CN106928051A - A kind of synthetic method of cis lanbda-cyhalothric acid - Google Patents
A kind of synthetic method of cis lanbda-cyhalothric acid Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims description 11
- RLLPVAHGXHCWKJ-HKUYNNGSSA-N (3-phenoxyphenyl)methyl (1r,3r)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-HKUYNNGSSA-N 0.000 claims abstract description 47
- 238000007127 saponification reaction Methods 0.000 claims abstract description 36
- 238000003379 elimination reaction Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 28
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001953 recrystallisation Methods 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- HYPBCSOYFJREHZ-CRCLSJGQSA-N (1S,3S)-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1([C@H]([C@@H]1CC(C(F)(F)F)(Cl)Cl)C(=O)O)C HYPBCSOYFJREHZ-CRCLSJGQSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 abstract description 14
- 229960000490 permethrin Drugs 0.000 abstract description 14
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- 230000008030 elimination Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 3
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000005874 Bifenthrin Substances 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Polymers CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RLLPVAHGXHCWKJ-MJGOQNOKSA-N (3-phenoxyphenyl)methyl (1r,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-MJGOQNOKSA-N 0.000 description 1
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种顺式三氟氯菊酸的合成方法，以顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝60-90：10-40)、碱的水溶液为原料，在相转移催化剂的作用下，经过高温带压皂化消除、无机酸调酸、有机溶剂重结晶后得到顺式三氟氯菊酸。本发明方法将传统的常压皂化消除调整为高温带压皂化消除，并加入相转移催化剂，可以将反式功夫酸转化成顺式三氟氯菊酸，顺式：反式≥99:1，即产物中顺式三氟氯菊酸的含量≥99.0％；该工艺提高了收率，收率大于80％，并且副反应少，合成三氟氯菊酸残液量少。The invention discloses a synthesis method of cis-trifluorochrysanthemum acid, which uses cis,trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethyl Cyclopropyl carboxylate (cis: trans = 60-90: 10-40), alkali aqueous solution as raw materials, under the action of a phase transfer catalyst, undergoes high temperature and pressure saponification elimination, inorganic acid acid adjustment, organic solvent heavy After crystallization, cis-permethrin is obtained. The method of the present invention adjusts the traditional normal pressure saponification elimination to high temperature pressure saponification elimination, and adds a phase transfer catalyst, which can convert the trans kung fu acid into the cis permethrin, cis: trans ≥ 99:1, That is, the content of cis-permethrin in the product is more than or equal to 99.0%; the process improves the yield, and the yield is greater than 80%, and there are few side reactions, and the amount of residual liquid for synthesizing permethrin is small.
Description
技术领域technical field
本发明涉及一种三氟氯菊酸的合成方法，具体涉及一种顺式三氟氯菊酸的合成方法。The invention relates to a synthesis method of permethrin, in particular to a synthesis method of cis-permethrin.
背景技术Background technique
新农药的发展趋势是：高效、安全、经济。拟除虫菊酯是一类在天然除虫菊酯化学结构研究的基础上发展而来的仿生药物，其特点是击倒快、杀虫作用强、广谱、低毒、低残留和易降解，对于高等动物和鸟类低毒性，使用安全，不污染环境。从六十年代后期起，特别是七十年代拟除虫菊酯菊酯的开发进入大发展时期，由于多卤代菊酸系列产品良好的杀虫活性和光稳定性，二氯苯醚菊酯、溴氰菊酯、氯氰菊酯、杀灭菊酯、联苯菊酯和功夫菊酯等优良品种不断出现，拟除虫菊酯的开发和应用有了迅速的发展，拟除虫菊酯已成为农用及卫生杀虫剂的主要支柱产品。但是由于拟除虫菊酯的合成工艺较复杂，成本较高，改进工艺，降低成本已成为拟除虫菊酯产业化的重大课题(顾可权,拟除虫菊酯,华东师范大学出版社)。The development trend of new pesticides is: efficient, safe and economical. Pyrethroids are a class of biomimetic drugs developed on the basis of the research on the chemical structure of natural pyrethroids. They are characterized by fast knockdown, strong insecticidal effect, broad spectrum, low toxicity, low residue and easy degradation. It has low toxicity to birds, is safe to use, and does not pollute the environment. Since the late 1960s, especially in the 1970s, the development of pyrethroids has entered a period of great development. Due to the good insecticidal activity and photostability of polyhalogenated chrysanthemic acid products, permethrin, bromcyanide Excellent varieties such as permethrin, cypermethrin, permethrin, bifenthrin and kungfu permethrin continue to emerge, and the development and application of pyrethroids have developed rapidly. Pyrethroids have become the main agricultural and sanitation insecticides. pillar products. However, since the synthesis process of pyrethroids is relatively complicated and the cost is high, improving the process and reducing costs has become a major issue in the industrialization of pyrethroids (Gu Kequan, Pyrethroids, East China Normal University Press).
