CN104230692A - Preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid - Google Patents
Preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid Download PDFInfo
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- CN104230692A CN104230692A CN201410414108.5A CN201410414108A CN104230692A CN 104230692 A CN104230692 A CN 104230692A CN 201410414108 A CN201410414108 A CN 201410414108A CN 104230692 A CN104230692 A CN 104230692A
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- dimethyl
- cyclopropane dicarboxylic
- dicarboxylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Abstract
The invention discloses a preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid, which comprises the following steps: sequentially adding 3-carene, cetyl sodium sulfate and water into a reactor, gradually adding potassium permanganate into the reactor, stirring uniformly, regulating the temperature of the reactor, carrying out oxidation reaction, filtering, collecting the filtrate and filtration residue for later use, washing the filtration residue with water, collecting the washing solution, merging the filtrate and washing solution to obtain a mixed solution, regulating the pH value of the mixed solution, adding benzene for extraction, collecting the water layer solution, regulating the pH value of the water layer solution, heating for concentration, filtering, washing with water, and drying to obtain the 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid. By preparing the 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid from the 3-carene, the method shortens the reaction route and lowers the production cost.
Description
Technical field
The present invention relates to technical field of chemical synthesis, the preparation method of especially a kind of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
Background technology
3,3-dimethyl-1,2-cyclopropane dicarboxylic acid is a kind of raw material of desirable synthetic drugs, and its molecular formula is C
7h
10o
4, structural formula is as follows:
At present, the synthesis of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid take chrysanthemum monocarboxylate as raw material, be prepared from through reactions such as peroxidation, saponification and acidifyings, its process is comparatively complicated, and chrysanthemum monocarboxylate expensive raw material price, finally cause the production cost of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid higher.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid, the method is with 3-carene for raw material, and object is the problem that solution 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid production cost is high.
In order to solve the problem, the technical solution used in the present invention is:
The preparation method of these 3,3-dimethyl-1,2-cyclopropane dicarboxylic acids, comprises the following steps:
A, 3-carene, Sodium palmityl sulfate and water to be added in reactor successively, in reactor, progressively add potassium permanganate, stir, regulate temperature of reactor to carry out oxidizing reaction;
B, the filtrate of collecting step A reaction gained respectively and filter residue, filtrate is stand-by, and filter residue adds water washing 8 times, collects washings, described filtrate and washings is merged and obtains mixing solutions;
C, described mixing solutions pH value is adjusted to 10, then adds benzene and extract 3 times ~ 5 times, collect water layer solution; Wherein, benzene and mixed liquor volume are than being 1:4;
D, the pH value of described water layer solution is adjusted to 2, heating is concentrated, filters, and washing is dried, namely obtained 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
In technique scheme, scheme can also be more specifically: 3-carene, Sodium palmityl sulfate, and the mass ratio of water and potassium permanganate is 1:0.05:3.5 ~ 10:2.5 ~ 9.
Further, oxidation time is 5 hours ~ 15 hours, and temperature is 5 DEG C ~ 35 DEG C.
Further, described potassium permanganate added in 3 hours.
Owing to have employed technique scheme, the present invention compared with prior art has following beneficial effect:
1, the present invention is with 3-carene for 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid prepared by raw material, has not only widened the range of application of 3-carene, and provides the preparation method of a kind of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acids completely newly.
