2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)-carbamoyloxy]benzofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)-carbamoyloxy]benzofuran
• 英文别名: 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl) carbamoyloxy]benzofuran；2,3-Dihydro-2,2-dimethyl-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl) carbamoyloxy]benzofuran；2,3-Dihydro-2,2-dimethyl-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)-carbamoyloxy]benzofuran；2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]benzofuran；2,3-dihydro-2,2-dimethyl-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy]benzofuran；(2,2-dimethyl-3H-1-benzofuran-7-yl) N-[carbonofluoridoyl(methyl)amino]sulfanyl-N-methylcarbamate
• 化学式: C₁₄H₁₇FN₂O₄S
• 分子量: 328.364
• InChiKey: LZKUFVAGTAODMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  84.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  聚甘氨酸 、 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)-carbamoyloxy]benzofuran 生成 2-[[[(2,2-dimethyl-3H-1-benzofuran-7-yl)oxycarbonyl-methylamino]sulfanyl-methylcarbamoyl]amino]acetic acid
  参考文献：
  名称：

  RAO, CHENNUPATI K.;DSILVA, THEMISTOCLES D.

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(N-methyl-N-fluorocarbonylamino)sulfide 、 呋喃酚 在 三乙胺 作用下， 以 1,4-二氧六环 、 乙酸乙酯 为溶剂， 生成 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)-carbamoyloxy]benzofuran
  参考文献：
  名称：

  Pesticidal symmetrical bis-sulfenylated-bis carbamate compounds

  摘要：

  双硫化双氨基甲酸酯化合物对昆虫和螨虫具有活性。

  公开号：

  US04400389A1

文献信息

• Pesticidal
  申请人：Union Carbide Corporation

  公开号：US04181734A1

  公开（公告）日：1980-01-01

  Unsymmetrical bis-[N-alkyl-N-arylcarbamate] sulfide compounds exhibit outstanding miticidal, nematocidal and insecticidal activity, coupled with substantially reduced mammalian toxicity and phytotoxicity.

  非对称双-[N-烷基-N-芳基氨基甲酸酯] 硫化物化合物表现出出色的杀螨、杀线虫和杀虫活性，同时具有显著降低的哺乳动物毒性和植物毒性。
• Carbamate-sulfenyl-carbamoyl fluoride compounds
  申请人：Union Carbide Corporation

  公开号：US04338450A1

  公开（公告）日：1982-07-06

  Carbamate-sulfenyl-carba moyl fluoride compounds are valuable insecticidal compositions and are also useful intermediates in the production of bis-carbamate compounds.

  碳酸酯硫醇羰基氟化物化合物是有价值的杀虫剂组合物，也是双碳酸酯化合物生产中有用的中间体。
• Pesticidal unsymmetrical bis-arylcarbamate sulfide compounds containing
  申请人：Union Carbide Corporation

