42576-02-3

• 常用中文名：5-(2,4-二氯苯氧基)-2-硝基苯甲酸甲酯
• 常用英文名：Bifenox
• CAS号：42576-02-3
• 分子式：C₁₄H₉Cl₂NO₅
• 分子量：342.131
• 相关类别： 化学农药原药 除草剂 二苯醚类除草剂
• 发布时间：2018-03-25 08:00:00
• 更新时间：2024-01-04 13:58:00
• 用作医药、农药中间体

名称

• 中文名: 甲羧除草醚
• 英文名: bifenox
• 中文别名: 茅毒; 5-(2,4-二氯苯氧基)-2-硝基苯甲酸甲酯; 治草醚
• 英文别名: 2,4-dichlorophenyl 3'-methoxycarbonyl-4'-nitrophenyl ether; Bifenox; 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid methyl ester; Caswell No. 561AA; Benzoic acid,5-(2,4-dichlorophenoxy)-2-nitro-,methyl ester; methyl 2-nitro-5-(2',4'-dichlorophenoxy)benzoate; MFCD00055314; Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate; Benzoic acid, 5-(2,4-dichlorophenoxy)-2-nitro-, methyl ester; Modown; EINECS 255-894-7; methyl 5-(2',4'-dichlorophenoxy)-2-nitrobenzoate; 2,4-Dichlorophenyl 3-(Methoxycarbonyl)-4-nitrophenyl Ether; Bifenox [ANSI:BSI:ISO]; MC-4379

物化性质

• 密度: 1.5±0.1 g/cm3
• 沸点: 421.0±45.0 °C at 760 mmHg
• 熔点: 83 - 85ºC
• 分子式: C₁₄H₉Cl₂NO₅
• 分子量: 342.131
• 闪点: 208.4±28.7 °C
• 精确质量: 340.985779
• PSA: 81.35000
• LogP: 4.52
• 蒸汽压: 0.0±1.0 mmHg at 25°C
• 折射率: 1.608
• 储存条件:

  密封、阴凉、干燥保存

• 稳定性:

  常规情况下不会分解，没有危险反应

  无严重吸入毒性，对眼无刺激。高剂量词喂大鼠和火不产生病理学及组织学变化。无致畸、致癌、致突变作用。

• 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:5

  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81.4

  7.重原子数量:22

  8.表面电荷:0

  9.复杂度:417

  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:0

  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

• 更多:

