• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for achieving nucleophilic substitution upon an unactivated monocyclic or polycyclic aromatic or heteroaromatic substrate bearing a suitable leaving group comprising the substitution of said leaving group by an anionic nucleophile is catalyzed with a cyclic or acyclic polydentate chelating ligand, e.g. a crown ether or a cyclic polyether. The process is applicable, inter alia, as the first step in the preparation of ortho-substituted benzenesulfonyl chloride derivatives, or ortho-benzenedithiol, from ortho-dichlorobenzene.
    公开号:SU1281171A3
    申请号:SU833593067
    申请日:1983-05-16
    公开日:1986-12-30
    发明作者:Двейн Джосей Ольден
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    eleven
    The invention relates to an improved method for the preparation of ortho-chlorophenyl alkyl sulfides, which are used as intermediates in the synthesis of herbicides.
    The aim of the invention is to increase the yield of target products and simplify the process.
    This goal is achieved by using O-dichlorobenzene (ODCB) as a starting material and carrying out the process in the presence of acyclic polyethylene glycol or an unbranched ether having an average mol. mass 300-2000 in the amount of 2-18 wt.% in terms of alkyl mercaptide at 95-195 C.
    Example. A mixture of 1 00 g of ODHB, 38 g of potassium propyl mercaptide and 5.7 g (15% by weight) of polyethylene 1 l of Sagr Wax {R) 2000 from Union Carbide is heated at reflux temperature under nitrogen for 2 hours. Behind
    this temperature rises from 175 to 195 ° C with the dissolution of the total amount of solids. The reaction is completed after 2 h (according to GLC). The precipitated amount of solids filtered off. According to GLC, the filtrate contains 49.7 wt.% O-chlorophenylpropyl sulfide (yield: 83.5%). By fractional distillation of the filtrate, 62.6 g (74%) of o-chlorophenylpropyl sulfide, b.p. 75 C (0.7 mm Hg).
    NMR spectrum (CDCls): 6.8-7.5 (m, 4H 1.6 (m, 2H); 2.85 (t, 2H); 1.0 (t, 3N).
    PRI mme R 2. Similar to example 1, but with the use of 5.8 g of polyethylene glycol Carbowax 300 of the company Union Carbide and with heating during
    5h get the output of sulphide 90% (according to GLC). The NMR spectrum and the GLC retention time of the product are the same as for the product of example 1.
    PRI me R 3. A mixture of 118 g of ODHB, 40 g of 85% propyl mercaptide potassium and
    6 g of an unbranched poly-, ether containing 63 mol.% Of ethylene oxide and 37 mol.% Of tetrahydrofuran monomer units with an average molecular weight of 1615 are heated at reflux temperature overnight. After cooling and filtering in order to separate the solids, filter 1712
    The distillate is distilled under vacuum to remove the solvent. Quantitative GLC indicates 85% yield of chlorophenylpropyl sulfide.
    Similarly to this example, but using methyl mercaptide instead of 1; -propyl mercaptan, o-chlorophenylmethylsulfide is obtained.
    To illustrate the effect of the catalyst on this reaction, a mixture of 147 g of ODCB and 43 g of potassium methyl mercaptide is prepared and, in the absence of the catalyst, stirred and heated for 1 hour at 957lOO C. After that, o-hdorfenylmethyl sulfide is hardly detected by GLC (area 0.002%). On the contrary, if Carbovax®300 polyethylene glycol (18% by weight, based on the weight of the mercaptide) is introduced at the beginning of the reaction, then after 30 minutes a filtrate is obtained with an area of 44%, and after 60 minutes - 47%. Upon reaching this value, the reaction is basically complete. A similar result is obtained when using Carbowax® 350 polyethylene glycol.
    EXAMPLE 4 A mixture of 80 g of Q — dichlorobenzene (ODCB), 23.5 g of anhydrous potassium methyl mercaptide, and 0.47 g (2% by weight) of Carbowax® 400 is heated to boiling point under a nitrogen atmosphere. After 2 hours with reflux, the data obtained by gas chromatography show the content of a mixture of ODHB in the mixture: an area of 82.6% and o-chlorophenylmethyl sulfide, an area of 16, 9%. After an additional 2 hours with reflux, the amounts of the components are 77.8 and 21%, respectively, which indicates a constant
    accumulation of the product.
