CN116354850B - 一种甲氰菊酯的制备方法 - Google Patents
一种甲氰菊酯的制备方法 Download PDFInfo
- Publication number
- CN116354850B CN116354850B CN202310286177.1A CN202310286177A CN116354850B CN 116354850 B CN116354850 B CN 116354850B CN 202310286177 A CN202310286177 A CN 202310286177A CN 116354850 B CN116354850 B CN 116354850B
- Authority
- CN
- China
- Prior art keywords
- fenpropathrin
- phenoxy
- preparation
- organic solvent
- oxo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XQUXKZZNEFRCAW-UHFFFAOYSA-N fenpropathrin Chemical compound CC1(C)C(C)(C)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 XQUXKZZNEFRCAW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 m-phenoxyl-2-oxo-phenylacetaldehyde oxime Chemical compound 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- FZCDBGYCFVKRDV-UHFFFAOYSA-N 1-(3-phenoxyphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1 FZCDBGYCFVKRDV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical group CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012414 tert-butyl nitrite Substances 0.000 claims abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical group FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000005837 enolization reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 239000002728 pyrethroid Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- DSQFSFBBPSALMS-UHFFFAOYSA-N 2-bromo-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(Br)C1=CC=CC(OC=2C=CC=CC=2)=C1 DSQFSFBBPSALMS-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种甲氰菊酯的制备方法,属于医药中间体技术领域。以间苯氧基苯乙酮为原料,首先在酸性条件下烯醇式化,并与亚硝酸叔丁酯α位取代得到间苯氧基‑2‑氧代苯乙醛肟,随后对羰基还原得到间苯氧基‑2‑羟基苯乙醛肟,最后与2,2,3,3‑四甲基环丙烷羧酸在催化剂作用下回流脱水得到甲氰菊酯,该方法原料易得,避免了采用剧毒性氰化物引入氰基,降低安全隐患,产品质量得到保障,化学纯度99.0%以上,适用于工业规模化生产。
Description
技术领域
本发明涉及一种甲氰菊酯的制备方法,属于医药中间体中的化学合成技术领域。
背景技术
拟除虫菊酯是一类重要的仿生型杀虫剂,是国家提倡推广的农药产品,其中甲氰菊酯是拟除虫菊酯类农药,对害虫具有很强的触杀、驱避和胃毒作用,即使在低温下也有较好的效果,它还克服了其他菊酯类农药不杀螨虫的特点,且对人畜中等毒性,被称为第三代新农药。
甲氰菊酯,CAS:64257-84-7,英文名称:Fenpropathrin,作为菊酯类典型的农药。甲氰菊酯具有低毒、杀虫谱广、用量少、无残毒、无公害、光稳定性好、杀螨特效,不仅能在农田中大规模使用,还可以用于防治室内害虫,甲氰菊酯可以通过对中枢神经***和末梢神经***的作用,阻断刺激物的传导,对害虫起迅速灭杀作用,因而具有较好的速效性。
