CN108530298A - A kind of synthetic method of intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters - Google Patents

A kind of synthetic method of intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters Download PDF

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CN108530298A
CN108530298A CN201810582576.1A CN201810582576A CN108530298A CN 108530298 A CN108530298 A CN 108530298A CN 201810582576 A CN201810582576 A CN 201810582576A CN 108530298 A CN108530298 A CN 108530298A
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methyl esters
sba
reaction
zno
acid methyl
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不公告发明人
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Xuzhou Medical Technology Co Ltd
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Xuzhou Medical Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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

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  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of synthetic method of 2,2 dinethyl cyclopropane carboxylic acid methyl esters of intermediate, CuCl, dichloromethane, senecioic acid methyl esters, CH2Br2, aluminium isopropoxide, SBA 15 and CH3COCl is primary raw material, the synthesis technology of the present invention obtains target product using the cyclopropanization reaction that senecioic acid methyl esters and methylene bromide pass through under the effect of the catalyst, whether there is or not catalyst to have apparent influence to the reaction, type is also to have obvious influence on the reaction, the problems such as catalyst activity is not high, and feed stock conversion is low in traditional preparation method is overcome, without poisonous and harmful substance in production process, the yield of product greatly improves, and can be used as productionization.

Description

A kind of synthetic method of intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters
Technical field
The present invention relates to a kind of synthetic methods of intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters, belong to chemical industry synthesis neck Domain.
Background technology
(structural formula is as follows for 2,2- dinethyl cyclopropane carboxylic acids methyl esters：) it is important medicine intermediate, Middle S- (+) -2,2- dinethyl cyclopropane carboxylic acid methyl esters is the key intermediate for synthesizing kidney dehydrogenation Dipeptidase inhibitor cilastatin, Cilastatin can be suitably used for a variety of bacterium co-infections and aerobic bacteria with the compound preparation Thailand of Imipenem and anaerobic bacteria mixes sense The treatment of dye.The synthesis of racemic modification 2,2- dinethyl cyclopropane carboxylic acid methyl esters has following several:2,2- diformazan basic ring propylene glycol For starting material, generated with cyaniding nak response after being esterified with p-methyl benzenesulfonic acid chlorine；With 2,2- dimethoxys ethylene oxide and three second Base phosphinylidyne yl acetate is raw material, and reacting cyclization through Witting generates；With the chloro- 4- methylpentanoic acid ethyl esters of 4- through intramolecular cyclization Obtain product；After senecioic acid esterification, cyclopropanization reaction synthesis is carried out with methylene bromide.Above several reaction route yields compared with It is low or poor as reaction raw materials thread environment friendly with the potassium cyanide of severe toxicity, it is not ideal reaction route.The present invention adopts It is not high that catalyst activity in traditional preparation method is overcome with self-control catalyst synthesis 2,2- dinethyl cyclopropane carboxylic acid methyl esters, it is former Expect the problems such as conversion ratio is low, without poisonous and harmful substance in production process, greatly improves product yield.
Invention content
The purpose of the present invention is to provide a kind of intermediate 2, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, the party Method can be catalyzed the cyclopropanization reaction of senecioic acid methyl esters and methylene bromide with optimal conditions, have higher product yield.
1, a kind of intermediate 2, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, it is characterised in that this method include with Lower step：
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 17.4g CH2Br2；
Step 2 waits for slowly stirring evenly, and 1.25gCH is slowly added dropwise3There is bubble releasing in COCl solution, be added dropwise, slowly rises Temperature reflux, is slowly added dropwise 52.2g CH after solution blackening2Br2With the mixed solution of 20m1 dichloromethane.
Step 3 is added dropwise, and 12h is reacted in gas phase tracking reaction.After reaction, first prepared saturation is slowly added dropwise Ammonium chloride solution removes the zinc salt generated in reaction system, and filtered on buchner funnel is used after cooling；