  1. 性状：黄色或浅褐色结晶。

  2. 密度（g/mL,25ºC）：未确定

  3. 相对蒸汽密度（g/mL,空气=1）： 未确定

  4. 熔点（ºC）：84～86

  5. 沸点（ºC）：421

  6. 沸点（ºC，19mm hg）：未确定

  7. 折射率：未确定

  8. 闪点（ºF）：未确定

  9. 比旋光度（ºC）：未确定

  10. 自燃点或引燃温度（ºC）： 未确定

  11. 蒸气压（kPa,20ºC）：2×10^-4

  12. 饱和蒸气压（kPa,60ºC）：未确定

  13. 燃烧热（KJ/mol）：未确定

  14. 临界温度（ºC）：未确定

  15. 临界压力（KPa）：未确定

  16. 油水（辛醇/水）分配系数的对数值：未确定

  17. 爆炸上限（%,V/V）：未确定

  18. 爆炸下限（%,V/V）：未确定

  19. 溶解性：未确定

MSDS

Section1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE Product identifiers Product name: Bifenox CAS-No.: 42576-02-3 Relevant identified uses of the substance or mixture and uses advised against Identified uses: Laboratory chemicals, Manufacture of substances Section2. HAZARDS IDENTIFICATION Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Acute aquatic toxicity (Category 1) Chronic aquatic toxicity (Category 1) Not a hazardous substance or mixture according to EC-directives 67/548/EEC or 1999/45/EC. Label elements Labelling according Regulation (EC) No 1272/2008 [CLP] Pictogram Signal wordWarning Hazard statement(s) H410Very toxic to aquatic life with long lasting effects. Precautionary statement(s) P273Avoid release to the environment. P501Dispose of contents/ container to an approved waste disposal plant. Supplemental Hazardnone Statements Other hazards - none Section3. COMPOSITION/INFORMATION ON INGREDIENTS Substances Synonyms: Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate Formula: C14H9Cl2NO5 Molecular Weight: 342,13 g/mol Section4. FIRST AID MEASURES Description of first aid measures General advice Consult a physician. Show this safety data sheet to the doctor in attendance. If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician. In case of skin contact Wash off with soap and plenty of water. Consult a physician. In case of eye contact Flush eyes with water as a precaution. If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician. Most important symptoms and effects, both acute and delayed Indication of any immediate medical attention and special treatment needed no data available Section5. FIREFIGHTING MEASURES Extinguishing media Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Special hazards arising from the substance or mixture Carbon oxides, nitrogen oxides (NOx), Hydrogen chloride gas Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary. Further information no data available Section6. ACCIDENTAL RELEASE MEASURES Personal precautions, protective equipment and emergency procedures Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Environmental precautions Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided. Methods and materials for containment and cleaning up Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed containers for disposal. Reference to other sections For disposal see section 13. Section7. HANDLING AND STORAGE Precautions for safe handling Provide appropriate exhaust ventilation at places where dust is formed.Normal measures for preventive fire protection. Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Specific end use(s) no data available Section8. EXPOSURE CONTROLS/PERSONAL PROTECTION Control parameters Components with workplace control parameters Exposure controls Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Personal protective equipment Eye/face protection Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Choose body protection in relation to its type, to the concentration and amount of dangerous substances, and to the specific work-place., The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Respiratory protection Respiratory protection is not required. Where protection from nuisance levels of dusts are desired, use type N95 (US) or type P1 (EN 143) dust masks. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU). Section9. PHYSICAL AND CHEMICAL PROPERTIES Information on basic physical and chemical properties a) AppearanceForm: solid Colour: yellow b) Odourno data available c) Odour Thresholdno data available d) pHno data available e) Melting point/freezing84 - 89 °C point f) Initial boiling point and no data available boiling range g) Flash pointno data available h) Evaporation rateno data available i) Flammability (solid, gas) no data available j) Upper/lowerno data available flammability or explosive limits k) Vapour pressureno data available l) Vapour densityno data available m) Relative densityno data available n) Water solubilityinsoluble o) Partition coefficient: n- log Pow: 4,48 octanol/water p) Auto-ignitionno data available temperature q) Decompositionno data available temperature r) Viscosityno data available s) Explosive propertiesno data available t) Oxidizing propertiesno data available Other safety information no data available Section10. STABILITY AND REACTIVITY Reactivity no data available Chemical stability no data available Possibility of hazardous reactions no data available Conditions to avoid no data available Incompatible materials Strong oxidizing agents Hazardous decomposition products Other decomposition products - no data available Section11. TOXICOLOGICAL INFORMATION Information on toxicological effects Acute toxicity LD50 Oral - rat - 6.400 mg/kg LC50 Inhalation - rat - > 200.000 mg/m3 LD50 Dermal - rabbit - > 20.000 mg/kg Skin corrosion/irritation no data available Serious eye damage/eye irritation no data available Respiratory or skin sensitization no data available Germ cell mutagenicity no data available Carcinogenicity IARC:No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC. Reproductive toxicity no data available Specific target organ toxicity - single exposure no data available Specific target organ toxicity - repeated exposure no data available Aspiration hazard no data available Potential health effects Inhalation May be harmful if inhaled. May cause respiratory tract irritation. IngestionMay be harmful if swallowed. SkinMay be harmful if absorbed through skin. May cause skin irritation. EyesMay cause eye irritation. Additional Information RTECS: DG7890000 Section12. ECOLOGICAL INFORMATION Toxicity Toxicity to fishLC50 - Oncorhynchus mykiss (rainbow trout) - > 0,18 mg/l - 96,0 h Toxicity to daphnia and EC50 - Daphnia magna (Water flea) - > 0,35 mg/l - 48 h other aquatic invertebrates Persistence and degradability no data available Bioaccumulative potential no data available Mobility in soil no data available Results of PBT and vPvB assessment no data available Other adverse effects Very toxic to aquatic life. Avoid release to the environment. no data available Section13. DISPOSAL CONSIDERATIONS Waste treatment methods Product Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. Contaminated packaging Dispose of as unused product. Section14. TRANSPORT INFORMATION UN number ADR/RID: 3077IMDG: 3077IATA: 3077 UN proper shipping name ADR/RID: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S. (Methyl 5-(2,4- dichlorophenoxy)-2-nitrobenzoate) IMDG: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S. (Methyl 5-(2,4- dichlorophenoxy)-2-nitrobenzoate) IATA:Environmentally hazardous substance, solid, n.o.s. (Methyl 5-(2,4-dichlorophenoxy)-2- nitrobenzoate) Transport hazard class(es) ADR/RID: 9IMDG: 9IATA: 9 Packaging group ADR/RID: IIIIMDG: IIIIATA: III Environmental hazards ADR/RID: yesIMDG Marine Pollutant: yesIATA: yes Special precautions for user Further information EHS-Mark required (ADR 2.2.9.1.10, IMDG code 2.10.3) for single packagings and combination packagings containing inner packagings with Dangerous Goods > 5L for liquids or > 5kg for solids. Section15. REGULATORY INFORMATION This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006. Safety, health and environmental regulations/legislation specific for the substance or mixture no data available Chemical Safety Assessment no data available Section16. OTHER INFORMATION Further information Copyright 2012 Co. LLC. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Corporation and its Affiliates shall not be held liable for any damage resulting from handling or from contact with the above product. See and/or the reverse side of invoice or packing slip for additional terms and conditions of sale.