甲氰菊酯难点往往是氰基引入,如专利US4254050,1981,A中,采用3-苯氧基苯甲醛、2,6-二甲基-2,6-二氮杂庚烷、***和2,2,3,3-四甲基环丙烷酰氯一锅法合成制备得到甲氰菊酯,该方法合成操作方便,但用到***这样剧毒产品,对安全生产产生很大隐患,不利于工业化规模生产。其反应方程式如下:
专利US4061664,1977,A报道采用α-氰基-3-苯氧基苄基溴与2,2,3,3-四甲基环丙烷羧酸在碳酸钾水溶液中,利用相转移催化剂作用下合成甲氰菊酯,该方法原料α-氰基-3-苯氧基苄基溴成本高,不利于规模化生产。其反应方程式如下:
文献[Journal ofAgricultural and Food Chemistry,1998,vol.46,#6,p.2211-2221]报道中采用α-氰基-3-苯氧基苄醇与2,2,3,3-四甲基环丙烷酰氯反应制备得到甲氰菊酯,反应效果特别好,但原料成本较高,不利于工业规模生产。其反应方程式如下:
针对上述方法的不足,有必要对合成工艺进行优化,寻找流程更为简便有效,可避免采用氰化物引入氰基,安全隐患低且总收率较高的制备方法,以适应工业化生产,满足日益增长的市场需求。
发明内容
为了克服上述技术缺陷,本发明公开了一种甲氰菊酯的制备方法。以间苯氧基苯乙酮为原料,首先在酸性条件下烯醇式化,并与亚硝酸叔丁酯α位取代得到间苯氧基-2-氧代苯乙醛肟,随后将用还原剂对羰基还原得到间苯氧基-2-羟基苯乙醛肟,最后与2,2,3,3-四甲基环丙烷羧酸在催化剂作用下回流脱水得到甲氰菊酯,该方法原料易得,避免了用到氰化物引入氰基,降低安全隐患,产品质量得到保障,化学纯度99.0%以上,适用于工业规模化生产。
本发明所述一种甲氰菊酯的制备方法,包括如下步骤:
第一步:将间苯氧基苯乙酮、盐酸和有机溶剂混合,加入亚硝酸酯反应,得到间苯氧基-2-氧代苯乙醛肟;
第二步:间苯氧基-2-氧代苯乙醛肟在有机溶剂中与还原剂反应,得到间苯氧基-2-羟基苯乙醛肟;
第三步:间苯氧基-2-羟基苯乙醛肟和2,2,3,3-四甲基环丙烷羧酸,在催化剂存在下,有机溶剂中升温回流分水,得到甲氰菊酯。
进一步地,在上述技术方案中,第一步中,所述有机溶剂选自四氢呋喃或2-甲基四氢呋喃,盐酸选自25-36%盐酸。
进一步地,在上述技术方案中,第一步中,所述亚硝酸酯选自亚硝酸叔丁酯或亚硝酸异戊酯。
进一步地,在上述技术方案中,第一步中,所述间苯氧基苯乙酮、盐酸与亚硝酸酯摩尔比为1:0.03-0.05:1.15-1.20。
进一步地,在上述技术方案中,第二步中,所述还原剂选自硼氢化钠、硼氢化钾或异丙醇铝。
进一步地,在上述技术方案中,第二步中,所述间苯氧基-2-氧代苯乙醛肟与还原剂摩尔比例为1:1.05-1.20。
进一步地,在上述技术方案中,第三步中,所述催化剂选自三(五氟苯基)硼烷。
进一步地,在上述技术方案中,第三步中,所述有机溶剂选自1,4-二氧六环/甲苯或1,4-二氧六环/正庚烷组成的混合溶剂。
进一步地,在上述技术方案中,第三步中,所述间苯氧基-2-羟基苯乙醛肟、2,2,3,3-四甲基环丙烷羧酸与催化剂摩尔比为1:0.95-1.02:0.01-0.05。
发明有益效果
1、采用绿色硝化试剂亚硝酸酯,其活性高,价格低廉,官能团兼容性好。
2、通过三(五氟苯基)硼烷这样非传统路易斯酸催化剂,实现缩合和脱水同时完成,脱水效率高。
3、避免了剧毒品***或***的使用,省去了繁琐的***购买流程,同时大大降低了安全隐患。
具体实施例
下面通过具体实例对本发明进行进一步说明。这些实施例应理解为仅用于说明本发明而不用于限制本发明的保护范围。在阅读了本发明记载的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等效变化和修改同样落入本发明权利要求所限定的范围。
实施例1
氮气保护下,室温下向反应瓶内加入间苯氧基苯乙酮212g(1.0mol)、浓盐酸5g和2-甲基四氢呋喃210mL,搅拌均匀后,降温至0-5℃下,控温0-10℃滴加亚硝酸异戊酯140.6g(1.20mol),滴加结束后缓慢升温至35-38℃反应2小时,取样HPLC原料剩余<4%,降温至0℃,加入水淬灭,静置分层,水相用2-甲基四氢呋喃萃取,合并有机相,30℃减压浓缩至不流液,加入正庚烷打浆,过滤得到间苯氧基-2-氧代苯乙醛肟196.9g,HPLC99.3%,收率81.6%。1HNMR(400MHz,CDCl3):8.56(s,1H),8.09-7.75(m,8H),7.48(dd,2H).
