methyl trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate | 59897-93-7

• 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
• 英文名称: methyl trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate
• 英文别名: methyl 2,2-dimethyl-3-(2,2-dichloroethenyl)cyclopropane-1-carboxylate；methyl 2,2-dimethyl-3-dichlorovinylcyclopropane-1-carboxylate；(1RS,3RS)-Permethrinsaeuremethylester；Cyclopropanecarboxylic acid, 3-(2,2-dichloroethenyl)-2,2-dimethyl-, methyl ester, (1R,3S)-rel-；methyl (1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 59897-93-7；59897-94-8；61898-95-1；61976-30-5；61976-31-6；63805-74-3；74561-29-8；84984-65-6；84984-66-7
• 化学式: C₉H₁₂Cl₂O₂
• 分子量: 223.099
• InChiKey: QJOOIMSFFIUFKX-VDTYLAMSSA-N

物化性质

• 沸点：
  234-235 °C
• 密度：
  1.304
• 溶解度：
  可溶于氯仿（少许）、甲醇（少许）
• 稳定性/保质期：
  <p>遵照规定使用和储存，则不会分解。</p>

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 储存条件：
  存放在阴凉干燥处。

SDS

Name:	Methyl 3-(2 2-dichlorovinyl)-2 2-dimethyl- Material Safety Data Sheet
Synonym:	3-(2,2-Dichloroethenyl)-2,2-dimethyl-cyclopropanecarboxylicacid, methyl este
CAS:	61898-95-1

Section 1 - Chemical Product MSDS Name:Methyl 3-(2 2-dichlorovinyl)-2 2-dimethyl- Material Safety Data Sheet
Synonym:3-(2,2-Dichloroethenyl)-2,2-dimethyl-cyclopropanecarboxylicacid, methyl este

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
61898-95-1	Methyl 3-(2,2-dichlorovinyl)-2,2-dimet	90%	263-308-6

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
Eye:
Causes eye irritation.
Skin:
Causes skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

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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 eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 61898-95-1: Personal Protective Equipment Eyes: Not available.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Clear liquid
Color: colorless
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 234 - 235 deg C
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: > 110 deg C (> 230.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density: 1.304
Molecular Formula: C9H12Cl2O2
Molecular Weight: 223.1

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Hydrogen chloride, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 61898-95-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl- (1-cyclopropane)carboxylate, cis/trans - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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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

IATA
No information available.
IMO
No information available.
RID/ADR
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 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 61898-95-1: No information available.
Canada
CAS# 61898-95-1 is listed on Canada's NDSL List.
CAS# 61898-95-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 61898-95-1 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
二氯菊酸甲酯是一种无色透明液体，沸点在72～74℃（54pa）左右，在0.27kPa（100～105℃）下沸腾。它难溶于水，但能溶于甲苯、苯、氯仿等有机溶剂。

用途
二氯菊酸甲酯的化学名称为(±)顺反-2,2-二甲基-3-(2,2-二氯乙烯基)环丙烷羧酸甲酯。它是拟除虫菊酯的重要中间体，可用于制备多种农药，如氯菊酯、顺式氯氰菊酯、氯氰菊酯、高效氯氰菊酯、四氯苯菊酯和氟氯苯菊酯等。

用途
该化合物主要用于生产菊酯类农药。

生产方法
二氯菊酸甲酯的合成方法主要有以下几种：

1. Farks法（重氮乙酸酯法）：异丁烯与三氯乙醛在AlCl₃催化下缩合，生成一烯醇，再经乙酰化、锌粉还原和酸催化异构化得到共轭双烯。接着，该共轭双烯与重氮乙酸甲酯（乙酯）在铜粉催化下反应，即得二氯菊酸甲酯（乙酯）。

2. 相模法：2-甲基丁烯[2]醇1与原乙酸甲酯（乙酯），在丙酸存在下的缩合Clasen重排，生成3,3-二甲基戊烯[4]酸甲(乙)酯[贲亭酸甲(乙)酯]。后者再与四氯化碳进行调聚加成，并在过氧化苯甲酰存在下得到3,3-二甲基-4,6,6,6-四氯己烯[5]酸甲(乙)酯，然后在甲醇钠存在下脱氯化氢环合而成二氯菊酸甲酯（乙酯）。

3. 相模-库拉莱法：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，生成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，得3,3-二甲基-4,6,6-三氯己烯[4]酸甲(乙)酯。在该过程中还生成部分二氯丁内酯。3,3-二甲基-4,6,6-三氯己烯[4]酸甲(乙)酯在乙醇钠存在下环合生成二氯菊酸甲(乙)酯，而二氯丁内酯可在甲（乙）醇溶液中用氯化氢或氯化亚砜开环生成3,3-二甲基-4,6,6-三氯己烯[4]酸甲(乙)酯，并再环合得到二氯菊酸甲(乙)酯。

4. 偏二氯乙烯法：与相模法类似，但使用的原料不同。从贲亭酸甲酯制备二氯菊酸甲酯的过程与相模法相同。

5. 用异戊二烯为原料的合成方法：先将异戊二烯与两分子氯化氢反应生成2,4,4,4-四氯丁腈，再水解、酰氯化生成2,4,4,4-四氯丁酰氯。在三乙胺存在下加压脱氯化氢生成烯酮，然后和异丁烯在压力下反应生成2-氯-2-三氯乙基-3,3-二甲基环丁酮，在三乙胺存在下经Clasen重排得2-三氯乙基-3,3-二甲基-4-氯环丁酮，再Favorski重排得3-三氯乙基-2,2-二甲基环丙烷羧酸。然后用碱处理脱氯化氢即得二氯菊酸。

6. 环丁酮法：由丙烯腈和四氯化碳在Cu催化剂作用下调聚反应生成2,4,4,4-四氯丁腈，进一步水解酰氯化生成2,4,4,4-四氯丁酰氯。再在三乙胺存在下加压脱氯化氢生成烯酮，经Clasen重排得2-三氯乙基-3,3-二甲基-4-氯环丁酮，然后Favorski重排得3-三氯乙基-2,2-二甲基环丙烷羧酸。最后用碱处理脱氯化氢即得二氯菊酸。

7. NRDC法：由蒈醛酸甲酯与三苯基亚甲基二氯化膦进行Wittig反应，得到二氯菊酸甲酯。

反应信息

• 作为反应物：
  描述：

  methyl trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate 在 sodium hydroxide 、 三乙胺 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 11.0h， 生成 生物氯菊酯
  参考文献：
  名称：

  Badanyan; Stepanyan; Mikaelyan, Russian Journal of Organic Chemistry, 1997, vol. 33, # 1, p. 34 - 41

  摘要：

  DOI：
• 作为产物：
  描述：

  5,5,5-trichloro-2E-pentenoic acid 在 对甲苯磺酸 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 63.0h， 生成 methyl trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate
  参考文献：
  名称：

  Tolstikov, G. A.; Galin, F. Z.; Davletov, R. G., Journal of Organic Chemistry USSR (English Translation), 1986, vol. 22, # 9, p. 1805

  摘要：

  DOI：

文献信息

• New catalytic system Cu(OAc)2—2,4-lutidine—ZnCl2 for olefin cyclopropanation with methyl diazoacetate
  作者：V. F. Gareev、R. M. Sultanova、R. Z. Biglova、V. A. Dokichev、Yu. V. Tomilov

  DOI：10.1007/s11172-008-0238-x

  日期：2008.8

  A new efficient catalytic system consisting of Cu(OAc)2, 2,4-lutidine, and ZnCl2 was found for the cyclopropanation of unsaturated compounds with methyl diazoacetate. In the case of conjugated dienes, the process occurs regioselectively at the most alkylated C=C bond.

  发现了一种由 Cu(OAc)2、2,4-二甲基吡啶和 ZnCl2 组成的新型高效催化体系，用于不饱和化合物与重氮乙酸甲酯的环丙烷化反应。对于共轭二烯，该过程区域选择性地发生在烷基化程度最高的 C=C 键处。
• Method for producing optically active cyclopropane carboxylic acid
  申请人：Sumitomo Chemical Company, Limited

  公开号：US05180671A1

  公开（公告）日：1993-01-19

  The present relates to a process for preparing optically active cyclopropane carboxylic acid derivatives of salts thereof represented by the formula (III) ##STR1## wherein X is chlorine atom, bromine atom, methyl group or trifluoromethyl group and R' is hydrogen atom or metal ion, by asymmetrically hydrolyzing cyclopropane carboxylic acid esters having the formula (II) ##STR2## wherein X is as defined above and R is C.sub.1-4 alkyl group or halogen-substituted C.sub.1-4 alkyl group with specific strains of microorganisms or esterase derived therefrom.

  本发明涉及一种制备光学活性环丙烷羧酸衍生物及其盐的过程，其化学式表示为(III)。其中X是氯原子、溴原子、甲基基团或三氟甲基基团，R'是氢原子或金属离子，通过使用具有特定菌株或酯酶的不对称水解环丙烷羧酸酯（化学式(II)）来实现。其中X如上所定义，R是C.sub.1-4烷基或卤代C.sub.1-4烷基。
• A Stereoselective Synthesis Of Methyl Trans- 3 - (2, 2 -Dichloroethenyl)- 2, 2 - Dimethylcyclopropanecarboxylate
  作者：Jun'an Ma、Runqiu Huang、Junran Cheng、Ruilian Shao、Zaiguo Li

  DOI：10.1080/00397919908086150

  日期：1999.5

  method is described for the stereoselective synthesis of methyl trans - 3 - (2, 2 -dichloroethenyl) - 2, 2 - dimethylcyclopropanecarboxylate (5) via methyl 3, 3 - dimethyl - 4, 6, 6, 6 -tetrachlorohexanoate (4) as a key intermediate, which was obtained by addition of carbon tetrachloride to methyl 3,3-dimethyl-4-pentenoate (3). Treatment of (4) with sodium methoxide in a single-vessel via methyl 4,6,6-trichloro-3

  摘要 描述了一种通过 3, 3 - 二甲基 - 4, 6, 6, 6 - 四氯己酸甲酯立体选择性合成反式 - 3 - (2, 2 - 二氯乙烯) - 2, 2 - 二甲基环丙烷羧酸酯 (5) 的简便方法（ 4) 作为关键中间体，由四氯化碳与 3,3-二甲基-4-戊烯酸甲酯 (3) 加成得到。在单容器中通过 4,6,6-三氯-3.3-氯甲基-5-己烯酸甲酯 (6) 用甲醇钠处理 (4) 以优异的产率得到富含反式的 (5)。
• Mild method for conversion of N-Alkoxyamides to esters using N-Chloro-N-(phenylsulfonyl)benzenesulfonamide
  作者：Sushant Bhalerao、Hemchandra Chaudhari

  DOI：10.1016/j.tetlet.2023.154539

  日期：2023.6

  An efficient, fast method for ester synthesis from N-alkoxyamides has been reported. This protocol used easily available N-Chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) for conversion of alkoxy amides to the corresponding esters. The present methodology is metal and ligand-free and takes place under mild reaction conditions. This transformation incorporates a wide variety of amides, prepared

  已经报道了一种从N-烷氧基酰胺合成酯的有效、快速的方法。该方案使用容易获得的N -氯-N-(苯磺酰基)苯磺酰胺 (NCBSI) 将烷氧基酰胺转化为相应的酯。本方法不含金属和配体，在温和的反应条件下进行。这种转化结合了多种酰胺，由芳基或烷基羧酸制备，导致功能化酯的形成，突出了其多功能性、化学选择性和高产率方面。
• Srinivas; Subba Reddy; Yadav, Journal of Chemical Research - Part S, 2000, # 8, p. 376 - 377
  作者：Srinivas、Subba Reddy、Yadav、Ramalingam

  DOI：——

  日期：——