毒性和生态

毒理学数据: 大鼠急性经口LD50> 6400mg /kg，家兔急性经皮LD50> 20000mg /kg.对鱼及水生生物高毒，虹蝉鱼LC50 >0.18mg/L(96h),鲤鱼LC50>1.22mg/L(48h),虾LC50为0 . 065mg /kg。对蜜蜂低毒，急性接触LD50> 1000μg/只。对鸟类低毒，鹤鹑急性经日LD50 >5000mg /kg. 生态学数据: 对水是稍微有危害的不要让未稀释或大量的产品接触地下水、水道或者污水系统，若无政府许可，勿将材料排入周围环境。 CHEMICAL IDENTIFICATION RTECS NUMBER : DG7890000 CHEMICAL NAME : Benzoic acid, 5-(2,4-dichlorophenoxy)-2-nitro-, methyl ester CAS REGISTRY NUMBER : 42576-02-3 LAST UPDATED : 199710 DATA ITEMS CITED : 6 MOLECULAR FORMULA : C14-H9-Cl2-N-O5 MOLECULAR WEIGHT : 342.14 WISWESSER LINE NOTATION : GR CG DOR DNW CVO1 HEALTH HAZARD DATA ACUTE TOXICITY DATA TYPE OF TEST : LD50 - Lethal dose, 50 percent kill ROUTE OF EXPOSURE : Oral SPECIES OBSERVED : Rodent - rat DOSE/DURATION : 6400 mg/kg TOXIC EFFECTS : Details of toxic effects not reported other than lethal dose value REFERENCE : 85ARAE "Agricultural Chemicals," Thomson, W.T., 4 vols., Fresno, CA, Thomson Publications, 1976/77 revision Volume(issue)/page/year: 2,15,1977 TYPE OF TEST : LC50 - Lethal concentration, 50 percent kill ROUTE OF EXPOSURE : Inhalation SPECIES OBSERVED : Rodent - rat DOSE/DURATION : >200 gm/m3 TOXIC EFFECTS : Details of toxic effects not reported other than lethal dose value REFERENCE : DEVEAA Defense des Vegetaux. (Federation Nationale des Groupements de Protection des Cultures, 149, rue de Bercy, 75595 Paris Cedex, 12, France) V.1- 1947- Volume(issue)/page/year: 37,3,1983 TYPE OF TEST : LD50 - Lethal dose, 50 percent kill ROUTE OF EXPOSURE : Oral SPECIES OBSERVED : Rodent - mouse DOSE/DURATION : 4556 mg/kg TOXIC EFFECTS : Details of toxic effects not reported other than lethal dose value REFERENCE : PEMNDP Pesticide Manual. (The British Crop Protection Council, 20 Bridport Rd., Thornton Heath CR4 7QG, UK) V.1- 1968- Volume(issue)/page/year: 9,71,1991 TYPE OF TEST : LD50 - Lethal dose, 50 percent kill ROUTE OF EXPOSURE : Administration onto the skin SPECIES OBSERVED : Rodent - rabbit DOSE/DURATION : >20 gm/kg TOXIC EFFECTS : Details of toxic effects not reported other than lethal dose value REFERENCE : DEVEAA Defense des Vegetaux. (Federation Nationale des Groupements de Protection des Cultures, 149, rue de Bercy, 75595 Paris Cedex, 12, France) V.1- 1947- Volume(issue)/page/year: 37,3,1983 *** U.S. STANDARDS AND REGULATIONS *** EPA FIFRA 1988 PESTICIDE SUBJECT TO REGISTRATION OR RE-REGISTRATION FEREAC Federal Register. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) V.1- 1936- Volume(issue)/page/year: 54,7740,1989

安全

• 符号: GHS09
• 信号词: Warning
• 危害声明: H410
• 警示性声明: P273-P501
• 个人防护装备: Eyeshields;Gloves;type N95 (US);type P1 (EN143) respirator filter
• 危害码 (欧洲): N: Dangerous for the environment;
• 风险声明 (欧洲): 50/53
• 安全声明 (欧洲): S60-S61
• 危险品运输编码: UN 3077 9/PG 3
• RTECS号: DG7890000
• 海关编码: 2918990090