由于顺式卤代菊酸生成的大部分酯的杀虫活性比反式的要高得多，因此选择性地合成顺式卤代菊酸一直是科学家们努力攻关的课题。然而在三氟氯菊酸结构中，三元环上2个手性C原子可产生1Rcis、1Scis，1Rtrans、1Strans等四个光学异构体，乙烯双键可产生z体、E体两个几何异构体，由此共有8个异构体；氰醇结构中有一个手性C原子，可生成R体、s体两个光学异构体，因此，由三氟氯菊酸和氰醇缩合而成的三氟氯氰菊酯共含有16个光学异构体，构成8对光学对映体。它们的构型可分别表述为：Z一1Rcis—S Z一1Scis—R Z一1Rtrans—S Z一1Strans—R E一1Rcis—S E一1Scis—R E一1Rtrans—S E一1Strans—RSince most of the esters generated by cis-halochrysanthemic acid have much higher insecticidal activity than trans-halochrysanthenic acid, the selective synthesis of cis-halochrysanthenic acid has been a subject that scientists have been working hard to tackle. However, in the structure of permethrin, the two chiral C atoms on the three-membered ring can produce four optical isomers such as 1Rcis, 1Scis, 1Rtrans, and 1Strans, and the ethylene double bond can produce two geometries of Z-body and E-body. Isomers, so there are 8 isomers in total; there is a chiral C atom in the cyanohydrin structure, which can generate two optical isomers, the R form and the s form. The resulting cyhalothrin contains a total of 16 optical isomers, constituting 8 pairs of optical enantiomers. Their configurations can be expressed as: Z-1Rcis-S Z-1Scis-R Z-1Rtrans-S Z-1Strans-RE-1Rcis-SE-1Scis-R E-1Rtrans-S E-1Strans-R
Z——1Rcis——R Z一1Scis—S Z一1Rtrans—R Z一1Strans—S E一1Rcis—R E一1Scis—S E一1Rtrans—R E一1Strans—S。Z——1Rcis——R Z—1Scis—S Z—1Rtrans—R Z—1Strans—S E—1Rcis—R E—1Scis—S E—1Rtrans—R E—1Strans—S.
而上述诸多结构的异构体中，彼此之间的生物活性差异很大，大量的研究结果表明，Z一1Rcis—S构型的活性最高，因此，上述8对光学对映体中，含有Z一1Rcis—S及Z一1Scis—R的一对对映体，相对其它对映体而言，表现出更高的生物活性；首先通过有择合成，定向环合仅含一对异构体的三氟氯菊酸，再与氰醇缩合而成的三氟氯氰菊酯得到的产物即为高效三氟氯氰菊酯(功夫菊酯，lampda—cyhalothrin)，这是著名的拟除虫菊酯杀虫剂品种，目前已在农业生产上广泛地应用。但是目前从文献报道情况来看，这类合成方法大多存在一定的弊端，主要的问题为产物纯度不高、合成顺反比偏低，需要进行多次重结晶才可以得到仅含一对异构体的三氟氯菊酸、收率低、副产物多。Among the isomers of the above-mentioned many structures, the biological activities are very different from each other. A large number of research results show that the Z-1Rcis-S configuration has the highest activity. Therefore, among the above-mentioned 8 pairs of optical enantiomers, Z A pair of enantiomers of 1Rcis-S and Z-1Scis-R has higher biological activity than other enantiomers; firstly, through selective synthesis, directional cyclization only contains a pair of isomers The product obtained by condensation of permethrin and cyhalothrin with cyanohydrin is high-efficiency cyhalothrin (lampda-cyhalothrin), which is a famous pyrethroid insecticide species. Widely used in agricultural production. However, judging from the current literature reports, most of these synthetic methods have certain drawbacks. The main problems are that the product purity is not high, the synthetic cis-trans ratio is low, and multiple recrystallizations are required to obtain only one pair of isomers. permethrin, low yield and many by-products.