Liquid separation goes out organic layer after step 4, filtering, and the organic matter in dichloromethane aqueous phase extracted is used in combination, uses saturated nacl aqueous solution It is washed till neutrality, liquid separation, which merges organic matter and depressurizes, steams solvent, and vacuum distillation obtains target product 2,2- dimethylcyclopropane first Sour methyl esters.
The ZnO@SBA-15-SO3H method for preparing catalyst is as follows：
Step 1 weighs the silicon-based mesoporous molecular sieve SBA-15s of 0.2g after drying and is dispersed in 10mL n-hexanes, in the item of stirring Under part, the aluminium isopropoxide of 0.6g is added into mixed system；Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation Water washing 3 times is collected by centrifugation and obtains ZnO@SBA-15 with 40 DEG C of vacuum drying；
ZnO@SBA-15 obtained by 0.2g above-mentioned steps are immersed in the sulfuric acid solution of 10ml 0.05mo1/L by step 2, are impregnated Product collected by being centrifuged after 4h is placed in Muffle furnace at 400 DEG C through 60 DEG C of vacuum drying and keeps 1h, obtains SBA-15 loads ZnO/SO4 2-Type solid acid；
Solid acid obtained by 0.5g above-mentioned steps is added in the mixed solution of 0.5ml MPTMS and 2ml toluene step 3, Back flow reaction is carried out at 100 DEG C, then centrifuges gains；
Step 4, the hydrogen peroxide that the solid product after above-mentioned centrifugation is added to 10ml30%, 2mL deionized waters and 5mL methanol In mixed solution, 5h is stirred at 30 DEG C, be then centrifuged for, be dried in vacuo obtain sulfonic group modification ZnO@SBA-15-SO3H is catalyzed Agent.
Advantageous effect：The present invention provides a kind of centre 2, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, senecioic acids The cyclopropanization reaction that methyl esters and methylene bromide pass through under the effect of the catalyst obtains target product, and whether there is or not catalyst the reaction Apparent to influence, type is also to have obvious influence on the reaction.When in reaction process use ZnO@SBA-15-SO3H is urged When changing reaction, within the time of control reaction, raw material can reach complete conversion substantially.On the one hand chloroacetic chloride eliminates minor amount of water pair The influence of the reaction system；On the other hand, the catalyst surface in the hydrogen chloride and reaction system of generation aoxidizes film reaction, makes oxygen Change zinc to be activated.Both there is obvious influence to cyclopropanization reaction.Using dichloromethane as single solvent When, raw material substantially completely converts, and dichloromethane improves the concentration and stability of Cabbeen in a solvent.Therefore, tradition is overcome The problems such as catalyst activity is not high in preparation method, and feed stock conversion is low can be used as without poisonous and harmful substance in production process Productionization.
Specific implementation mode
Embodiment 1
1, a kind of intermediate 2, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, it is characterised in that this method includes following step Suddenly：
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 17.4g CH2Br2；
Step 2 waits for slowly stirring evenly, and 1.25gCH is slowly added dropwise3There is bubble releasing in COCl solution, be added dropwise, slowly rises Temperature reflux, is slowly added dropwise 52.2g CH after solution blackening2Br2With the mixed solution of 20m1 dichloromethane.
Step 3 is added dropwise, and 12h is reacted in gas phase tracking reaction.After reaction, first prepared saturation is slowly added dropwise Ammonium chloride solution removes the zinc salt generated in reaction system, and filtered on buchner funnel is used after cooling；
Liquid separation goes out organic layer after step 4, filtering, and the organic matter in dichloromethane aqueous phase extracted is used in combination, uses saturated nacl aqueous solution It is washed till neutrality, liquid separation, which merges organic matter and depressurizes, steams solvent, and vacuum distillation obtains target product 2,2- dimethylcyclopropane first Sour methyl esters.
The ZnO@SBA-15-SO3H method for preparing catalyst is as follows：
Step 1 weighs the silicon-based mesoporous molecular sieve SBA-15s of 0.2g after drying and is dispersed in 10mL n-hexanes, in the item of stirring Under part, the aluminium isopropoxide of 0.6g is added into mixed system；Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation Water washing 3 times is collected by centrifugation and obtains ZnO@SBA-15 with 40 DEG C of vacuum drying；
ZnO@SBA-15 obtained by 0.2g above-mentioned steps are immersed in the sulfuric acid solution of 10ml 0.05mo1/L by step 2, are impregnated Product collected by being centrifuged after 4h is placed in Muffle furnace at 400 DEG C through 60 DEG C of vacuum drying and keeps 1h, obtains SBA-15 loads ZnO/SO4 2-Type solid acid；
Solid acid obtained by 0.5g above-mentioned steps is added in the mixed solution of 0.5ml MPTMS and 2ml toluene step 3, Back flow reaction is carried out at 100 DEG C, then centrifuges gains；
