 1:3～8.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention mainly shows:
(1) the present invention adopts tin tetrachloride or tin protochloride or the tetrabutyl titanate catalyzer as esterification, its good catalytic activity;
(2) adopt toluene, dimethylbenzene etc. as reaction solvent, effectively improved speed of response;
(3) mol ratio of 3-amino-4-chloro-benzoic acid and hexadecanol is reduced to about 1:1.2, reduced the consumption of hexadecanol greatly, improved production capacity;
(4) need not to reclaim excessive hexadecanol, simplified the postorder treatment process;
(5) raw material is easy to separate with product, and product yield and purity are all significantly better than the prior art optimum value.
Embodiment
3-amino-4-cetyl chlorobenzoate is a kind of important sensitive materials intermediate, be used for synthetic multiple sensitive materials, can form yellow colour coupler with the derivative of glycolylurea class, this type of yellow colour coupler is compared with present used CP116 has higher activity and photographic property, for shutterbugs provide more better choice, also the creation for photography art provides more wide space, and its demand is big, and market outlook are good.
The invention provides the preparation method of a kind of 3-amino-4-cetyl chlorobenzoate, with 3-amino-4-chloro-benzoic acid and hexadecanol is the main reaction raw material, select for use tin tetrachloride or tin protochloride or tetrabutyl titanate as catalyzer, by the solvent refluxing dehydration, prepare 3-amino-4-cetyl chlorobenzoate through esterification.Reaction solvent adopts common toluene, dimethylbenzene and chlorobenzene etc., is reflected at and carries out under the reflux state, and reaction process is easy to control, and terminal point is judged easily.
Following illustrative example is to specify technical solution of the present invention.But this is an application example, and they only provide as an example, is not considered as application limitations of the present invention.Being equal to of all operational conditions replaced or equivalent transformation, all drops within protection scope of the present invention.
Embodiment 1:
The four neck round-bottomed flasks of a 1000ml have mechanical stirring, thermometer, water trap, prolong, add 200g toluene in flask successively, the 3-amino-4-chloro-benzoic acid of 200g and the hexadecanol of 335g.After the rising temperature for dissolving, stir adding 5g tin tetrachloride down.The temperature rising reflux dehydration goes out backsight for reacting end when no longer including moisture.Decompression and solvent recovery, gained toluene can be recycled, and residuum under agitation adds in the 1400ml methyl alcohol, is cooled to 25 ℃ of filtrations, gets crude product.After crude product was used the 1400ml refining methanol, oven dry can get 3-amino-4-cetyl chlorobenzoate finished product 330g, yield 72%.Efficient liquid phase chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 99.5% in the product, and gas chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 98.6% in the product.
Embodiment 2:
The four neck round-bottomed flasks of a 2000ml have mechanical stirring, thermometer, water trap, prolong, add 500g dimethylbenzene in flask successively, the 3-amino-4-chloro-benzoic acid of 200g and the hexadecanol of 335g.After the rising temperature for dissolving, stir adding 40g tin tetrachloride down.The temperature rising reflux dehydration goes out backsight for reacting end when no longer including moisture.Decompression and solvent recovery, gained dimethylbenzene can be applied mechanically repeatedly, and residuum under agitation adds in the 1400ml methyl alcohol, is cooled to 25 ℃ of filtrations, gets crude product.After crude product was used the 1400ml refining methanol, oven dry can get 3-amino-4-cetyl chlorobenzoate finished product 300g, yield 65%.Efficient liquid phase chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 99.4% in the product, and gas chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 98.5% in the product.
Embodiment 3:
The four neck round-bottomed flasks of a 1000ml have mechanical stirring, thermometer, water trap, prolong, add 200g toluene in flask successively, the 3-amino-4-chloro-benzoic acid of 200g and the hexadecanol of 335g.After the rising temperature for dissolving, stir adding 5g tin protochloride down.The temperature rising reflux dehydration goes out backsight for reacting end when no longer including moisture.Decompression and solvent recovery, gained toluene can be applied mechanically repeatedly, and residuum adds in the 1400ml methyl alcohol in stirring down, is cooled to 25 ℃ of filtrations, gets crude product.After crude product was used the 1400ml refining methanol, oven dry can get 3-amino-4-cetyl chlorobenzoate finished product 320g, yield 70%.Efficient liquid phase chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 99.4% in the product, and gas chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 98.5% in the product.
Embodiment 4:
The four neck round-bottomed flasks of a 1000ml have mechanical stirring, thermometer, water trap, prolong, add the 200g chlorobenzene in flask successively, the 3-amino-4-chloro-benzoic acid of 200g and the hexadecanol of 330g.After the rising temperature for dissolving, stir adding 6g tetrabutyl titanate down.The temperature rising reflux dehydration goes out backsight for reacting end when no longer including moisture.Decompression and solvent recovery, gained toluene can be applied mechanically repeatedly, and residuum adds in the 1500ml normal hexane in stirring down, is cooled to 25 ℃ of filtrations, gets crude product.After crude product was used the 1400ml refining methanol, oven dry can get 3-amino-4-cetyl chlorobenzoate finished product 320g, yield 70%.Efficient liquid phase chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 99.2% in the product, and gas chromatographic analysis shows that the content of 3-amino-4-cetyl chlorobenzoate is 98.0% in the product.