发明内容Contents of the invention
本发明所要解决的技术问题是针对现有技术中存在的不足，而提供一种顺式三氟氯菊酸的合成方法，该方法可以转变产物的构型使之转化成顺式三氟氯菊酸，合成的顺式三氟氯菊酸顺反比高，顺式：反式≥99:1；并且该方法副反应少，残液少。The technical problem to be solved by the present invention is to provide a synthetic method of cis-permethrin for the deficiencies in the prior art, which can change the configuration of the product to convert it into cis-permethrin acid, the synthesized cis-permethrin has a high cis-trans ratio, cis:trans ≥ 99:1; and this method has less side reactions and less residual liquid.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种顺式三氟氯菊酸的合成方法，以顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯、碱的水溶液为原料，在相转移催化剂的作用下，经过高温、微正压皂化消除反应、无机酸调酸、有机溶剂重结晶后得到顺式三氟氯菊酸，方法具体包括以下步骤：A kind of synthetic method of cis-trifluorochrysanthemum acid, with cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropanecarboxylic acid The aqueous solution of ester and alkali is used as the raw material, and under the action of a phase transfer catalyst, cis-permethrin is obtained after saponification elimination reaction under high temperature and slight positive pressure, acid adjustment with inorganic acid, and recrystallization with organic solvent. The method specifically includes the following steps :
(1)皂化消除反应：顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯、碱的水溶液在相转移催化剂的催化作用下，在温度40-170℃、压力0-1.0MPa的条件下进行皂化消除反应，保温2-20h至皂化消除反应结束；(1) Saponification elimination reaction: cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropanecarboxylate and alkali in aqueous solution Under the catalysis of the transfer catalyst, the saponification elimination reaction is carried out at a temperature of 40-170°C and a pressure of 0-1.0MPa, and the temperature is kept for 2-20h until the saponification elimination reaction is completed;
所述的顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯，其顺式：反式为60-90：10-40之间；The cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropanecarboxylate, its cis: trans is 60- 90: between 10-40;
(2)无机酸调酸：皂化消除反应结束后，向反应液中添加无机酸进行调酸，调节pH至6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸；(2) Acid adjustment with inorganic acid: after the saponification elimination reaction is completed, add an inorganic acid to the reaction solution for acid adjustment, adjust the pH to 6.0-6.8, and crystallize and centrifuge the crude product cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于有机溶剂中，经重结晶、离心后得精品顺式三氟氯菊酸。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) is dissolved in an organic solvent, and after recrystallization and centrifugation, the refined cis-permethrin is obtained.
上述技术方案中，步骤(1)中，所述的碱的水溶液与顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯的质量比为1-10:1；优选为1-4:1。In the above technical scheme, in step (1), the aqueous alkali solution and cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethyl The mass ratio of cyclopropanecarboxylate is 1-10:1; preferably 1-4:1.
上述技术方案中，步骤(1)中，所述的相转移催化剂与顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯的质量比为0.02-1:1，优选为0.02-0.2:1。In the above technical scheme, in step (1), the phase transfer catalyst and cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethyl The mass ratio of cyclopropanecarboxylate is 0.02-1:1, preferably 0.02-0.2:1.
上述技术方案中，步骤(1)中，所述的温度优选为100-160℃，压力优选为0-0.5MPa，保温时间优选为6-8h。In the above technical solution, in step (1), the temperature is preferably 100-160°C, the pressure is preferably 0-0.5MPa, and the holding time is preferably 6-8h.
上述技术方案中，步骤(1)中，所述的碱的水溶液，碱的质量分数为30～48％；所述的碱为氢氧化钾、氢氧化钠、TBK中的任意一种，优选为氢氧化钾。In the above technical scheme, in step (1), the aqueous alkali solution has a mass fraction of alkali of 30% to 48%; the alkali is any one of potassium hydroxide, sodium hydroxide, and TBK, preferably Potassium hydroxide.
上述技术方案中，步骤(1)中，所述的相转移催化剂为四丁基溴化铵、苄基三乙基氯化铵、十二烷基三甲基溴化铵、十六烷基三甲基溴化铵、季铵盐、聚乙二醇中的任意一种，优选为四丁基溴化铵或苄基三乙基氯化铵。In the above technical scheme, in step (1), the phase transfer catalyst is tetrabutylammonium bromide, benzyltriethylammonium chloride, dodecyltrimethylammonium bromide, cetyltrimethylammonium Any one of methyl ammonium bromide, quaternary ammonium salt, polyethylene glycol, preferably tetrabutyl ammonium bromide or benzyl triethyl ammonium chloride.