Step 4, the hydrogen peroxide that the solid product after above-mentioned centrifugation is added to 10ml30%, 2mL deionized waters and 5mL methanol In mixed solution, 5h is stirred at 30 DEG C, be then centrifuged for, be dried in vacuo obtain sulfonic group modification ZnO@SBA-15-SO3H is catalyzed Agent.
Embodiment 2
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 13.4g senecioic acids methyl esters and 17.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 3
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 15.4g senecioic acids methyl esters and 17.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 4
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 17.4g senecioic acids methyl esters and 17.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 5
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 19.4g senecioic acids methyl esters and 17.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 6
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 21.4g senecioic acids methyl esters and 17.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 7
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 20.4g CH2Br2；Remaining Step is the same as embodiment 11.
Embodiment 8
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 23.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 9
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 26.4g CH2Br2；Remaining Step is the same as embodiment 1.
Embodiment 10
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 29.4g CH2Br2；Remaining Step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, use the ZnO of equivalent as catalyst, remaining step with Embodiment 1 is identical.
Reference examples 2
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, catalyst is not added, remaining step and embodiment 1 It is identical.
Reference examples 3
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, replace SBA-15, remaining step with the kaolin of equivalent It is identical with embodiment 1.
Reference examples 4
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, replace SBA-15, remaining step with the white carbon of equivalent It is identical with embodiment 1.
Reference examples 5
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, aluminium isopropoxide is not added, remaining step and embodiment 1 is identical.
Reference examples 6
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, the isopropanol of equivalent is added dropwise into mixed system Titanium, remaining step are identical with embodiment 1.
Reference examples 7
It is with 1 difference of embodiment：In the synthesis step 2 of catalyst, soak sulfuric acid concentration is 0.5mol/L；Remaining step It is identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment：In the synthesis step 2 of catalyst, soak is changed to concentration of nitric acid and remains unchanged；Remaining step Suddenly identical with embodiment 1.
Reference examples 9
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, MPTMS and volume of toluene ratio 1：4, remaining step and reality It is identical to apply example 1.
Reference examples 10
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, MPTMS and volume of toluene ratio 1：1, remaining step and reality It is identical to apply example 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
The experimental results showed that catalyst has good catalytic effect to the synthetic reaction of senecioic acid methyl esters and methylene bromide, In one timing of reaction condition, intermediate yield is higher, and catalytic performance is better, otherwise poorer；Senecioic acid methyl esters, methylene bromide matter Amount is than being 2：When 3, other dispensings are fixed, and synthetic effect is best, with embodiment 1 the difference lies in that embodiment 2 to embodiment 10 is divided Not Gai Bian primary raw material senecioic acid methyl esters, methylene bromide dosage and proportioning, in spite of certain effect, but not as good as implement 1 high income of example；Reference examples 1 do not add composite catalyst to reference examples 2 and use ZnO as catalyst, the complete phase of other steps Together, cause product yield to be substantially reduced, it is very big to illustrate that the product of composite catalyst reaction influences；Reference examples 3 to reference examples 4 are used high Respectively as carrier, effect is still bad for ridge soil and white carbon, illustrates that SBA-15 zeolites are preferable carrier materials；Reference examples 5 Aluminium isopropoxide is not added to reference examples 6 and is replaced with isopropyl titanate, and effect is still bad；Reference examples 7 to reference examples 8 use nitric acid Replace and improve sulfuric acid concentration, be catalyzed the variation with obvious effects of reaction, illustrates that sulfuric acid is preferable to catalyst improvement；Reference examples 9 to reference examples MPTMS and volume of toluene ratio change, the surface-active of catalyst changes, and reaction effect is obviously deteriorated, Product yield is substantially reduced；Therefore the synthesis using the catalyst of the present invention to intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters Reaction has excellent catalytic effect.