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制备

以苯甲酰氯、氯气、2，4-二氯苯酚为主要原料，进行下列反应而得。

1.间氯苯甲酰氯的制备 将苯甲酰氯281g、铁粉1.4g及硫黄0.56g投入反应瓶中。保持温度20℃，通氯氯化，约2.5h。然后通氮气赶除光气和反应生成的氯化氢气体而得。

2.间氯苯甲酸甲酯的制备 将甲醇慢慢地加入搅拌下的间氯苯甲酰氯中（酰氯：甲醇=1.0：1.1摩尔比）。在25-68℃之间行酯化反应，回流2-3h，反应过程中有大量氯化氢放出，回收过量的甲醇而得。3. 5-氯-2-硝基苯甲酸甲酯的制备 往反应瓶中加入853g间氯苯甲酸甲酯，和500g 1，2-二氯乙烷，冷却至-10℃，滴加338g 95%的发烟硝酸（5.1mol）和816g 96%硫酸（8mol）的混合酸，约3h滴完。在-10℃下搅拌反应2h，再升温至30℃搅拌反应3h。分出有机层，过滤，干燥而得。

4.甲酯除草醚的制备 将固体碳酸钾（97%）189g，加入搅拌下的2，4-二氯苯酚（97%）419g及960ml二甲基甲酰胺溶剂中，加热回流1h，伴有二氧化碳放出，约50%的二甲基甲酰胺蒸出之后，将5-氯-2-硝基苯甲酸甲酯（80%）638g加入搅拌下的95%的酚盐中。加完后，在100℃反应3h，脱溶后加甲醇使产品溶解，冷却，滤除氯化钾。滤液冷却结晶而得，熔点84-86℃。配制成10%颗粒剂，21%乳油，25%可湿性粉剂。

5.水解反应将772g三氯化苄、0.25g三氯化铁混合后，升温至120℃，再将75g水于一定时间内恒温滴加，滴毕继续搅拌30min，得苯甲酰氯633g，收率96%。

6.氯化反应投入苯甲酰氯281g，铁粉1.4g，硫黄0.56g，于20℃通氯反应2.5h，赶走余氯和氯化氢气体，得间氯苯甲酰氯粗品，收率70%～80%。

7.酯化反应将甲醇滴加到间氯苯甲酰氯中，配比为1∶1（mol），于25～68℃范围内反应，反应过程有轻微放热现象，可以调节加料速度，控制反应温度，回流2～3h，反应过程有大量氯化氢逸出，过量的甲醇与残余氯化氢气体用真空排除，得无色间氯苯甲酸甲酯液体，收率98%～99%。

8.硝化反应将853g间氯苯甲酸甲酯（纯度94%）和500g1,2-二氯乙烷混合后，冷却至－10℃，再滴加338g 95%发烟硝酸和816g 96%的硫酸（混酸），约在3h内滴毕，将反应物在－10℃下搅拌２犺后，再在0～30℃搅拌3h，倾去有机层（1,2-二氯乙烷），过滤、干燥，得829g5-氯-2-硝基苯甲酸甲酯，收率76.9%。

9.缩合反应将固体碳酸钾1.61mol加入到2,4-二氯苯酚2.49mol及960mol DMF溶液中，升温回流1h，伴有二氧化碳气体逸出。把近1/2的犇犕犉（夹带生成的水）溶剂蒸出后，将5-氯-2-硝基苯甲酸甲酯2.37mol加入温度为95℃的酚盐溶液中。加毕于100℃反应3h，真空蒸出犇犕犉，加1000mL甲醇使粗品溶解，大约冷至65℃，滤出犓犆犾，母液冷冻结晶，得纯甲羧除草醚420g，收率50%。

10.制备方法二

海关

海关编码	2918990090
中文概述	2918990090. 其他含其他附加含氧基羧酸（包括酸酐、酰卤化物、过氧化物和过氧酸及该税号的衍生物）. 增值税率:17.0%. 退税率:13.0%. 监管条件:无. 最惠国关税:6.5%. 普通关税:30.0%
申报要素	品名, 成分含量, 用途
Summary	2918990090. other carboxylic acids with additional oxygen function and their anhydrides, halides, peroxides and peroxyacids; their halogenated, sulphonated, nitrated or nitrosated derivatives. VAT:17.0%. Tax rebate rate:13.0%. . MFN tariff:6.5%. General tariff:30.0%