上述技术方案中，步骤(2)中，所述的无机酸为盐酸或者硫酸，优选为盐酸。In the above technical solution, in step (2), the inorganic acid is hydrochloric acid or sulfuric acid, preferably hydrochloric acid.
上述技术方案中，步骤(2)中，所述的无机酸与顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯的摩尔比为0.3-0.8:1，优选为0.4-0.6:1。In the above technical scheme, in step (2), the inorganic acid and cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclo The molar ratio of propionate is 0.3-0.8:1, preferably 0.4-0.6:1.
上述技术方案中，步骤(3)中，所述的有机溶剂为甲醇、乙醇或者氯仿中的任意一种。In the above technical solution, in step (3), the organic solvent is any one of methanol, ethanol or chloroform.
上述技术方案中，步骤(3)中，所述的有机溶剂，与顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯的摩尔比为0.2-1.0:1；优选为0.2-0.6:1。In the above technical scheme, in step (3), the organic solvent, with cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethyl The molar ratio of cyclopropanecarboxylate is 0.2-1.0:1; preferably 0.2-0.6:1.
本发明技术方案的优点在于：本发明方法将传统的常压皂化消除调整为高温微正压皂化消除，并加入相转移催化剂，可以将反式三氟氯菊酸转化成顺式三氟氯菊酸，顺式：反式≥99:1，即产物中顺式三氟氯菊酸的含量≥99.0％；该工艺提高了收率，收率大于80％，并且副反应少，合成三氟氯菊酸残液量少。The advantage of the technical solution of the present invention is that: the method of the present invention adjusts the traditional atmospheric pressure saponification elimination to high temperature micro positive pressure saponification elimination, and adds a phase transfer catalyst, which can convert trans permethrin into cis permethrin Acid, cis: trans ≥ 99:1, that is, the content of cis permethrin in the product ≥ 99.0%; The residual liquid of chrysanthemic acid is less.
具体实施方式detailed description
以下对本发明技术方案的具体实施方式详细描述，但本发明并不限于以下描述内容：The specific implementation of the technical solution of the present invention is described in detail below, but the present invention is not limited to the following description:
实施例1：Example 1:
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝80:20，分子量293，相对含量100％)、100g质量分数为48％的氢氧化钾水溶液和2g相转移催化剂四丁基溴化铵；升温，温度达到110℃时紧闭反应系统，继续升温至160℃，且将系统内的压力升为0.3MPa，在此条件下进行皂化消除反应，保温8h；(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis-form: trans-form=80:20, molecular weight 293, relative content 100%), 100g mass fraction is the aqueous potassium hydroxide solution of 48% and 2g phase-transfer catalyst tetrabutyl ammonium bromide; Heating up, temperature Close the reaction system when it reaches 110°C, continue to heat up to 160°C, and increase the pressure in the system to 0.3MPa, carry out saponification elimination reaction under this condition, and keep warm for 8h;
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节pH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸68g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after the central control is qualified, and 30g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0-6.8. The crude product after crystallization and centrifugation 68g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精顺式三氟氯菊酸66.7g，经气谱内标法分析其中顺式三氟氯菊酸含量99.95％，收率80.59％。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) was dissolved in 35g of methanol, and after recrystallization and centrifugation, 66.7g of refined cis-permethrin was obtained, which was analyzed by gas spectrometry The content of cis-permethrin was analyzed by internal standard method to be 99.95%, and the yield was 80.59%.
实施例2：Example 2:
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝90:10，分子量293，相对含量100％)、100g质量分数为48％的氢氧化钾水溶液和5g相转移催化剂四丁基溴化铵；升温，温度达到110℃时紧闭反应系统，继续升温至160℃，且将系统内的压力升为0.3MPa，在此条件下进行皂化消除反应，保温8h；(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis-form: trans-form=90:10, molecular weight 293, relative content 100%), 100g mass fraction is the potassium hydroxide aqueous solution of 48% and 5g phase-transfer catalyst tetrabutyl ammonium bromide; Heating up, temperature Close the reaction system when it reaches 110°C, continue to heat up to 160°C, and increase the pressure in the system to 0.3MPa, carry out saponification elimination reaction under this condition, and keep warm for 8h;
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节pH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸68.5g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after the central control is qualified, and 30g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0-6.8. The crude product after crystallization and centrifugation 68.5g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精顺式三氟氯菊酸67.5g，其中顺式三氟氯菊酸含量99.93％，收率81.56％。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) was dissolved in 35g of methanol, and after recrystallization and centrifugation, 67.5g of refined cis-permethrin was obtained, of which cis- The content of permethrin is 99.93%, and the yield is 81.56%.