Claims (2)

1. a kind of intermediate 2, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, it is characterised in that this method includes following step Suddenly：
Step 1, in the 250m1 four-hole boiling flasks equipped with condenser pipe, thermometer and constant pressure funnel, sequentially add 52g ZnO@ SBA-15-SO3H, 7.96g CuCl, 40m1 dichloromethane solvent, 11.4g senecioic acids methyl esters and 17.4g CH2Br2；
Step 2 waits for slowly stirring evenly, and 1.25gCH is slowly added dropwise3There is bubble releasing in COCl solution, be added dropwise, slowly rises Temperature reflux, is slowly added dropwise 52.2g CH after solution blackening2Br2With the mixed solution of 20m1 dichloromethane;
Step 3 is added dropwise, and 12h is reacted in gas phase tracking reaction;
After reaction, first prepared saturated ammonium chloride solution is slowly added dropwise and removes the zinc salt generated in reaction system, it is cooling After use filtered on buchner funnel；
Liquid separation goes out organic layer after step 4, filtering, and the organic matter in dichloromethane aqueous phase extracted is used in combination, uses saturated nacl aqueous solution It is washed till neutrality, liquid separation, which merges organic matter and depressurizes, steams solvent, and vacuum distillation obtains target product 2,2- dimethylcyclopropane first Sour methyl esters.
2. a kind of intermediate 2 according to claim 1, the synthetic method of 2- dinethyl cyclopropane carboxylic acid methyl esters, feature exist In
The ZnO@SBA-15-SO3H method for preparing catalyst is as follows：
Step 1 weighs the silicon-based mesoporous molecular sieve SBA-15s of 0.2g after drying and is dispersed in 10mL n-hexanes, in the item of stirring Under part, the aluminium isopropoxide of 0.6g is added into mixed system；Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation Water washing 3 times is collected by centrifugation and obtains ZnO@SBA-15 with 40 DEG C of vacuum drying；
ZnO@SBA-15 obtained by 0.2g above-mentioned steps are immersed in the sulfuric acid solution of 10ml 0.05mo1/L by step 2, are impregnated Product collected by being centrifuged after 4h is placed in Muffle furnace at 400 DEG C through 60 DEG C of vacuum drying and keeps 1h, obtains SBA-15 loads ZnO/SO4 2-Type solid acid；
Solid acid obtained by 0.5g above-mentioned steps is added in the mixed solution of 0.5ml MPTMS and 2ml toluene step 3, Back flow reaction is carried out at 100 DEG C, then centrifuges gains；
Step 4, the hydrogen peroxide that the solid product after above-mentioned centrifugation is added to 10ml30%, 2mL deionized waters and 5mL methanol In mixed solution, 5h is stirred at 30 DEG C, be then centrifuged for, be dried in vacuo obtain sulfonic group modification ZnO@SBA-15-SO3H is catalyzed Agent.
CN201810582576.1A 2018-06-07 2018-06-07 A kind of synthetic method of intermediate 2,2- dinethyl cyclopropane carboxylic acid methyl esters Pending CN108530298A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112920017A (en) * 2021-01-27 2021-06-08 格林生物科技股份有限公司 Preparation method of dicyclopropyl alkyl derivative compound

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN106311345A (en) * 2016-07-25 2017-01-11 江苏大学 Acid-base bifunctional solid catalyst and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN106311345A (en) * 2016-07-25 2017-01-11 江苏大学 Acid-base bifunctional solid catalyst and preparation method thereof

Non-Patent Citations (1)

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Title
仲崇超: "西司他丁中间体合成工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112920017A (en) * 2021-01-27 2021-06-08 格林生物科技股份有限公司 Preparation method of dicyclopropyl alkyl derivative compound

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Application publication date: 20180914