实施例2
氮气保护下,室温下向反应瓶内加入间苯氧基苯乙酮212g(1.0mol)、浓盐酸5g和四氢呋喃200mL,搅拌均匀后,降温至0-5℃下,控温0-10℃滴加亚硝酸叔丁酯118.6g(1.15mol),滴加结束后缓慢升温至35-38℃反应2小时,取样HPLC原料剩余3%,降温至0℃,加入水淬灭,加入甲基叔丁基醚,静置分层,水相用甲基叔丁基醚萃取,合并有机相,30℃减压浓缩至不流液,加入正庚烷打浆,过滤得到间苯氧基-2-氧代苯乙醛肟203.4g,HPLC99.4%,收率84.3%。
实施例3
氮气保护下,反应瓶中将间苯氧基-2-氧代苯乙醛肟48.3g(0.2mol)和300mL异丙醇搅拌溶清,接着滴加异丙醇铝49g(0.24mol)/240mL甲苯混合溶液。滴加结束后升温至50-55℃反应4小时,随后降温至0℃,加入8%酒石酸钾钠水溶液淬灭,静置分层,蒸馏除去异丙醇,水相二氯甲烷萃取,合并有机相,饱和食盐水洗涤,有机相减压浓缩至不流液,加入正庚烷热打浆纯化,得到间苯氧基-2-羟基苯乙醛肟41.6g,HPLC 97.8%,收率85.5%。1HNMR(400MHz,CDCl3):10.98(s,1H),7.76-7.24(m,10H),6.79(dd,2H).
实施例4
氮气保护下,反应瓶中加入间苯氧基-2-氧代苯乙醛肟48.3g(0.2mol)和350mL四氢呋喃混合,降温至0℃,分批加入硼氢化钠7.9g(0.21mol),随后室温反应1.5小时,加入0.5M盐酸淬灭,加入甲基叔丁基醚萃取,静置分层,保留有机相,水相用二氯甲烷萃取,合并有机相,减压浓缩,加入正庚烷热打浆纯化,得到间苯氧基-2-羟基苯乙醛肟44.1g,HPLC96.1%,收率90.6%。
实施例5
反应瓶中加入间苯氧基-2-羟基苯乙醛肟24.3g(0.1mol)、2,2,3,3-四甲基环丙烷羧酸13.9g(0.098mol)、三(五氟苯基)硼烷2.6g(0.005mol)、1,4-二氧六环100mL和甲苯130mL混合,升温至60℃反应1小时,随后继续升温至回流分水7小时,降温后减压浓缩蒸馏剩余至3.0-3.5倍质量,加入正庚烷打浆纯化得到甲氰菊酯31.9g,收率91.2%,HPLC99.8%。1HNMR(400MHz,CDCl3):7.42-7.01(m,9H),6.36(s,1H),1.27(s,3H),1.26(s,1H),1.22(s,3H),1.21(s,3H),1.18(s,3H).
实施例6
反应瓶中加入间苯氧基-2-羟基苯乙醛肟24.3g(0.1mol)、2,2,3,3-四甲基环丙烷羧酸13.9g(0.098mol)、三(五氟苯基)硼烷2.6g(0.005mol)、1,4-二氧六环140mL和正庚烷140mL混合,升温至60℃反应1小时,随后继续升温至回流分水10小时,降温后减压浓缩蒸馏剩余至3.5-4.0倍质量,加入正庚烷打浆纯化得到甲氰菊酯32g,收率91.6%,HPLC 99.4%。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种甲氰菊酯的制备方法,其特征在于,包括如下步骤:
第一步:将间苯氧基苯乙酮、盐酸和有机溶剂混合,加入亚硝酸酯反应,得到间苯氧基-2-氧代苯乙醛肟;
第二步:间苯氧基-2-氧代苯乙醛肟在有机溶剂中与还原剂反应,得到间苯氧基-2-羟基苯乙醛肟;所述还原剂选自硼氢化钠或异丙醇铝;
第三步:间苯氧基-2-羟基苯乙醛肟和2,2,3,3-四甲基环丙烷羧酸,在催化剂存在下,有机溶剂中升温回流分水,得到甲氰菊酯;所述催化剂选自三(五氟苯基)硼烷。
2.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第一步中,所述有机溶剂选自四氢呋喃或2-甲基四氢呋喃,盐酸选自25-36%盐酸。
3.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第一步中,所述亚硝酸酯选自亚硝酸叔丁酯或亚硝酸异戊酯。
4.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第一步中,所述间苯氧基苯乙酮、盐酸与亚硝酸酯摩尔比为1:0.03-0.05:1.15-1.20。
5.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第二步中,所述间苯氧基-2-氧代苯乙醛肟与还原剂摩尔比为1:1.05-1.20。
6.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第三步中,所述有机溶剂选自1,4-二氧六环/甲苯或1,4-二氧六环/正庚烷组成的混合溶剂。
7.根据权利要求1所述甲氰菊酯的制备方法,其特征在于:第三步中,所述间苯氧基-2-羟基苯乙醛肟、2,2,3,3-四甲基环丙烷羧酸与催化剂摩尔比为1:0.95-1.02:0.01-0.05。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310286177.1A CN116354850B (zh) | 2023-03-23 | 2023-03-23 | 一种甲氰菊酯的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310286177.1A CN116354850B (zh) | 2023-03-23 | 2023-03-23 | 一种甲氰菊酯的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116354850A CN116354850A (zh) | 2023-06-30 |
CN116354850B true CN116354850B (zh) | 2024-02-13 |
