• 专利附录
  • 专利说明
  • 权利要求
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  • 引用文献
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  • 优先权
    • 专利摘要:
    Compounds are prepared of the formula <IMAGE> (I) where R' is a t-alkyl group having 4 to 18 carbon atoms, preferably t-butyl, t-amyl or t-octyl and R is a straight or branched chain alkyl group with 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms or an alkyl group substituted with one or more phenyl group or a halogen atom, particularly a chlorine atom, or a cycloalkyl group with 3 to 8 carbon atoms, particularly cyclopropyl, which can be substituted by one or more 1 to 3 carbon atom alkyl groups or one or more halogen atoms, preferably chlorine, or phenyl or naphthyl or a five membered heterocyclic group or such phenyl, naphthyl or heterocyclic group substituted by halogen atoms, nitro groups, alkyl or alkoxy with 1 to 5 carbon atoms by condensing in acid medium an acyl cyanide of the formula R-CO-CN (II) where R is as defined above with either (a) a tertiary alcohol of the formula HO-R'(III) in which R' is as defined above, or preferably (b) an alkene of the formula <IMAGE> (IV) where R1 and R2 are the same or different and are hydrogen or an alkyl group and wherein R3 and R4 are the same or different and wherein the alkyl groups in each case can be 1 to 15 carbon atoms. Some of the compounds are new. They are useful as intermediates for synthesizing herbicides and can be used directly as fungicides.
    公开号:SU797573A3
    申请号:SU782639444
    申请日:1978-07-19
    公开日:1981-01-15
    发明作者:Клееманн Аксель；Кленк Херберт；Офферманнс Хериберт；Шерберих Пауль；Шварце Вернер
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING N-SUBSTITUTED AMIDES OF A-KETOKARBONIC ACIDS
    A large excess of K11; 1ich (.c1ne. For example, from 1 to 10 times 1-1.5 mol of acid is used per 1 mole of acylshanide.
    Sulfuric acid is preferable as an acid, but sulphonic acids can also be used. for example, benzenesulfonic acid.
     After hydrolysis with a reaction mixture, amide ketocarboxylic acids are isolated by known methods, for example, crystalline; by
    distillation.
    Example 1. In arfnapar, with (removed by a mixer and protected from moisture, 131 g (1.0 mol) of benzoyl cyanide, 148 g (2.0 mol) of tert-butanol and 50 ml of methylene chloride) are placed and stirred at approximately 5 150 g (1.5 mol) of concentrated sulfuric acid are added dropwise to the mixture. After stirring the droplets, the reaction mixture is kept stirring at room temperature for 1 h, and then the whole mixture is poured onto 400 g of ice and the xopoiuo is stirred. extracted with methylene chloride and the methylene chloride solution evaporated. As a result, 19 5 g of N-tert.-25 butylamide phenylglyoxylic acid, which corresponds to a yield of 95%, calculated on the used. Amide has a melting point of 76-77 ° C.
    According to the method described in Example 1, the following compounds of the PCOCOMNS (CH3) s (Table 1) are obtained, which are obtained either in pure form or purified by distillation or recrystallization.
    Example 2. The experiment was carried out as decomposed in Example 1, however, instead of tert-butanol, 176 g (2.0 mol) of tert-amyl alcohol (2-methyl-butanol-2) was used.
    210 g of N-tert.-amylamide of phenylglyoxylic acid are recovered, corresponding to a yield of 40–96%, of the yield per used cyanide of acid. The amide has a melting point of 29-30 C.
    Calculated,%: C 71.2; H 7.8; N,
    Found,%: C 71.06; H 7.97; N.
    According to the method described in Example 2, the following compounds YOSOCOMNS (CH3) 2C2H5 (Table 2) are obtained, which are purified either by distillation or recrystallization.
    Example Z. In an apparatus equipped with a stirrer and protected from moisture, 50 111 g (1.0 mol) of pivaloyl dianide, 150 g (5 mol) of concentrated sulfuric acid and 150 ml of glacial acetic acid are placed and stirred at 0-5 ° C 112 g (2.0 mol) of isobutylene are passed through for 1 hour. Immediately, the reaction mixture is then heated to room temperature and continued to stir for 4 hours. Then the mixture is poured onto 500 g of ice and after good mixing.
    sucked amide precipitated. After drying in a vacuum oven, 161 g of pure N-t-butylamide trimethyl pyruvic acid was isolated for analysis, corresponding to a yield of 87%, based on the cyanide used. The amide melts at 65 ° C. According to the method described in Example 3, the following compounds of the POCOMNS (CH3) -z (Table 3) are obtained, which are either isolated as pure products or purified by distillation.
    Example 4. The experiment was carried out as described in example 3, however, instead of introducing isobutylene, 140 g (2.0 mol) of 2-methyl butene-2 was added dropwise. 169 g of M-tert.butylamide of trimethylpyruvic acid were isolated, which corresponds to a yield of 85%, based on the added cyanide of acid. The amide has a melting point of 36 ° C.
    Example 5. The experiment was carried out as described in example 4, however, instead of pyvoylocycylide, 69 g (1.0 mol) of acetyl cyanide was used. After the reaction mixture was poured into ice, the solution was extracted with ether, after which the ether was evaporated and the residue was fractionated.
    88 g of N-tert.-amylamide of pyruvic acid are recovered, which corresponds to a yield of 56% based on the used planid acid. Amide has a boiling point of 79 ° C at 14 mm Hg. Art.
    Calculated 7o: C 60.7; H 9.6; N 8,85.
    Found,%; C 59.9; H 9.92; N 8.38.
    Example 6. The test was carried out as described in Example E, however, instead of passing isobutylene, 224 g (2.0 mol) of 2,4,4-trimethylpentene-2 (L-diisobutylene) was added dropwise. After the reaction mixture is poured onto ice, all of the methylene chloride is extracted and the organic phase is immediately evaporated in a rotary evaporator at a bath temperature of 70 ° C. 125 g of oil is obtained, which crystallizes in a refrigerator. This corresponds to a yield of 52%, calculated on the injected cyanide acid. N-t-octylamide trimethylpyruvic acid has so pl. 20-2 G C.
    Calculated, With 69,66; H 11.27; N 5.80,
    Found,%: C 69,22; H 11.42; N 5.78.
    The structure is confirmed by the PMR spectrum.
    Example 7. In a moisture protected apparatus, 131 g (1.0 mol) of benzoyl cyanide are mixed, 48 g (2.0 mol) of tert-butanol and 200 ml of methylene chloride, and 150 g (1 , 5 mol) concentrated sickle it acid. After the completion of the dropping, the mixture is stirred for another 1 hour at room temperature and then the whole mixture is poured onto 400 g, and mixed. It is then extracted with methylene chloride and the methylene chloride solution is evaporated. 191 g of N-tert.butylMID of phenylglyoxylic acid are obtained.
    5. 79
    which corresponds to the yield of 937f in terms of used Sch1a (acid id.
    Example 1: The experiment was carried out as in Example 1, but 1,2-dichloroethane was used instead of methylene chloride. Sulfuric acid is added dropwise at 50 ° C.
    Get 180, 5 tons of amide, which corresponds to a yield of 88%,
    The amides of a - ketocarboxylic acids, which can be obtained by the proposed method, are new. They can be used as intermediates for the synthesis of herbicides. For example, they can be converted to 1,2,4-triazinones by reacting with a thiocarbohydrazide in the presence of a polar solvent (alcohols, water, dimethyl sulfoxide, dimethylformamide, etc.) and, if appropriate, in the presence of an acid catalyst (hydrochloric acid or sulfuric acid). acid). Immediately after this, the methylation of the sulfur atom can be carried out. In addition, these compounds can be directly used as fungicides.
    Amides of a-ketocarbonyl 1 x acids can be converted by hydrolysis to free a-keto carboxylic acids, which in turn are important intermediates in the synthesis of amino acids.
     Table 1
    ABOUT
    85
    0
    (SNE) zS73
    , d.
    but
    56
    Connecting
    7.22
    6,69
    m.p. 42-43 7.46 6.63
    7.02
    m.p. 34-36
    7.09
    5.84
    m.p. 140-142
    6.11
    Taolitsa 3
    Physical properties, C
    Output, %
    m.p. 77
    权利要求:
    Claims (1)
    [1]
    CHC (CHj), Formula of the Invention. Method of producing N-substituted amides of a-ketocarboxylic acids of general formula T () in R-C-C NHR
    m.p. 69-71
    m.p. 85
    m.p. 37 where H is -normal or iso-alkyl, Cg-Cg-cycloalkyl, unsubstituted or substituted with C, -C-alkyl or one or more -. K, chlorine atoms, phenyl, unsubstituted or substituted by methyl or chlorine, or o; -furyl, R - C -Cft-tert.alkyl.
    9 . 79757310
    characterized in that the acyl cyanide wherein R is as defined above, or
    General formula GI corresponding alkene in an acidic environment with
    R-CO-CNtemperature from -20 to + 50 ° C.
    where R has the above values, information sources,
    bathe with tertiary alcohol total fqp-j taken into account during the examination
    mules. J.Ugi, U.Fetzer, Ber., 94, 1961. 1116
     HO-R 21.
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    同族专利:
    公开号 | 公开日
    DE2733181A1|1979-02-08|
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    FR2398047B1|1984-01-20|
    BE869140A|1979-01-19|
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    引用文献:
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    GB1028812A|1962-08-28|1966-05-11|Ici Ltd|Indole derivatives|
    DE1290138B|1965-08-17|1969-03-06|Basf Ag|Process for the preparation of carbonic acid amides|
    DE1542873C3|1966-04-16|1978-07-13|Bayer Ag, 5090 Leverkusen|Herbicidal agent based on 4-amino-1,2,4-triazin-5-ones|
    DE1618007A1|1967-05-09|1970-10-29|Thomae Gmbh Dr K|Process for the production of new amino-monohalophenylaethanolamines|
    FR2127265A5|1971-03-02|1972-10-13|Ugine Kuhlmann|
    DE2165554A1|1971-12-30|1973-07-05|Bayer Ag|3,4,6-substd 1,2,4-triazin-5-ones - with herbicidal activity prepd from acid halides,isonitriles and hydrazine derivs|
    FR2167265A5|1972-01-11|1973-08-24|Pitner Alfred|
    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|
    US4096184A|1976-01-19|1978-06-20|Sumitomo Chemical Company, Limited|Process for preparing acid amides|
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