    权利要求:
    Claims (4)
    [1]
    11 The invention relates to an improved method for the preparation of ortho-chlorophenyl alkyl sulfides, which are used as intermediates in the synthesis of herbicides. The aim of the invention is to increase the yield of target products and simplify the process. This goal is achieved by using O-dichlorobenzene (ODCB) as a starting material and carrying out the process in the presence of acyclic polyethylene glycol or an unbranched ether having an average mol. mass 300-2000 in the amount of 2-18 wt.% in terms of alkyl mercaptide at 95-195 C. Example. A mixture of 1 00 g of ODHB, 38 g of potassium propyl mercaptide and 5.7 g (15 wt.%) Polyethylene 1 l of Sagwawax {R) 2000 from Union Carbide is heated at reflux temperature under nitrogen for 2 hours. During this time, the temperature rises from 175 to 195 ° C with the dissolution of the total amount of solids. The reaction is completed after 2 h (according to GLC). The amount of solids precipitated upon cooling is filtered off. According to GLC, the filtrate contains 49.7 wt.% O-chlorophenylpropyl sulfide (yield: 83.5%). By fractional distillation of the filtrate, 62.6 g (74%) of o-chlorophenylpropyl sulfide are obtained, b.p. 75 C (0.7 mm Hg). Nuclear Magnetic Resonance Spectrum (CDCls): 6.8-7.5 (m, 4H 1.6 (m, 2H); 2.85 (t, 2H); 1.0 (t, 3N). P m and m R
    [2]
    2. Example 1 is similar, but with the use of 5.8 g of polyethylene glycol Carbowax 300 from Unio Carbide and with heating for 5 hours, a 90% sulfide yield is obtained (according to GLC). The NMR spectrum and GLC hardening time of the product are the same as for the product of example 1. EXAMPLE
    [3]
    3. A mixture of 118 g of ODHB, 40 g of 85% potassium propyl mercaptide and 6 g of unbranched poly, ether containing 63 mol.% Of ethylene oxide and 37 mol.% Of tetrahydrofuran monomer units with an average molecular weight of 1615 is heated at reflux temperature overnight. After cooling and filtration to remove the solids, the 12 filter is distilled under vacuum to remove the solvent. Quantitative GLC indicates 85% yield of chlorophenylpropyl sulfide. Similar to this example, but using methyl mercaptide instead of 1; -propyl mercaptan, o-chlorophenyl methyl sulfide is obtained. To illustrate the effect of the catalyst on this reaction, a mixture of 147 g of ODCB and 43 g of potassium methyl mercaptide is prepared and, in the absence of the catalyst, stirred and heated for 1 hour at 957lOO C. After that, o-hdorfenylmethyl sulfide is hardly detected by GLC (area 0.002%). On the contrary, if Carbovax®300 polyethylene glycol (18% by weight, based on the weight of the mercaptide) is introduced at the beginning of the reaction, then after 30 minutes a filtrate is obtained with an area of 44%, and after 60 minutes - 47%. Upon reaching this value, the reaction is basically complete. A similar result is obtained in the case of the use of polyethylene glycol Carbowax® 350.
    [4]
    4. A mixture of 80 g of Q dichlorobenzene (ODCB), 23.5 g of anhydrous potassium methyl mercaptide, and 0.47 g (2% by weight) of Carbowax 400 is heated to boiling point under a nitrogen atmosphere. After 2 hours with reflux, the data obtained by gas chromatography show the content of a mixture of ODHB in an mixture: an area of 82.6% and o-chlorophenylmethyl sulfide with an area of 16, 9%. After an additional 2 hours with reflux, the amounts of the components are 77.8 and 21%, respectively, which indicates a constant accumulation of the product. The invention method for producing ortho-chlorophenylalkyl sulfides based on chlorobenzene derivative by heat, is characterized by the fact that ortho-dichlorobenzene, which is reacted with C, is used as a derivative of chlorobenzene, which is reacted with C (-Cd alkali metal alkyl mercaptide in the presence of acyclic polyethylene as a catalyst 3 12811714
    glycol or unbranched simply-17.05.82. As a catalyst
    th polyester with an average mol. by weight. use acyclic
    300-2000 in the amount of 2-18 wt.% In polyethylene glycol.
    in terms of alksherkaptid at 11.04,83. As a catalyst
    95-195 C. 5 are used unbranched. Priority on the grounds: ny simple ether.
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    同族专利:
    公开号 | 公开日
    IE831130L|1983-11-17|
    CA1216290A|1987-01-06|
    DK217883A|1983-11-18|
    EP0094821B1|1990-08-08|
    AU1456883A|1983-11-24|
    GR81340B|1984-12-11|
    ES522411A0|1986-09-01|
    ES8609187A1|1986-09-01|
    IL68712D0|1983-09-30|
    DK217883D0|1983-05-16|
    IL68712A|1991-07-18|
    EP0094821A1|1983-11-23|
    BR8302508A|1984-01-17|
    DE3381789D1|1990-09-13|
    AU567874B2|1987-12-10|
    NZ204235A|1986-06-11|
    IE56017B1|1991-03-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3484466A|1966-09-30|1969-12-16|Upjohn Co|Preparation of aromatic sulfonyl isocyanates|
    OA05625A|1976-04-07|1981-04-30|Du Pont|N- aryl sulfonamides herbicides, compositions containing them and methods using them.|
    US4169719A|1976-04-07|1979-10-02|E. I. Du Pont De Nemours And Co.|Herbicidal sulfonamides|
    BR8003393A|1979-06-04|1980-12-30|Du Pont|PROCESS TO PREPARE AN ARYLSULPHONYL ISOCIANATE|
    FR2459792B1|1979-06-27|1982-11-05|Rhone Poulenc Ind|
    AU543161B2|1980-03-07|1985-04-04|E.I. Du Pont De Nemours And Company|Pyrimidine or s.triazine derivatives|
    US4310346A|1980-03-14|1982-01-12|E. I. Du Pont De Nemours And Company|N N' ureas|US4603523A|1984-06-20|1986-08-05|H. H. Robertson Company|Underfloor access housing|
    US4678498B1|1985-06-12|1989-01-24|
    DE3530709A1|1985-08-28|1987-03-05|Hoechst Ag|METHOD FOR PRODUCING HALOGENPHENYL-OXETHYLSULFIDES AND THEIR OXIDATION PRODUCTS|
    DE3530710A1|1985-08-28|1987-03-05|Hoechst Ag|METHOD FOR PRODUCING HALOGENPHENYL-OXETHYL SULFIDES AND THEIR OXIDATION PRODUCTS|
    JP3814696B2|1995-04-17|2006-08-30|住友精化株式会社|Process for producing aromatic or heteroaromatic sulfonyl halides|
    TWI232214B|1998-04-16|2005-05-11|Shionogi & Co|Preparation of aryl sulfenyl halide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US37899382A| true| 1982-05-17|1982-05-17|
    US48187483A| true| 1983-04-11|1983-04-11|
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