二氯菊酸乙酯 | 59609-49-3

• 物质功能分类: 化学农药原药 - 杀虫剂中间体
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 二氯菊酸乙酯
• 英文名称: ethyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
• 英文别名: ethyl 3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate；ethyl 3-(2,2-dichloro-ethenyl)-2,2-dimethylcyclopropanecarboxylate；ethyl 3-(2,2-dichlorethenyl)-2,2-dimethylcyclopropanecarboxylate；3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid ethyl ester；2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropanecarboxylic acid ethyl ester；2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ethyl ester；Cyclopropanecarboxylic acid, 3-(2,2-dichloroethenyl)-2,2-dimethyl-, ethyl ester；ethyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 59609-49-3
• 化学式: C₁₀H₁₄Cl₂O₂
• 分子量: 237.126
• InChiKey: QPTWKDNRYCGMJM-UHFFFAOYSA-N

物化性质

• 沸点：
  338.48°C (rough estimate)
• 密度：
  1.2191 (rough estimate)
• 稳定性/保质期：

  二氯菊酸乙酯是一种无色透明的液体，沸点在93～94℃/101pa和78～88℃/27pa之间，折射率(n²₀ᴰ)为1.4833，相对密度为1.1170。它不溶于水，能溶解于苯、甲苯、氯仿等有机溶剂。

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

SDS

Name:	Ethyl 3-(2 2-dichlorovinyl)-2 2-dimethyl-1 Material Safety Data Sheet
Synonym:
CAS:	59609-49-3

Section 1 - Chemical Product MSDS Name:Ethyl 3-(2 2-dichlorovinyl)-2 2-dimethyl-1 Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
59609-49-3	Cyclopropanecarboxylic acid,3-(2,2-dic	3-(2,2-D	261-826-7

Hazard Symbols: XI
Risk Phrases: 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
The toxicological properties of this material have not been investigated. Use appropriate procedures to prevent opportunities for direct contact with the skin or eyes and to prevent inhalation.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower lids. Get medical aid immediately.
Skin:
Get medical aid. Flush skin with plenty of soap and water for at least 15 minutes while removing contaminated clothing and shoes.
Remove contaminated clothing and shoes.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk or water.
Get medical aid immediately.
Inhalation:
Get medical aid immediately. Remove from exposure to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
Notes to Physician:
Treat symptomatically and supportively.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use agent most appropriate to extinguish fire.
Autoignition Temperature: Not available.
Flash Point: 110 deg C ( 230.00 deg F) NFPA Rating: Not published.
Explosion Limits, Lower: Not available.
Upper: Not available.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Clean up spills immediately, observing precautions in the Protective Equipment section.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Avoid contact with eyes, skin, and clothing. Avoid ingestion and inhalation.
Storage:
Store in a cool, dry place. Keep container closed when not in use.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use process enclosure, local exhaust ventilation, or other engineering controls to control airborne levels.
Personal Protective Equipment Eyes: Wear chemical goggles.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to minimize contact with skin.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements must be followed whenever workplace conditions warrant a respirator's use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Not available.
Appearance: clear, colorless
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Vapor Density: Not available.
Evaporation Rate: Not available.
Viscosity: Not available.
Boiling Point: 119.0 - 120.0 deg C @ 15.00mm Hg
Freezing/Melting Point: 0 deg C
Decomposition Temperature: Not available.
Solubility: Not available.
Specific Gravity/Density: 1.1170g/cm3
Molecular Formula: C10H14Cl2O2
Molecular Weight: 237.13

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, strong oxidants.
Incompatibilities with Other Materials:
Not available.
Hazardous Decomposition Products:
Irritating and toxic fumes and gases.
Hazardous Polymerization: Not available.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 59609-49-3 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Cyclopropanecarboxylic acid,3-(2,2-dichloroethenyl)-2,2-dimethyl-,ethylester - Not listed by ACGIH, IARC, NIOSH, NTP, or OSHA.
See actual entry in RTECS for complete information.

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Section 12 - ECOLOGICAL INFORMATION
For further information, contact Fisher Scientific.

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

CDG/CPL
IMO
Not regulated as a hazardous material.
IATA
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.
Canadian TDG
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 59609-49-3:
Canada
CAS# 59609-49-3 is listed on Canada's DSL/NDSL List.
WHMIS: Not available.
CAS# 59609-49-3 is not listed on Canada's Ingredient Disclosure List.
Exposure Limits
US FEDERAL
TSCA
CAS# 59609-49-3 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

化学性质
二氯菊酸乙酯是一种无色透明液体。其沸点在101帕斯卡下为93～94℃，在27帕斯卡下的沸点为78～88℃。该化合物的折射率为1.4833，相对密度为1.1170。它不溶于水，但能溶解于苯、甲苯、氯仿等有机溶剂中。

用途
二氯菊酸乙酯是合成拟除虫菊酯类农药的重要中间体，可用于制备如氯菊酯、氯氰菊酯、高效氯氰菊酯、四氟苯菊酯和氟氯氰菊酯等多种农药。

生产方法
该化合物的制备方法包括以下几种：

1. Farks法（重氮乙酸酯法） 通过异丁烯与三氯乙醛在AlCl₃催化下缩合，再经乙酰化、锌粉还原和酸催化异构化得到共轭双烯，即1,1-二氯-4-甲基戊二烯-[1,3]。随后，在铜粉的催化作用下与重氮乙酸甲酯（或乙酯）反应生成二氯菊酸甲酯（或乙酯）。

2. 相模法 由2-甲基丁烯[2]-醇[1]（异戊烯醇）和原乙酸甲酯（或乙酯），在丙酸存在下的酸性条件下进行缩合Clasen重排，生成3,3-二甲基戊烯[4]酸甲(乙)酯。该化合物与四氯化碳在过氧化苯甲酰的催化下调聚加成，得3,3-二甲基-4,6,6,6-四氯己烯[5]酸甲(乙)酯。随后，在甲醇钠的作用下脱除氯化氢并环合而成二氯菊酸甲酯（或乙酯）。

3. 相模-库拉莱法 由1,1,1-三氯-2-羟基-4-甲基戊烯[4]经对甲基苯磺酸催化异构化，得到1,1,1-三氯-2-羟基-4-甲基戊烯-[3]。再与原乙酸三甲（乙）酯进行缩合Clasen重排反应，生成3,3-二甲基-4,6,6-三氯己烯[4]酸甲(乙)酯。在环合过程中还生成部分的二氯丁内酯。3,3-二甲基-4,6,6-三氯己烯[4]酸甲（乙）酯再于乙醇钠存在下环合成二氯菊酸甲（乙）酯，而二氯丁内酯通过氯化氢或氯化亚砜在甲（乙）醇溶液中开环生成3,3-二甲基-4,6,6-三氯己烯[4]酸甲(乙)酯并环合成二氯菊酸甲(乙)酯。

4. 偏二氯乙烯法 该方法与相模法类似，但原料不同。避免了使用烯醇和原乙酸酯生成贲亭酸甲酯的步骤，其后续工艺与相模法相同。

5. 用异戊二烯为原料的方法 首先通过与两分子氯化氢反应生成1,3-二氯-3-甲基丁烷，再与偏二氯乙烯反应生成1,1,5-三氯-3,3-二甲基环丁酮。在三乙胺的存在下经Cine重排得2-三氯乙基-3,3-二甲基-4-氯环丁酮，再进行Favorski重排得3-三氯乙基-2,2-二甲基环丙烷羧酸。最后通过碱处理脱去氯化氢即得到二氯菊酸。

6. NRDC法 由蒈醛酸甲酯与三苯基亚甲基二氯化膦进行Wittig反应，生成二氯菊酸甲酯。

反应信息

• 作为反应物：
  描述：

  二氯菊酸乙酯 在 盐酸 、 sodium hydroxide 、 十六烷基三甲基溴化铵 作用下， 以 正己烷 、 水 为溶剂， 生成 二氯菊酸
  参考文献：
  名称：

  Process for the preparation of dihalovinylcyclopropanecarboxylic acids

  摘要：

  本发明涉及一种制备环丙烷羧酸的新工艺，其中环丙烷羧酸的化学式为（I）##STR1## 其中X和Y独立地代表卤素，通过相转移催化剂存在下，在或不在水溶性有机溶剂中，通过相应的具有1到6个碳原子的烷基酯的碱性水解来实现。水解是在2至50重量％的碱性氢氧化物溶液中进行的。如果需要，在适当条件下，可以改变最终产物中原始酯的顺反异构比。化学式（I）的环丙烷羧酸以高纯度获得，并且是杀虫活性拟除虫菊酯的有用中间体。

  公开号：

  US04419524A1
• 作为产物：
  描述：

  3.3-二甲基-4.6,6-三氯己烯[5]酸乙酯 以78%的产率得到二氯菊酸乙酯
  参考文献：
  名称：

  Process for preparation of substituted cyclopropane carboxylic acids and

  摘要：

  当1-卤代-3-烯基-2-醇与邻位羧酸酯和/或酮缩醛反应时，主要反应产物是γ-卤代-δ-不饱和羧酸酯。当这种中间体与碱性物质反应时，形成取代环丙烷羧酸酯。这种酯可以直接用作杀虫剂或农药，也可以在将酯的醇残基转化为其他醇残基后使用。

  公开号：

  US04113968A1

文献信息

• Production of insecticidally active vinyl-cyclopropane carboxylic acid
  申请人：Bayer Aktiengesellschaft

  公开号：US04291176A1

  公开（公告）日：1981-09-22

  Insecticidally active vinyl-cyclopropane carboxylic acid esters of the formula ##STR1## are prepared by reacting ##STR2## in which R.sup.12 is a radical selected from the group consisting of ##STR3## with an alcoholate of the formula M--O--R.sup.8. Various processes for making the intermediates are also described. Many of the intermediates and end products are new.

  公式为##STR1##的杀虫活性乙烯-环丙烷羧酸酯可通过将##STR2##与R.sup.12为从##STR3##中选择的基团反应，与公式M--O--R.sup.8的醇酸盐反应制备而成。还描述了制备中间体的各种方法。许多中间体和最终产品都是新的。
• A Practical and Efficient Synthesis of Fluorinated Pyrethroids.<i>cis</i>-3-(2-Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates
  作者：Mayumi Nishida、Takamasa Fuchikami、Kiyosi Kondo

  DOI：10.1246/cl.1994.703

  日期：1994.4

  A practical and efficient route to fluorinated pyrethroids has been developed which involves the selective formation of the cis cyclopropane ring using intramolecular alkylation of the haloaldehyde and a novel transformation of the aldehydes to the corresponding esters via the cyanohydrins.

  已开发出一种实用且有效的氟化拟除虫菊酯途径，该途径涉及使用卤醛的分子内烷基化选择性形成顺式环丙烷环，并通过氰醇将醛转化为相应的酯。
• Process for preparing dihalovinylcyclopropanecarboxylates
  申请人：Sagami Chemical Research Center

  公开号：US04214097A1

  公开（公告）日：1980-07-22

  Novel syntheses of dihalovinylcyclopropanecarboxylates, including potent insecticides, are described. The processes begin with the reaction between an alkenol and an orthoester to produce a .gamma.-unsaturated carboxylate, followed by the catalyzed addition of a carbon tetrahalide to the double bond and dehydrohalogenation to produce a cyclopropane derivative.

  描述了二卤乙烯基环丙烷羧酸酯的新合成方法，其中包括强效杀虫剂。该过程始于烯醇与正酯之间的反应，产生γ-不饱和羧酸酯，随后通过催化加入碳四卤化物到双键，并进行脱卤化反应，生成环丙烷衍生物。
• A novel chain reaction induced by cathodic reduction. Addition of trichloromethyl anion to aldehydes or vimyl acetate
  作者：Tatsuya Shono、Hiroshi Ohmizu、Souta Kawakami、Shinji Nakano、Naoki Kise

  DOI：10.1016/0040-4039(81)80018-4

  日期：1981.1

  A novel chain reaction induced by cathodic reduction was found in the reaction system consisting of carbon tetrachloride, chloroform, and electrophiles such as aldehydes or vinyl acetate. The current efficiency of addition of trichloromethyl anion to electrophiles was extremely high. Synthesis of an analogue of ethyl chrysanthemate using this new reaction was also described.

  在由四氯化碳，氯仿和亲电子试剂（如醛或乙酸乙烯酯）组成的反应体系中，发现了一种通过阴极还原诱导的新型链反应。目前向亲电子试剂中添加三氯甲基阴离子的效率非常高。还描述了使用该新反应合成菊花酸乙酯的类似物。
• Transition metal catalyzed reactions of diazoesters
  作者：A.J. Anciaux、A. Demonceau、A.F. Noels、R. Warin、A.J. Hubert、P. Teyssié

  DOI：10.1016/s0040-4020(01)91934-9

  日期：——

  of carbenes generated by catalyzed decomposition of diazoesters in the presence of Rh, Pd and Cu catalysts can be controlled to some extent by selecting proper reaction parameters. For a particular diene, the regioselectivity depends both on the catalyst and on the nature of the double-bond (conjugation, substitution).

  在Rh，Pd和Cu催化剂存在下，通过重氮催化催化重氮酸酯分解生成的卡宾的环加成反应，多烯环丙烷化的区域选择性可以在一定程度上控制。对于特定的二烯，区域选择性既取决于催化剂又取决于双键的性质（共轭，取代）。

表征谱图