59609-49-3

• 常用中文名：二氯菊酸乙酯
• 常用英文名：ethyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylate
• CAS号：59609-49-3
• 分子式：C₁₀H₁₄Cl₂O₂
• 分子量：237.12300
• 相关类别： 化学农药原药 杀虫剂中间体
• 发布时间：2018-07-17 23:03:49
• 更新时间：2024-01-08 20:03:29

• 二氯菊酸乙酯是拟除虫菊酯的重要中间体，可以制备氯菊酯、氯氰菊酯、高效氯氰菊酯、四氟苯菊酯、氟氯氰菊酯等。

名称

• 中文名: 二氯菊酸乙酯
• 英文名: Ethyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
• 英文别名: ethyl 2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropane-carboxylate; 3-(2,2-dichloroacetyl)-4-hydroxy-1-methyl-1,2-dihydroquinolin-2-one; 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ethyl ester; 2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropanecarboxylic acid ethyl ester; (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate; EINECS 261-826-7; ethyl 3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate; 3-Dichloroacetyl-4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinoline; (3-phenoxyphenyl)methyl (1RS)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate; ethyl 2,2-dimethyl-3-(2,2-dichloro-1-ethenyl)cyclopropanecarboxylate; m-phenoxybenzyl (RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; 3-(2,2-dichloroacetyl)-4-hydroxy-1-methylquinolin-2(1H)-one; 3-(2,2-dichloroacetyl)-2-hydroxy-1-methylquinolin-4-one; 3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid ethyl ester; 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl)-methyl ester; 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate

物化性质

• 密度: 1.263g/cm3
• 沸点: 239.3ºC at 760 mmHg
• 分子式: C₁₀H₁₄Cl₂O₂
• 分子量: 237.12300
• 闪点: 93.5ºC
• 精确质量: 236.03700
• PSA: 26.30000
• LogP: 3.14070
• 折射率: 1.545
• 稳定性:

  二氯菊酸乙酯为无色透明液体，b.p.93～94℃/101pa，78～88℃/27pa，n²⁰_D 1.4833，相对密度 1.1170，不溶于水，溶于苯、甲苯、氯仿等有机溶剂。

• 分子结构:

  1、 摩尔折射率：50.19

  2、 摩尔体积（cm³/mol）：155.6

  3、 等张比容（90.2K）：389.7

  4、 表面张力（dyne/cm）：39.3

  5、 极化率（10-24cm3）：19.89

• 计算化学:

  1.疏水参数计算参考值（XlogP）:无

  2.氢键供体数量:0

  3.氢键受体数量:2

  4.可旋转化学键数量:4

  5.互变异构体数量:无

  6.拓扑分子极性表面积26.3

  7.重原子数量:14

  8.表面电荷:0

  9.复杂度:267

  10.同位素原子数量:0

  11.确定原子立构中心数量:0

  12.不确定原子立构中心数量:2

  13.确定化学键立构中心数量:0

  14.不确定化学键立构中心数量:0

  15.共价键单元数量:1

MSDS

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: 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 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. 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. 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. 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. 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. 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. 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 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. 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. Section 12 - ECOLOGICAL INFORMATION For further information, contact Fisher Scientific. Section 13 - DISPOSAL CONSIDERATIONS Dispose of in a manner consistent with federal, state, and local regulations. 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. 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. SECTION 16 - ADDITIONAL INFORMATION N/A

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制备

其制备方法有以下几种。
Farks法(重氮乙酸酯法)
由异丁烯与三氯乙醛在AlCl₃催化下缩合成一烯醇，再经乙酰化、锌粉还原和酸催化异构化得到共轭双烯，即1，1-二氯-4-甲基戊二烯-[1，3]，最后与重氮乙酸甲酯(乙酯)在铜粉催化下进行反应，即得二氯菊酸甲酯(乙酯)。002$S相模法
由2-甲基丁烯[2]醇[1](异戊烯醇)与原乙酸甲酯(乙酯)，在酸性催化剂如丙酸存在下，进行缩合Clasen重排，生成3，3-二甲基戊烯[4]酸甲(乙)酯[贲亭酸甲(乙)酯]，后者与四氯化碳在过氧化苯甲酰存在下调聚加成，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进行脱氯化氢，环合而成二氯菊酸甲酯(乙酯)。
相模-库拉莱法
由1，1，1-三氯-2-羟基-4-甲基戊烯[4]即上述Farkas法中由异丁烯与三氯乙醛生成的烯醇，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，得3，3-二甲基-4，6，6-三氯己烯[4]酸甲(乙)酯，在反应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，而二氯丁内酯可用氯化氢或氯化亚砜在甲(乙)醇溶液中开环而生成3，3-二甲基-4，6，6-三氯己烯[4]酸甲(乙)酯，再环合得到二氯菊酸甲(乙)酯。
偏二氯乙烯法
与相模法相似，但用的原料不一样，避免了用烯醇与原乙酸酯的反应生成贲亭酸甲酯，从贲亭酸甲酯制备二氯菊酸甲酯与相模法一样。
用异戊二烯为原料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-3，3-二甲基戊烯[1]，再用浓H₂SO₄或碱水解，得5-氯-3，3-二甲基戊酸，用甲醇在酸性介质中酯化，生成相应的5-氯-3，3-二甲基戊酸甲酯，再用甲醇钠脱氯化氢，得3，3-二甲基戊烯[4]酸甲酯，即贲亭酸甲酯。
环丁酮法
由丙烯腈和四氯化碳在加压下，以Cu为催化剂，进行调聚反应，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，再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Cine重排得2-三氯乙基-3，3-二甲基-4-氯环丁酮，再经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。
NRDC法
由蒈醛酸甲酯与三苯基亚甲基二氯化膦进行Wittig反应，而得到二氯菊酸甲酯。