2, the present invention is with 3-carene for 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid prepared by raw material, shortens reaction scheme, reduces production cost.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
By 100 grams of 3-carenes, 5 grams of Sodium palmityl sulfates and 350 grams of water add in reactor successively, progressively add 600 grams of potassium permanganate in reactor, within 3 hours, add, stir, and controlling temperature of reaction is 35 DEG C, reacts 5 hours; Filter, collect filtrate and filter residue respectively, filtrate is stand-by, filter residue adds water washing 8 times, collects washings, filtrate and washings is merged and obtains mixing solutions, regulate mixing solutions pH value to 10, the benzene adding 1/4th volumes in mixing solutions extracts 3 times, collects water layer solution, the hydrochloric acid soln regulator solution pH adding 0.1mol/L in water layer solution is that at 2,90 DEG C, heating is concentrated, filters, washing, dries, obtains 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
Embodiment 2
By 1 kilogram of 3-carene, 50 grams of Sodium palmityl sulfates and 10 kg water add in reactor successively, progressively add 2.5 kilograms of potassium permanganate in reactor, within 3 hours, add, stir, and controlling temperature of reaction is 20 DEG C, reacts 10 hours; Filter, collect filtrate and filter residue respectively, filtrate is stand-by, filter residue adds water washing 8 times, collects washings, filtrate and washings is merged and obtains mixing solutions, regulate mixing solutions pH value to 10, the benzene adding 1/4th volumes in mixing solutions extracts 5 times, collects water layer solution, the hydrochloric acid soln adding 0.1mol/L in water layer solution regulates pH to be that at 2,90 DEG C, heating is concentrated, filters, washing, dries, obtains 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
Embodiment 3
By 10 kilograms of 3-carenes, 100 grams of Sodium palmityl sulfates and 70 kg water add in reactor successively, progressively add 90 kilograms of potassium permanganate in reactor, within 3 hours, add, stir, and controlling temperature of reaction is 5 DEG C, reacts 15 hours; Filter, collect filtrate and filter residue respectively, filtrate is stand-by, filter residue adds water washing 8 times, collects washings, filtrate and washings is merged and obtains mixing solutions, regulate mixing solutions pH value to 10, the benzene adding 1/4th volumes in mixing solutions extracts 4 times, collects water layer solution, the hydrochloric acid soln regulator solution pH adding 0.1mol/L in water layer solution is that at 2,90 DEG C, heating is concentrated, filters, washing, dries, obtains 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
Claims (4)
1. the preparation method of dimethyl-1, a 2-cyclopropane dicarboxylic acid, is characterized in that comprising the following steps:
A, 3-carene, Sodium palmityl sulfate and water to be added in reactor successively, in reactor, progressively add potassium permanganate, stir, regulate temperature of reactor to carry out oxidizing reaction;
B, the filtrate of collecting step A reaction gained respectively and filter residue, filtrate is stand-by, and filter residue adds water washing 8 times, collects washings, stand-by filtrate and washings is merged and obtains mixing solutions;
C, described mixing solutions pH value is adjusted to 10, then adds benzene and extract 3 times ~ 5 times, collect water layer solution; Wherein, benzene and mixed liquor volume are than being 1:4;
D, the pH value of described water layer solution is adjusted to 2, heating is concentrated, filters, and washing is dried, namely obtained 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid.
2. the preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acids according to claim 1, is characterized in that: the mass ratio of 3-carene, Sodium palmityl sulfate, water and potassium permanganate is 1:0.05:3.5 ~ 10:2.5 ~ 9.
3. the preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acids according to claim 1 and 2, it is characterized in that: described oxidation time is 5 hours ~ 15 hours, temperature is 5 DEG C ~ 35 DEG C.
4. the preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acids according to claim 1 and 2, is characterized in that: described potassium permanganate added in 3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410414108.5A CN104230692A (en) | 2014-08-21 | 2014-08-21 | Preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid |
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| CN201410414108.5A CN104230692A (en) | 2014-08-21 | 2014-08-21 | Preparation method of 3,3-dimethyl-1,2-cyclopropane dicarboxylic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151279A (en) * | 2014-08-26 | 2014-11-19 | 广西梧松林化集团有限公司 | Synthesis method of caronic anhydride |
| CN115368328A (en) * | 2022-06-07 | 2022-11-22 | 中耀生物科技(苏州)有限公司 | Preparation method and application of caronic anhydride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637823A (en) * | 1969-10-20 | 1972-01-25 | Us Interior | Preparation of caronic acid from delta-3-carene |
-
2014
- 2014-08-21 CN CN201410414108.5A patent/CN104230692A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637823A (en) * | 1969-10-20 | 1972-01-25 | Us Interior | Preparation of caronic acid from delta-3-carene |
Non-Patent Citations (3)
| Title |
|---|
| NAVES,ET AL.: "Etudes sur les matihres vegetales volatiles CLXXV）Sur les produits obtenus a partir de l’ozonolyse du (+)-carene", 《HELVETICA CHIMICA ACTA》, vol. 44, no. 72, 31 December 1961 (1961-12-31), pages 637 - 642 * |
| 边庆花等: "内消旋1,2-环丙烷二羧酸衍生物的合成", 《化学试剂》, vol. 28, no. 4, 31 December 2006 (2006-12-31), pages 237 - 238 * |
| 陈良: "由蒈烯-[2]合成拟除虫菊酸的新方法", 《化学世界》, no. 2, 31 December 1982 (1982-12-31), pages 39 - 40 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151279A (en) * | 2014-08-26 | 2014-11-19 | 广西梧松林化集团有限公司 | Synthesis method of caronic anhydride |
| CN115368328A (en) * | 2022-06-07 | 2022-11-22 | 中耀生物科技(苏州)有限公司 | Preparation method and application of caronic anhydride |
| CN115368328B (en) * | 2022-06-07 | 2023-11-10 | 中耀生物科技(苏州)有限公司 | Preparation method and application of caronic anhydride |
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