  公开号：US04124721A1

  公开（公告）日：1978-11-07

  Unsymmetrical bis-[N-alkyl-N-arylcarbamate] sulfide compounds exhibit outstanding miticidal, nematocidal and insecticidal activity, coupled with substantially reduced mammalian toxicity and phytotoxicity. SUMMARY OF THE INVENTION This invention relates to a novel class of unsymmetrical bis-arylcarbamate sulfide compounds and to methods of preparing them. This invention also relates to insecticidal, nematocidal and miticidal compositions comprising an acceptable carrier and an insecticidally or miticidally effective amount of a compound of this invention as well as to a method of controlling insects, mites and nematodes by subjecting them to an insecticidally, miticidally or nematocidally effective amount of a compound of this invention. The bis-carbamate compounds of this invention exhibit wide spectrum high level insecticidal activity as well as relatively low mammalian toxicity. This unique combination of high insecticidal activity and low mammalian toxicity permit the use of the novel unsymmetrical bis-carbamate compounds of this invention in relative safety. DESCRIPTION OF THE INVENTION This invention relates to compounds of the formula: ##STR1## wherein: R' and R" are the same or different and are alkyl having from 1 to 4 carbon atoms; R.sub.1 and R.sub.2 are individually hydrogen or alkyl having from 1 to 4 carbon atoms; R.sub.3 is: (A) naphthyl, benzodioxolanyl, tetrahydronaphthyl, indanyl or benzothienyl, all of which may be either unsubstituted or substituted with one or more alkyl groups. (B.) phenyl either unsubstituted or substituted with one or more alkyl having from 1 to 12 carbon atoms, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, dialkylamino or nitro groups; With the proviso that R.sub.3 may not include more than eight aliphatic carbon atoms, except as noted. Other compounds which are illustrative of the new compounds of this invention are: N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[3-(1-methylpropyl)phenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[(4-dimethylamino-3,5-xylylmethylcarbamate] sulfide. N-[2,3-dihydro-2-methyl-7-benzofuranylmethylcarbamate] N-[2-isopropoxyphenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate] N-[4-benzothienyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate] N-[5,6,7,8-tetrahydronaphthyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate] N-[3,4,5-trimethylphenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate] N-[4-methylthio-3,5-xylylmethylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate] N-[4-dimethylamino-3-tolyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[4-indanylmethylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[2-ethylthiomethylphenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[2-ethylsulfinylmethylphenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[4-methylsulfinyl-3,5-xylylmethylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[3,5-diisopropylphenyl methylcarbamate] sulfide. N-[2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] N-[2,2-dimethylbenzodioxolanyl-4-methylcarbamate] sulfide. All of the compounds within the purview of the generic formula set forth above exhibit miticidal and insecticidal activity to a lesser or greater extent. Accordingly, these compounds are extremely useful for the control of insect, nematode and mite pests. Some of these compounds exhibit very high levels of miticidal, nematocidal and insecticidal activity in extremely small dosages while others require larger dosages to be effective. In general, the compounds of this invention are either totally lacking in phytotoxicity or exhibit only minimal phytotoxicity with respect to economically important crop species. In addition, these compounds exhibit substantially reduced levels of mammalian toxicity as compared to known pesticidal compounds having a comparable spectrum of activity against insect, arachnid and nematode pests. Preferred because of their higher levels of miticidal and insecticidal activity are the compounds of this invention in which: R', r", r.sub.1 and R.sub.2 are methyl; R.sub.3 is naphthyl, or phenyl substituted with one or more alkoxy, alkyl, alkylthio or dialkylamino groups. The unsymmetrical bis-[N-alkyl-N-arylcarbamate] sulfide compounds of this invention can be conveniently prepared by a variety of methods. One preferred method is illustrated by the