实施例3：Example 3:
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝75:25，分子量293，相对含量100％)、125g质量分数为30％的氢氧化钠水溶液和5g相转移催化剂四丁基溴化铵；升温，温度达到110℃时紧闭反应系统，继续升温至160℃，且将系统内的压力升为0.3MPa，在此条件下进行皂化消除反应，保温8h；(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis: trans=75:25, molecular weight 293, relative content 100%), 125g mass fraction is 30% sodium hydroxide aqueous solution and 5g phase transfer catalyst tetrabutyl ammonium bromide; Heating up, temperature Close the reaction system when it reaches 110°C, continue to heat up to 160°C, and increase the pressure in the system to 0.3MPa, carry out saponification elimination reaction under this condition, and keep warm for 8h;
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节pH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸69.5g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after the central control is qualified, and 30g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0-6.8. The crude product after crystallization and centrifugation 69.5g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精顺式三氟氯菊酸67.3g，其中顺式三氟氯菊酸含量99.90％，收率81.32％。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) was dissolved in 35g of methanol, and after recrystallization and centrifugation, 67.3g of refined cis-permethrin was obtained, of which cis- The content of permethrin is 99.90%, and the yield is 81.32%.
实施例4：Example 4:
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝80:20，分子量293，相对含量100％)、125g质量分数为30％的氢氧化钠水溶液和5g相转移催化剂四丁基溴化铵；升温，温度达到110℃时紧闭反应系统，继续升温至140℃，且将系统内的压力升为0.2MPa，在此条件下进行皂化消除反应，保温8h；(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis:trans=80:20, molecular weight 293, relative content 100%), 125g mass fraction is 30% sodium hydroxide aqueous solution and 5g phase transfer catalyst tetrabutyl ammonium bromide; Heating up, temperature Close the reaction system when it reaches 110°C, continue to raise the temperature to 140°C, and increase the pressure in the system to 0.2MPa, carry out saponification elimination reaction under this condition, and keep it warm for 8 hours;
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节pH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸69.5g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after the central control is qualified, and 30g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0-6.8. The crude product after crystallization and centrifugation 69.5g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精品顺式三氟氯菊酸67.1g，其中顺式三氟氯菊酸含量99.93％，收率81.08％。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) was dissolved in 35g of methanol, and after recrystallization and centrifugation, 67.1g of fine cis-permethrin was obtained, of which cis- The content of permethrin is 99.93%, and the yield is 81.08%.
实施例5：Example 5:
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝65:35，分子量293，相对含量100％)、125g质量分数为30％的氢氧化钠水溶液和5g相转移催化剂四丁基溴化铵；升温，温度达到110℃时紧闭反应系统，继续升温至160℃，且将系统内的压力升为0.3MPa，在此条件下进行皂化消除反应，保温12h；(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis:trans=65:35, molecular weight 293, relative content 100%), 125g mass fraction is 30% sodium hydroxide aqueous solution and 5g phase transfer catalyst tetrabutyl ammonium bromide; Heating up, temperature Close the reaction system when it reaches 110°C, continue to heat up to 160°C, and increase the pressure in the system to 0.3MPa, carry out saponification elimination reaction under this condition, and keep warm for 12h;
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节pH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸68g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after the central control is qualified, and 30g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0-6.8. The crude product after crystallization and centrifugation 68g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精品顺式三氟氯菊酸66.9g，其中顺式三氟氯菊酸含量99.95％，收率80.84％。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) is dissolved in 35g of methanol, and after recrystallization and centrifugation, 66.9g of fine cis-permethrin is obtained, wherein cis- The content of permethrin is 99.95%, and the yield is 80.84%.
对比实施例1：常压条件下合成顺式三氟氯菊酸Comparative Example 1: Synthesis of cis-permethrin under normal pressure conditions
一种顺式三氟氯菊酸的合成方法，具体包括以下步骤：A synthetic method for cis-permethrin, specifically comprising the following steps:
(1)皂化消除反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝80:20，分子量293，相对含量100％)、116g质量分数为30％的氢氧化钠水溶液；升温回流常压下进行皂化消除反应，保温12h(1) Saponification elimination reaction: In a 500ml four-necked flask, add 100g cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcycline Propylcarboxylate (cis:trans = 80:20, molecular weight 293, relative content 100%), 116g of 30% sodium hydroxide aqueous solution by mass fraction; saponification elimination reaction was carried out under reflux and normal pressure, and kept for 12h
(2)无机酸调酸：皂化消除反应结束后，中控合格后降温至20℃，向反应液水层中添加30g盐酸进行调酸，调节PH＝6.0～6.8，经结晶、离心后的粗品顺式三氟氯菊酸60g；(2) Acid adjustment with inorganic acid: After the saponification and elimination reaction is completed, the temperature is lowered to 20°C after passing the central control, and 30 g of hydrochloric acid is added to the aqueous layer of the reaction solution for acid adjustment, and the pH is adjusted to 6.0 to 6.8. The crude product after crystallization and centrifugation 60g of cis-permethrin;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于35g甲醇中，经重结晶、离心后得精品顺式三氟氯菊酸58g，其中顺式三氟氯菊酸含量99.90％，收率70.08％。(3) Organic solvent recrystallization: the crude product cis-permethrin that step (2) obtains is dissolved in 35g methanol, after recrystallization, centrifugation, obtain fine-quality cis-permethrin 58g, wherein cis-3 The content of bifenthrin is 99.90%, and the yield is 70.08%.
对比实施例2：本领域制备顺式三氟氯菊酸的传统方法Comparative example 2: the traditional method of preparing cis-permethrin in this area
(1)皂化反应：在500ml四口烧瓶中，依次加入100g顺,反-3-(2,2-二氯-3,3,3-三氟丙基)-2,2-二甲环丙羧酸酯(顺式：反式＝80:20，分子量293，相对含量100％)、116g质量分数为30％的氢氧化钠水溶液、60g无水甲醇；升温回流进行皂化消除反应，反应到中控指标合格即为皂化反应终点。反应结束后，脱出甲醇；(1) Saponification reaction: In a 500ml four-neck flask, add 100g of cis, trans-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropane in sequence Carboxylate (cis: trans=80:20, molecular weight 293, relative content 100%), 116g mass fraction is 30% sodium hydroxide aqueous solution, 60g anhydrous methanol; Refluxing temperature rises and carries out saponification elimination reaction, reacts in The control index qualified is the end point of saponification reaction. After the reaction finishes, methanol is removed;
(2)无机酸调酸：皂化反应脱甲醇结束后，降温至20℃，向反应液水层中添加35g盐酸进行调酸，调节pH＝2.0～4.0，经结晶、离心后的粗品顺式三氟氯菊酸60g，含顺体在93％；(2) Acid adjustment with inorganic acid: After the saponification reaction of methanol removal is completed, cool down to 20°C, add 35g of hydrochloric acid to the aqueous layer of the reaction solution for acid adjustment, and adjust the pH to 2.0 to 4.0. After crystallization and centrifugation, the crude product cis-tri Flupermethrin 60g, containing 93% cis-body;
(3)有机溶剂重结晶：将步骤(2)得到的粗品顺式三氟氯菊酸溶于60g甲醇中，经重结晶、离心后得精品顺式三氟氯菊酸58g，干燥后即得到白色粉状结晶三氟氯菊酸工业品，其中顺式三氟氯菊酸含量98％，收率70％左右。(3) Organic solvent recrystallization: the crude product cis-permethrin obtained in step (2) is dissolved in 60g of methanol, after recrystallization and centrifugation, 58g of fine cis-permethrin is obtained, which is obtained after drying White powdery crystalline permethrin industrial product, wherein the content of cis-permethrin is 98%, and the yield is about 70%.
上述实例只是为说明本发明的技术构思以及技术特点，并不能以此限制本发明的保护范围。凡根据本发明的实质所做的等效变换或修饰，都应该涵盖在本发明的保护范围之内。The above examples are only for illustrating the technical concept and technical characteristics of the present invention, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention shall fall within the protection scope of the present invention.
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