Family
ID=86941324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310286177.1A Active CN116354850B (zh) | 2023-03-23 | 2023-03-23 | 一种甲氰菊酯的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116354850B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835176A (en) * | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
JPH093029A (ja) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | α−シアノベンジルエステル誘導体の製造方法 |
CN1357538A (zh) * | 2000-12-06 | 2002-07-10 | 南开大学 | 甲氰菊酯的制备方法 |
CN104513178A (zh) * | 2013-09-29 | 2015-04-15 | 青岛好利特生物农药有限公司 | 一种甲氰菊酯的制备方法 |
-
2023
- 2023-03-23 CN CN202310286177.1A patent/CN116354850B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835176A (en) * | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
JPH093029A (ja) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | α−シアノベンジルエステル誘導体の製造方法 |
CN1357538A (zh) * | 2000-12-06 | 2002-07-10 | 南开大学 | 甲氰菊酯的制备方法 |
CN104513178A (zh) * | 2013-09-29 | 2015-04-15 | 青岛好利特生物农药有限公司 | 一种甲氰菊酯的制备方法 |
Non-Patent Citations (1)
Title |
---|
Hai-Yan Shi等.Food and Agricultural Immunology.2011,第22卷(第1期),69-76. * |
Also Published As
Publication number | Publication date |
---|---|
CN116354850A (zh) | 2023-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113651710A (zh) | 3,5-取代-4-氨基三氟苯乙酮及其衍生物的制备方法 | |
CN112707799A (zh) | 一种由苯醚甲环唑异构体制备3,4′-二氯二苯醚的方法 | |
CN116354850B (zh) | 一种甲氰菊酯的制备方法 | |
CN103288635A (zh) | 玉米螟性信息素中12-十四碳烯醇乙酸酯的制备方法 | |
CN112920079A (zh) | 一种酰胺化合物的制备方法 | |
CN109678662B (zh) | 一种乙酸7e,9z-十二碳二烯酯的合成方法 | |
CN110963937B (zh) | 秋水仙碱和别秋水仙碱的不对称合成方法 | |
CN113292399B (zh) | 一种四氟苯菊酯中间体的合成方法 | |
JPH0246590B2 (zh) | ||
CN107915610B (zh) | 一种环十五烷酮的制备方法 | |
CN110066268B (zh) | 3-氨基-2,4-二甲基噻吩的制备方法 | |
US3156725A (en) | Substituted 2-phenoxy and phenylthio-cyclopropylamines | |
CN109180439A (zh) | 一种麦草畏的合成方法 | |
CN110256229A (zh) | 一种制备3-异丁基戊二酸的方法 | |
CN101209968B (zh) | 一种茶毛虫性信息素的改进合成方法 | |
US4212830A (en) | Process for preparing insect pheromones | |
CN112645902B (zh) | 一种1-(4-溴苯基)哌啶的合成方法 | |
CN109699646B (zh) | 一种水稻螟虫信息素成分的制备方法 | |
CN108383723B (zh) | 高纯度、高收率β-甲基戊二酸单甲酯的制备方法 | |
CN106674029B (zh) | 一种他喷他多中间体的制备方法 | |
JPS605582B2 (ja) | 新規の脂環式ケトエステルおよび関連化合物の製法 | |
KR20240033428A (ko) | 매미나방의 성페로몬인 시스-7,8-에폭시-2-메틸옥타데칸의 합성방법 | |
CN116355693A (zh) | 一种橙花醇缩醛酸可控释放茶香精、制备方法及其应用 | |
Derieg et al. | Base-catalyzed elimination reactions of substituted 2-(4-pyridyl) ethylamines | |
CN114751814A (zh) | 一种倍半萜类化合物的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |