• 专利附录
  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    Urea derivatives of the formula <IMAGE> (wherein Ar represents a residue of 5- or 6-membered heteroaromatic ring; R represents a hydrogen atom or a C1-C6 alkyl group; R1 represents a C1-C6 alkyl group; and R2 represents a C1-C6 alkyl, C2-C6 alkenyl, or C1-C6 alkoxy group) are produced by reacting an amine of the formula Ar-NH-R (wherein Ar and R have the significance given above) with a carbamoyl halogenide of the formula <IMAGE> (wherein X represents a halogen atom, and R1 and R2 have the significance given above) in the presence of a Lewis acid in an inert solvent.
    公开号:SU1091853A3
    申请号:SU782608147
    申请日:1978-04-28
    公开日:1984-05-07
    发明作者:Макисуми Ясуо；Сасатани Такаси；Мирабаяси Акира
    申请人:Сионоги Энд Ко, Лтд (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for the preparation of urea derivatives of the general formula (I) Ar-K-C O-JS c. “Where Ar is oxazol, which may be en C —C2 alkyl with phenyl, pyridyl, thiazolyl which may be substituted by one or two methyl groups, benzthiazolyl; hydrogen, ,, - alkyl) C -C-alkyl, Kd - with -C-alkyl, allyl, methoxy which can be used as herbicides of selective action. A known method for the preparation of transient ureas of the general formula (I), in particular 1,1-dimethyl-3- (5-tert.-butyl-3-isoxazolyl) urea, which consists in the interaction of n6-5-tert-butylnsoxazole with H, N-dimethylcarbamoyl chloride in the presence of a base, such as pyridine, at 50-70 ° C. This method has the disadvantage that the yield of the reaction product is inevitably reduced as a result of the formation of 1,3-bis- (5-tert-butyl-3-isoxazolyl urea, an undesirable by-product of the reaction. Yield 60%. The purpose of the invention is to increase the yield The desired product is achieved by the method of obtaining urea derivatives of general formula (I) by reacting an amine of general formula (II) Ar-NH-E where Ar and R have the indicated values with carbamoyl chloride of general formula. (III) (Ji- (JO- K where R2 and RI have the indicated values at the temperature of boiling in the presence of a Lewis acid in an inert solvent environment. Preferably, aluminum chloride is used as Lewis acids. when heated, preferably at a temperature approximately equal to the boiling point of the solvent. The ratio of the carbamoyl halide of formula (III) to the starting amine of formula (II) may be approximately 1.0 to 1.2 mole, eq., preferably about 1.0 to 1.1 mol. equiv. The ratio of Lewis acid to the starting amine of formula (II) may be about 1 to 1.2 mol. Equiv., Advantageously about 1 to 1.1 mol. Sec. Example 1. S, N-Dimethylcarbamoyl chloride (7, .91 g) and aluminum chloride (9.80 g) are added to toluene (100 ml) and the mixture is stirred at room temperature for 30 minutes. H-amino-5-tert.-butylisoxazole (9.81 g) is added to this mixture and the resulting reaction mixture is heated with reflux for 6 h with simultaneous stirring. After cooling, the reaction mixture is mixed with water, stirred at room temperature and shaken with toluene. The organic layer was evaporated to remove toluene, resulting in 1,1-dimethyl-3- (5-tert.-butyl-3-isoxazolyl) urea (14.63 g). The product yield is 98.9%. M.p. this colorless crystalline substance 119-120,5 ° C (after recrystallization from benzene). Examples 2-5. The reaction is carried out analogously to example 1, but using the Lewis cells listed below instead of aluminum chloride; 1,1-dimethyl-3- (5-tert.-butyl-3-isoxazolyl) urea is obtained as a result of this reaction with the corresponding yields: Yield,% Examples Lewis Acid Examples 6-12. The reaction is carried out analogously to example 1, but using the following starting
    310U1853 4
    substances of formula (II) and substances form the corresponding urine derivatives (111); as a result of this reaction, half of formula 1, as shown in Table. one .
    Rik2 5.5
    S1COKG N
    RI
    R.
    -Ttf- /
    V3
    -iL 1gЛП-
    K Oh
    Table 1
    Abbreviations in Note H are hydrogen. M group, Pr - pa pas, Ph - phenyl t - tertiary. Example 13. K, M-Dimethylcarbamoyl chloride (1.29 g) and aluminum chloride (1.60 g) were dissolved in toluene (40 ml) and the mixture was stirred at room temperature for 45 minutes at room temperature for 45 minutes. H-amino-5-phenylisothiazole (1.76 g) is added to this mixture, and the resulting reaction mixture is refluxed for 6 hours. After cooling, the reaction mixture is mixed with water and stirred with toluene. The organic layer is separated, washed with water, dried and evaporated to dryness, resulting in a yield of 1., 1-dimethyl-3- (5-phenyl-3-isothiazolyl) urea (2.38 g). The product yield is 96.4%. M.p. This colorless Table 2 has the following e values: - methyl 1 per group, Et - ethyl opil group, Bi - butyl group, Br - bromine, i-iso. crystalline material 129130, 5 С (after recrystallization from a mixture of benzene / petroleum ether). Example 14. A mixture containing 2-amino-4-methylthiazole (1.14 g), N, N-dimethylcarbamoyl chloride (1.29 g), aluminum chloride (1.60 g) and xylene (40 ml) is heated in reverse by refluxing for 20 hours. The reaction mixture is treated in the same manner as in Example 1, resulting in 1,1-dimethyl-3- (4-methyl-2-thiazolyl) urea (1.73 g) . The product yield of 93.5%. M.p. 97-98 ° C (pure product is recrystallized from diethyl ether / petroleum ether) ..
    Example 15 A mixture comprising 2-amino-4,5-: dimethylthiazole (1.28 g), N, N-dimethylcarbamoyl chloride is used. (1.29 g), aluminum chloride (1.60 g) and xylene (40 ml), and the reaction is 5 as in example 1, yielding 1,1-dimets-3- (D, 5- dimethyl-2-thiazolyl) urine1 inu (1.82 g). The product yield of 91.5%. M.p. 202.5 ° С204 С (after recrystallization from O ethyl acetate).
    Example 16. A mixture containing 2-aminobenzothiazole (1.50 g) S, H-dimethylcarbamoyl chloride (1, 29 g), aluminum chloride (1.60 g) and trichloro-15 ethylene (40 ml) is used, the reaction is carried out similarly Example 1, but refluxing is continued for 40 hours. As a result of this reaction, 1,1-dimethyl-3- (2-bsi-20-thiazolyl) urea (2.16 g) is obtained. The output of urea 97,7%, T, pl. - more (after recrystallization from ethanol),
    Example 17 A mixture containing 2-aminopyridine (941 g), S, M-dim8Tyl-25 carbamoyl chloride (1.29 g), aluminum chloride (1.60 g) and xylene (30 ml) is heated to reflux. After 8 hours, after cooling, this reaction mixture is made alkaline with sodium hydroxide and stirred together with chloroform. The organic layer is separated, washed with water, dried and evaporated, removing the solvent, yielding 1.1 dimeTIII-3- (2-pyridyl) urea (1.57 g) as an oily product. salt picric acid) has so pl. 187-18955 ° C (melting with decomposition). before
    Example 18. A mixture containing 3-amino-5-tert-butylisoxazole and N-ethyl-N-methylcarbamoyl chloride is used. The reaction is carried out analogously to Example 1, whereby 1-ethyl-1-methyl-3- (5-tert-butyl-3 isoxazolyl) urea is obtained. The output of urea is 96.1%. M.p. 88.5-89 ,.
    Example 19. Use a mixture containing 3-amino-5-tert.-butylizok
    sazol and N-allyl-Y-methylcarbamoyl chloride, and the reaction is carried out as in Example 1, whereby 1-allyl-1-methyl-3- (5-tert.-butyl-3-isoxazolyl) urea is obtained. The product yield of 90.5%. M.p. 90.0-91 ,.
    Example 20 A mixture containing 3-amino-5-tert.-butylisoxazole and L-methoxy-N-methylcarbamoyl chloride was used, and the reaction was carried out as in Example 1, resulting in 1-meto-1-methyl-3- ( 5-tert-butyl-3-isoxazolyl) urea. The output of urea 94,7%. M.p. 106.0-107.0 ° C.
    Example21. The reaction mixture containing 3-amino-5-tert.-butylisoxazole and L M-diethylcarbamoyl chloride is used, and the reaction is carried out as in Example 1, yielding 1,1-diethyl-3- (5-tert.-butyl-3 -isoxazolyl) urea. The urea yield is 98.2%. M.p. 122.0-123.5С.
    Example 22. Using the procedure of example 1, the reaction mixture was heated in chloroform at its reflux temperature (61.2 C) for 70 hours,
    The yield of the target product is 89%.
    Example 23. Using the procedure of example 1, the reaction mixture is heated in benzene at its reflux temperature (80.1 ° C) for 20 hours. The yield of the desired product is 98%.
    Example 24. Using methyl n-butylcarbamoyl chloride instead of dimethylcarbamoyl chloride according to the method of example 1, 1-methyl-1-n-butyl-3 - (5-tert-butyl-3-isoxazole) urea is obtained in the form of crystals with m.p. 63.5-65.5 C. Yield 96%.
    Comparative Example 184 of the prototype shows that the reaction of 3-amino-tert-butylisoxazole with dimethylcarbamoyl chloride in the presence of pyridine results in 1,1-dimethyl-3- (5-methyl-3-isoxazolyl) urea in 56% yield, compared with with a prototype.
    ABOUT
    sn.
    II
    (;-to(
    /
    sh.
    Table 2 presents examples of the preparation of compounds of formula (I) according to
    the proposed method in comparison with the control.
    table 2
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING UREA DERIVATIVES OF GENERAL FORMULA
    Λ
    Ar-K-CO-N where Ar is oxazolyl which may be substituted by Cp-C 2 _ alkyl, phenyl, pyridyl, thiazolyl which may be substituted by one or two methyls, benzthiazolyl,
    R is hydrogen, C and -C 2 alkyl,
    R 2 ~ C ^ -C ^ -alkyl,
    R - C l-C ~ -alkyl, allyl, methoxy, by reaction of an amine of the general formula. Ar-NH-Rp where Ar and R have the indicated meanings, with carbamoyl chloride of the general formula D 2 "5 where R, and R- have the indicated meanings,
    4 0 - Q when heated, distinguishing - <d with the fact that, in order to increase the yield of the target product, the process is carried out at the boiling point in the presence of Lewis acid in an inert solvent.
    [2]
    2. The method of pop. 1, characterized in that the aluminum chloride is used as the Lewis acid.
    SU <, "1091853>
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    同族专利:
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    引用文献:
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    US2755285A|1956-07-17|I-xsubstituted |
    US2756135A|1955-07-13|1956-07-24|Du Pont|1-methyl-3--ureas and their use as herbicides|
    DE1209801B|1963-05-11|1966-01-27|Bayer Ag|Weed control in Rueben|
    US3293257A|1964-09-14|1966-12-20|United States Borax Chem|Pyridyl urea compounds|
    FR1533184A|1965-04-06|1968-07-19|Pechiney Saint Gobain|Thiazole derivatives|
    DE1620448C3|1965-05-08|1974-08-29|Schering Ag, 1000 Berlin Und 4619 Bergkamen|Urea or thiourea derivatives of 3-methylisothiazole|
    US3622593A|1967-08-09|1971-11-23|Fmc Corp|1,1-dimethyl-3-urea|
    US3547940A|1967-10-31|1970-12-15|Du Pont|Substituted ureido isoxazoles|
    GB1266769A|1969-08-15|1972-03-15|
    JPS5031039A|1973-07-27|1975-03-27|
    US4062861A|1973-07-27|1977-12-13|Shionogi & Co., Ltd.|3-Isoxazolylurea derivatives|
    US4013706A|1973-11-14|1977-03-22|Sucreries Du Soissonnais Et Compagnie Sucriere|Derivatives of substituted urea, acyl ureas, and sulphonyl ureas, and a process for producing the same|
    US4046770A|1974-08-30|1977-09-06|Eli Lilly And Company|N--N'-phenyl ureas|
    JPS5810361B2|1974-10-04|1983-02-25|Shionogi Seiyaku Kk|GB8422461D0|1984-09-05|1984-10-10|Wyeth John & Brother Ltd|Pyridine derivatives|
    US4808722A|1985-10-31|1989-02-28|Fmc Corporation|Pyridinylurea N-oxide compounds and agricultural uses|
    ES2062248T3|1989-11-10|1994-12-16|Agrolinz Agrarchemikalien|PROCEDURE FOR OBTAINING PURE UREAS, ASYMMETRICALLY DISUBSTITUTED.|
    DE3940261A1|1989-12-06|1991-06-13|Agrolinz Agrarchemikalien Muen|Prodn. of di:substd. urea herbicides and fungicides, e.g. fenuron - by reacting amine with N-alkyl- or N,N-di:alkyl-urea in presence of corresp. alkyl- or di:alkylamine|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP52049629A|JPS6033109B2|1977-04-28|1977-04-28|
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