CN102070439B - Method for preparing (+/-)-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid - Google Patents
Method for preparing (+/-)-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid Download PDFInfo
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- CN102070439B CN102070439B CN 201110006557 CN201110006557A CN102070439B CN 102070439 B CN102070439 B CN 102070439B CN 201110006557 CN201110006557 CN 201110006557 CN 201110006557 A CN201110006557 A CN 201110006557A CN 102070439 B CN102070439 B CN 102070439B
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Abstract
The invention discloses a method for preparing (+/-)-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid, which takes (+/-)-2,2-dimethyl-3-chloroethynylcyclopropanecarboxylic acid as a raw material, and sequentially comprises the steps of: adding low-level fatty alcohol, the (+/-)-2,2-dimethyl-3-chloroethynylcyclopropanecarboxylic acid taken as the raw material, a Lindlar catalyst and an acid binding agent into a reactor; adding hydrogen into the reactor until the pressure is between 0.1 and 1.0MPa for reaction; performing vacuum suction filtration on an obtained reaction product, and performing rotary evaporation on an obtained filtrate under reduced pressure to obtain distillation residue; and performing the corresponding after-treatment on the distillation residue to obtain the (+/-)-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid. The preparation of the (+/-)-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid by adopting the method has the characteristics of concise process, simple and convenient operation, high yield and low cost.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly (±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic ((±)
-2,2-dimethyl-3-vinylcyclopropanecarboxylic acid) synthetic method.
Background technology
(±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic, its molecular formula is C
8H
12O
2, its structural formula is shown in S-1, and sterling is white or faint yellow solid, 39 ~ 43 ℃ of fusing points.This compound is the key intermediate during chrysanthemumic acid and natural chrysanthemum element synthesize.
S-1 。
According to document (P. R. Ortiz de Montellano and S. E. Dinizo,
The Journal of Organic Chemistry 1978,
434323-4328.) report; (±)-2; the prior synthesizing method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is with (±)-2; 2-dimethyl-3-formyl radical methyl cyclopropanecarboxylate (popular name (±)-carane aldehydic acid methyl esters) is raw material, makes through the Wittig reaction with first base three phenyl phosphonium bromides, obtains required carboxylic acid through saponification and acidifying again; total recovery 58% is shown in S-3.
S-2 。
Summary of the invention
The technical problem to be solved in the present invention provides (±) that a kind of technique is succinct, easy and simple to handle, yield is high, cost is low-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic preparation method.
In order to solve the problems of the technologies described above, the invention provides a kind of (±)-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic: with (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid is raw material, may further comprise the steps successively:
1), in reactor, add lower aliphatic pure and mild (±) as raw material-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid behind material dissolution, adds Lindlar catalyzer and acid binding agent; The mol ratio of Lindlar catalyzer and raw material is 1% ~ 10%, and the mol ratio of acid binding agent and raw material is 1.1 ~ 1.3:1;
2), to add hydrogen to pressure in the reactor be 0.1MPa ~ 1.0MPa, reaction is 2 h ~ 14 h under 20 ℃ ~ 50 ℃ temperature of reaction;
3), with step 2) reaction product of gained carries out vacuum filtration, behind the filtrate decompression rotary evaporation of gained, gets the distillation residuum;
4) wash separatory with water after, the distillation residuum is dissolved in toluene; Organic layer with anhydrous sodium sulfate drying after, decompression rotary evaporation desolventizing toluene, the gained light yellow viscous liquid at room temperature leaves standstill after fixing, (±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic.
As (±) of the present invention-2, the preparation method's of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic improvement: acid binding agent is triethylamine, yellow soda ash or salt of wormwood.
As (±) of the present invention-2, the preparation method's of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic further improvement: lower aliphatic alcohols is methyl alcohol, ethanol, n-propyl alcohol or Virahol; The volume/weight ratio of lower aliphatic alcohols and raw material is: 5 mL/g ~ 10mL/g.
As (±) of the present invention-2, the preparation method's of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic further improvement: ethanol is industrial alcohol or the dehydrated alcohol of massfraction 〉=95%.
In the present invention, step 2) hydrogenation reaction gained reaction product is mixture, contains product (i.e. (±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic), catalyzer and byproduct salt in this mixture; Mixture carries out that the gained filter residue is catalyzer and salt behind the vacuum filtration, but uses after the catalyzer flush away salt again; The desolventizing of gained filtrate decompression rotary evaporation, solvent is recyclable to be used again.
The present invention is with (±)-2, and 2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid is raw material, in alcoholic solution, with 5%Pd/BaSO
4(be commercial Lindlar catalyzer, Chinese name: lindlar catalyst) be catalyzer, the adding alkaline matter is acid binding agent, carries out the hydrodechlorination reaction.Products therefrom solution distills desolventizing after filtering, obtains target product (±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic.
The present invention prepares (±)-2, and the reaction equation of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is as follows:
(±) of the present invention-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic has following advantage:
1, directly with (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid rather than methyl esters or ethyl ester are raw material, and (for example JP 52014748 for the existing relevant bibliographical information of the preparation of this compound, JP 52122345, DE 2925570), can save esterolytic reaction, simplified reaction;
2, than the Wittig reaction of carane aldehydic acid and phosphorus ylide, cost of material is more cheap, the reaction conditions milder, and byproduct of reaction is few, and Atom economy is higher;
3, under the Lindlar catalyst action, hydrogenation and one step of dechlorination reaction finish, and can finish reaction under normal pressure and low pressure, and technique is succinct, and side reaction is few, clean and safe;
4, raw material is easy to get.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is (±)-2, the mass spectrum of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic.
Embodiment
Embodiment 1, a kind of (±)-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic, with (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid is raw material, carries out successively following steps:
The adding massfraction is 95% industrial alcohol 100 mL in 250 mL autoclaves, add raw material (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid 17.3 g(100.0 mmol), behind material dissolution, add again acid binding agent triethylamine 12.1 g(120.0 mmol) and Lindlar catalyzer (5%Pd/BaSO
4) 10.7 g(5.0 mmol Pd).Autoclave is hunted leak with nitrogen, uses the interior air of hydrogen exchange still three times, is filled with hydrogen, and still internal pressure 0.1 MPa opens mechanical stirring, is heated to 50 ℃ of reactions, and sampling GC monitoring reaction fills hydrogen to 0.1 MPa behind every sub-sampling, and behind 12 h, raw material transforms complete substantially.The gained reaction mixture is poured out, vacuum filtration, and filtrate adopts decompression rotary evaporation (15 mmHg, 40 ℃) to remove etoh solvent, and solvent is recyclable to be used again.The gained distillation residue are dissolved in the 100 mL toluene, wash (50 mL * 3) with water, tell organic layer (being positioned at the upper strata) with 3 g anhydrous sodium sulfate dryings, rotary evaporation (15 mmHg, 60 ℃) remove solvent toluene, the gained light yellow viscous liquid at room temperature leaves standstill after fixing, obtains solid 12.27 g(yields 87.5%).
Embodiment 2, a kind of (±)-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic, with (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid is raw material, carries out successively following steps:
The adding massfraction is 95% industrial alcohol 100 mL in 250 mL autoclaves, add raw material (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid 17.3 g(100.0 mmol), behind material dissolution, add again acid binding agent yellow soda ash 12.7 g(120.0 mmol), Lindlar catalyzer (5%Pd/BaSO
4) 10.7 g(5.0 mmol Pd).Autoclave is hunted leak with nitrogen, uses the interior air of hydrogen exchange still three times, is filled with hydrogen, and still internal pressure 1.0 MPa open mechanical stirring, are heated to 50 ℃ of reactions, and sampling GC monitoring reaction fills hydrogen to 1.0 MPa behind every sub-sampling, and behind 3 h, raw material transforms complete substantially.The gained reaction mixture is poured out, vacuum filtration, and filtrate adopts decompression rotary evaporation (15 mmHg, 40 ℃) to remove etoh solvent, and solvent is recyclable to be used again.The gained distillation residue are dissolved in the 100 mL toluene, wash (50 mL * 3) with water, tell organic layer with 3 g anhydrous sodium sulfate dryings, rotary evaporation (15 mmHg, 60 ℃) remove solvent toluene, the gained light yellow viscous liquid at room temperature leaves standstill after fixing, obtains solid 12.8 g(yields 91.3 %).
Substrate ((±)-2 of embodiment 3 ~ 10 and embodiment 2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid) consumption is identical with operation steps, but adopt different solvents, catalyst levels, acid binding agent type, reaction pressure, temperature of reaction and reaction times, therefore each reaction conditions and the result with embodiment 3 ~ 10 classifies table 1 as, so that contrast:
Table 1
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. (±)-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is characterized in that: with (±)-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid is raw material, may further comprise the steps successively:
1), in reactor, add lower aliphatic pure and mild (±) as raw material-2,2-dimethyl-3-chloroacetylene basic ring propane carboxylic acid behind material dissolution, adds Lindlar catalyzer and acid binding agent; The mol ratio of Lindlar catalyzer and raw material is 1% ~ 10%, and the mol ratio of acid binding agent and raw material is 1.1 ~ 1.3:1;
2), to add hydrogen to pressure in the reactor be 0.1MPa ~ 1.0MPa, reaction is 2 h ~ 14 h under 20 ℃ ~ 50 ℃ temperature of reaction;
3), with step 2) reaction product of gained carries out vacuum filtration, behind the filtrate decompression rotary evaporation of gained, gets the distillation residuum;
4) wash separatory with water after, the distillation residuum is dissolved in toluene; Organic layer with anhydrous sodium sulfate drying after, decompression rotary evaporation desolventizing toluene, the gained light yellow viscous liquid at room temperature leaves standstill after fixing, (±)-2,2-dimethyl-3-vinylcyclopropanecaracidlic acidlic.
2. (±) according to claim 1-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is characterized in that: described acid binding agent is triethylamine, yellow soda ash or salt of wormwood.
3. (±) according to claim 2-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is characterized in that: described lower aliphatic alcohols is methyl alcohol, ethanol, n-propyl alcohol or Virahol; The volume/weight ratio of described lower aliphatic alcohols and raw material is: 5 mL/g ~ 10mL/g.
4. (±) according to claim 3-2, the preparation method of 2-dimethyl-3-vinylcyclopropanecaracidlic acidlic is characterized in that: described ethanol is industrial alcohol or the dehydrated alcohol of massfraction 〉=95%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL56391A (en) * | 1978-01-10 | 1981-11-30 | Bayer Ag | Process for the separation of stereoisomeric 2,2-dimethyl-3(2-substituted vinyl)cyclopropanecarboxylic acids |
| CN86102323A (en) * | 1985-04-18 | 1986-12-03 | 拜尔公司 | The method for preparing vinyl cyclopropane-carboxylic acid fat |
| CN1397542A (en) * | 2001-07-18 | 2003-02-19 | 住友化学工业株式会社 | Process to enable recemation of optical rotatary vinyl substituted cyclopropane carboxylic compound |
-
2011
- 2011-01-13 CN CN 201110006557 patent/CN102070439B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL56391A (en) * | 1978-01-10 | 1981-11-30 | Bayer Ag | Process for the separation of stereoisomeric 2,2-dimethyl-3(2-substituted vinyl)cyclopropanecarboxylic acids |
| CN86102323A (en) * | 1985-04-18 | 1986-12-03 | 拜尔公司 | The method for preparing vinyl cyclopropane-carboxylic acid fat |
| CN1397542A (en) * | 2001-07-18 | 2003-02-19 | 住友化学工业株式会社 | Process to enable recemation of optical rotatary vinyl substituted cyclopropane carboxylic compound |
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