reaction scheme set forth below in which R', R", R.sub.1, R.sub.2 and R.sub.3 are as described above, except as noted: ##STR2## METHOD I is a two-step reaction sequence which can be conducted either in-situ or the carbamate-sulfenyl carbamoyl halide intermediate (III) of Step A can be isolated and used as the reactant of Step B at some latter time. In Step A, one equivalent of an appropriately substituted hydroxyl reactant, either 2,2-dimethyl-2,3-dihydrobenzofuran-7-ol or R.sub.3 OH is reacted with one equivalent of the bis-(N-alkyl-N-fluorocarbonylamino) sulfide reactant (II), in the presence of at least one equivalent of an acid acceptor, preferably in an aprotic solvent to yield the intermediate carbamate sulfenyl carbamoyl halide (III). In Step B, an equivalent of the intermediate carbamate sulfenyl carbamoyl halide (III) reactant is then reacted with second equivalent of a hydroxyl reactant, R.sub.3 OH if 2,2-dimethyl-2,3-dihydrobenzofuran-7-ol was used as the hydroxyl reactant in step A or 2,2-dimethyl-2,3-dihydrobenzofuran-7-ol if R.sub.3 OH was used as the hydroxyl reactant of Step A. Step B is also conducted in the presence of at least one equivalent of an appropriate acid acceptor and in an aprotic solvent, to yield the desired bis-arylcarbamate compound (V). The reactions of METHOD I is normally conducted in an aprotic organic solvent. Illustrative of aprotic organic solvents which are suitable as reaction solvents in the practice of the preferred embodiments of this invention are saturated and unsaturated aliphatic and aromatic hydrocarbons, e.g. hexane, cyclohexane, octane, dodecane, naphtha, decalin, kerosene, tetrahydronaphthalene, benzene, toluene, xylene, naphthalene, alkylnaphthalene, or the like, ethers such as tetrahydrofuran, tetrahydropyran, diethyl ether, dioxane, 1,2-dimethoxybenzene, 1,2-ethoxybenzene, the dialkyl ethers of ethylene glycol, of butylene glycol, or diethylene glycol, of dipropylene glycol, or chlorinated aliphatic hydrocarbons as for example, chloroform, dichloromethane, carbon tetrachloride or the like. The acid acceptor utilized in the conduct of the reaction of METHOD I may be either an organic or inorganic base. Illustrative of organic bases that are useful as acid acceptors are tertiary amines, alkali metal alkoxides or the like. Bases such as sodium hydroxide, potassium hydroxide or the like are illustrative of inorganic bases which are useful in the conduct of this reaction. Preferred acid acceptors are aromatic and aliphatic tertiary amines, such as triethylamine, pyridine, trimethylamine, 1,4-diazobicyclo [2.2.2] octane and the like. When an inorganic base is used as the acid acceptor, phase transfer agents may be used to facilitate the transfer of the acid acceptor across the organic/inorganic phase interface. Illustrative of useful phase transfer agents are crown ether compounds, quaternary ammonium halide compounds or the like. In these reactions, the reaction temperature is not critical and can be varied over a wide range. The reaction is preferably conducted at a temperature of from about -30.degree. C. and upwards to approximately 130.degree. C. Particularly preferred reaction temperatures are from about 0.degree. C. to about 75.degree. C. Reaction pressures are not critical. The process can be conducted at either subatmospheric, atmospheric or superatmospheric pressure. For convenience the reaction is usually conducted at atmospheric or autogeneous pressure. Hydroxylated aryl compounds employed as reactants in the reactions of METHOD I are well known compounds that can be prepared by well known synthetic procedures or obtained from commercial sources. The bis-(N-alkyl-N-fluorocarbonylamino) sulfide precursors can be conveniently prepared by reacting sulfur dichloride with N-alkylcarbamoyl fluoride in toluene in the presence of an acid acceptor as for example triethylamine or pyridine. This procedure is described in more detail in U.S. Pat. No. 3,639,471.

  非对称双-[N-烷基-N-芳基碳酰胺]硫化物化合物展现出卓越的杀螨、杀线虫和杀虫活性，并且显著降低了哺乳动物毒性和植物毒性。本发明涉及一类新颖的非对称双-芳基碳酰胺硫化物化合物及其制备方法。本发明还涉及包含有效载体和本发明化合物的杀虫或杀螨有效量的杀虫、杀线虫和杀螨组合物，以及通过使害虫、螨类和线虫接触本发明化合物的杀虫、杀螨或杀线虫有效量来控制它们的方法。本发明的双碳酰胺化合物展现出广谱高水平杀虫活性以及相对较低的哺乳动物毒性。这种独特的杀虫活性高和哺乳动物毒性低的特点使得可以在相对安全的情况下使用本发明的新型非对称双碳酰胺化合物。
• DSILVA, T. D. J.
  作者：DSILVA, T. D. J.

  DOI：——

  日期：——
• RAO, CHENNUPATI K.;DSILVA, THEMISTOCLES D.
  作者：RAO, CHENNUPATI K.、DSILVA, THEMISTOCLES D.

  DOI：——

  日期：——