Above embodiment shows that product yield of the present invention and purity are all significantly better than the prior art optimum value.After tested, the quality index of product is as follows:
| Proterties | Light brown to the off-white color crystalline powder, tasteless, be dissolved in ethanol, benzene and sherwood oil, water insoluble |
| Content | ≥98.5％(GC) |
| Fusing point | 70.0℃～72.0℃ |
| Weight loss on drying | ≤0.5％ |
| Moisture | ≤0.3％ |
In sum, the present invention adopts novel catalyst, selects butter of tin, stannous chloride or butyl titanate---and especially preferred butter of tin, can carry out esterification under higher temperature, and it is excessive 20% that the consumption of hexadecanol reduces to, and efficiently solves the purification problem of product. Adopt toluene, dimethylbenzene or chlorobenzene as reaction dissolvent---especially preferred toluene, the water in the reaction is constantly taken out of, it is relatively thorough that balanced reaction is carried out. Obviously, the present invention compared with prior art need not large excessive hexadecanol, and aftertreatment technology is simple and direct, and production capacity is strong, and product purity is high; Its technique is simple, and is easy to operate, can realize large-scale industrial production.
Claims (6)
1. the preparation method of 3-amino-4-cetyl chlorobenzoate is a raw material with 3-amino-4-chloro-benzoic acid and hexadecanol, it is characterized in that: comprise following processing step---
1. 3-amino-4-chloro-benzoic acid and hexadecanol are joined in the organic solvent, the mol ratio of 3-amino-4-chloro-benzoic acid and hexadecanol is 1:1.0～1.5;
2. rising temperature for dissolving adds tin tetrachloride or tin protochloride or tetrabutyl titanate as catalyzer under stirring, and carries out esterification;
3. reflux dewatering goes out to no longer including moisture;
4. after reaction finishes, reclaim solvent, add refining organic solvent crystallization then;
5. filter out solid, with refining organic solvent recrystallization, oven dry gets 3-amino-4-cetyl chlorobenzoate finished product.
2. by the preparation method of the described 3-amino of claim 1-4-cetyl chlorobenzoate, it is characterized in that: the mol ratio of the 1. middle 3-amino of step-4-chloro-benzoic acid and hexadecanol is 1:1.2.
3. by the preparation method of claim 1 or 2 described 3-amino-4-cetyl chlorobenzoates, it is characterized in that: the organic solvent that 1. step is adopted is toluene or dimethylbenzene or chlorobenzene.
4. by the preparation method of claim 1 or 2 described 3-amino-4-cetyl chlorobenzoates, it is characterized in that: step 1. in the consumption of organic solvent be 1～3 times of 3-amino-4-chloro-benzoic acid weight.
5. by the preparation method of claim 1 or 2 described 3-amino-4-cetyl chlorobenzoates, it is characterized in that: the step 2. add-on of middle catalyzer is that the mol ratio of catalyzer and 3-amino-4-chloro-benzoic acid is 0.02～0.4:1.
6. by the preparation method of claim 1 or 2 described 3-amino-4-cetyl chlorobenzoates, it is characterized in that: 4. step is methyl alcohol, ethanol, Virahol, normal hexane or sherwood oil with the refining organic solvent that 5. step is adopted.
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| CN100463900C true CN100463900C (en) | 2009-02-25 |
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| CN110183336A (en) * | 2019-06-10 | 2019-08-30 | 河北工业大学 | A kind of preparation method of 3- amino -4- cetyl chlorobenzoate |
| CN112266331A (en) * | 2020-12-14 | 2021-01-26 | 苏州开元民生科技股份有限公司 | Preparation method of 3-amino-4-chlorobenzoic acid cetyl ester |
| CN114057591B (en) * | 2022-01-14 | 2022-04-05 | 苏州开元民生科技股份有限公司 | Synthesis method of 3-amino-4-chlorobenzoic acid cetyl ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286766A (en) * | 1996-04-23 | 1997-11-04 | Fuso Kagaku Kogyo Kk | Production of higher alcohol ester of amino-chlorobnenzoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286766A (en) * | 1996-04-23 | 1997-11-04 | Fuso Kagaku Kogyo Kk | Production of higher alcohol ester of amino-chlorobnenzoic acid |
Non-Patent Citations (6)
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| DOTP酯化反应规律的研究. 曾崇余.南京化工学院学报，第16卷第4期. 1994 |
| DOTP酯化反应规律的研究. 曾崇余.南京化工学院学报，第16卷第4期. 1994 * |
| 四氯化锡催化剂在精细有机合成中的应用研究进展. 张敏等.零陵学院学报，第25卷第6期. 2004 |
| 四氯化锡催化剂在精细有机合成中的应用研究进展. 张敏等.零陵学院学报，第25卷第6期. 2004 * |
| 无水氯化亚锡催化合成苯甲酸乙酯. 牛梅菊等.聊城师院学报(自然科学版)，第9卷第1期. 1996 |
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Owner name: SUZHOU KAIYUAN MINSHENG SCIENCE +. TECHNOLOGY CO., Free format text: FORMER OWNER: SUZHOU SUZHOU KAIYUAN MINSHENG SCI+TECH CORP. LTD. Effective date: 20090605 |
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