• 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:

    公开号:SU725555A1
    申请号:SU2652698
    申请日:1978-08-24
    公开日:1980-03-30
    发明作者:Хаэкель Райнер；Оэллерих Михаэль；Хеердт Рут；Хюбнер Манфред；Хельмут Шмидт Феликс
    申请人:Берингер Маннхайм Гмбх (Фирма)；
    IPC主号:
    专利说明:

    Preferably, water, a lower alcohol or acetic acid is used as the diluent. The process takes place at room temperature or slightly heated. In appropriate cases, the process is carried out in the presence of sodium acetate.
    The desired product is recovered in cieu aspirated form or converted into salts using free bases, carbonates or alcoholates.
    Example 1.2- (2-Cyclohexylethylhydrazono) -propionic acid,
    2.7 g (2-cyclohexylethyl) -hydrazisulphate (mp. 185-187 ° C with decomposition) is dissolved in 50 MP BOjjfJ and with stirring at room temperature 1.1 g of pyruvic acid and 3.0 g are added to the solution sodium acetate (trihydrate) in 10 ml of water. At the same time, an oil first precipitates which soon crystallizes. The substance is sucked off on a: filter, dissolved in water with the addition of 6 ml of 2N. sodium hydroxide and slowly acidified with 2N. hydrochloric acid. At first, the first portion falling out contains impurities, then I suck it on the filter and take it out. The bulk of the product, which precipitates upon further acidification, does not contain impurities and is dried in an ericator over calcium chloride. Output 1.6 g (67% of theoretical); so pl. 47C.
    Similarly, obtained by the interaction of pyruvic acid with:
    isobutylgyrazine sulfate; (m.p. 127c with decomposition); 2- {Isobutylhydrazono) -propionic acid; m.p. {recrystallization of vaccine and isooctane);
    methylallyl hydrazinoxalate (mp. 160-16lc with decomposition); 2- (methylallylhydrazono) propionic acid; m.p. 68-69 ° C (recrystallized from a mixture of isooctantroluol);
    2- {propylhydrazono) -propionic acid propylhydrazine saline; m.p. 56-58 ° C (recrystallized from a mixture of ligrointoluene);
    isopentyl hydrazine hydrochloride (mp. 128-130 with decomposition) 2- (isopentyl hydrazono) -propionic acid; m.p. 48-50 C (recrystallized from isoactane);
    octylhydrazine hydrochloride 2- (octylhydrazono) propionic acid; m.p. 37-38 С;
    cyclohexylmethylamine hydrochloride 2- (cyclohexylmethylhydrazono) -propionic acid; m.p. 81-82C (PeroLrytallized from isooctantoluene mixture);
    isopropylhydrazine hydrochloride, 2- (isopropylhydro-3o) propionic acid; m.p. 83-84 ° C (recrystallized from ligroin); .
    2- (allylhydrazono) propanoic acid allylhydrazine hydrochloride; m.p. 47-48 seconds (recrystallized from methylene chloride);
    butylhydrazine sulfate 2- (butylhydrazono) propionic acid; m.p. 56-57c (recrystallized from cyclohexane);
    sec-butylhydrazine sulfate 2- (sec-butylhydrazono) -propionic acid; m.p. 67-68c (reproach in the soda-hydrochloric acid system); tert-butyl hydrazine hydrochloride
    2- (tert-butylhydrazono) -propionic acid; m.p. 99-100 ° C (recrystallized from a mixture of isopropanol - water);
    hexylhydrazine hydrochloride, idom 25 - (hexylhydrazono) -propionic acid; m.p. (soda-hydrochloric acid is sedimented in the system);
    4-methylpentylhydrazine hydrochloride (crude product) 2- (4-methylpentyl0-hydrazono) -propionic acid-oil;
    2-ethylbutyl hydrazine hydrochloride {so pl. 118-125s; Cllroy product) 2- (2-ethylbutylhydrazono) propionic acid; m.p. 83-86 s (recrystallize water from isopropanol from the mixture);
    5-hexenyl hydrazine hydrochloride (mp. 130-135 s, crude product) 2- (5-hexenyl hydrazono) -propionic acid Q, oil;
    heptylhydrazine hydrochloride 2- (heptylhydrazono) -propionic acid; m.p. 4, (recrystallized from ligroin); , cyclopentyl hydrazine 2- (cyclopentyl hydrazono) -propionic acid; m.p. 87-88 ° C (recrystallized from a mixture of isooctane-toluene). (2-cyclopentylethyl) -hydrazine hydrochloride (mp. 160 ° C, crude) 0 2- (2-cyclopentylethylhydrazono) -propionic acid; m.p. 64-65C (recrystallized from a mixture of ligroin - ether);
    2- (3-cyclohexen-1-yl) -ethyl hydra5 with hydrochloride (so pl. 98-138s,
    crude product) (3-cyclohexen-1-yl) ethylhydranzono-propionic acid; m.p. 67-68 0 (recrystallized from a mixture of isopropanol - water; P 2-cyclohexylethylhydrazine hydrochloride (mp. 132-145 C, crude product) 2- (2-cycloheptylethylhydrazono) propionic acid, mp 59-61 s (recrystallized from cyclohexane decylhydrazine hydrochloride
    (mp. 94С with decomposition) 2- (decylhydrazono) -propionic acid; m.p. (recrystallized from isooctane);
    nonylhydrazine hydrochloride Loride 0 (mp. with decomposition); 2- (nonylhydrazono) -propionic acid; m.p. 4b-47 ° C (recrystallized from isooctane);
    (3-cyclohexylpropyl) -hydrazin5 hydrochloride (mp. 220-225C) 2- (3-cyclohexylpropylhydrazono) -propionic acid; butter. Example 2.2- (Pentyl hydrazo) sodium propionate. 2.3 g of pentyl hydrazine hydrochloride is dissolved in 10 ml of water and mixed with a solution of 1.5 ml of pyruvic acid and 2.2 g of sodium acetate in 5 ml of water. An oil is formed. The mixture is stirred for approximately 1 hour, the oil is extracted with methylene chloride, the solution is washed with water, dried out with sodium sulfate and evaporated from methylene chloride. The oily residue is dissolved in 8 ml of ethanol and 3 ml of 30% sodium methoxide solution are added with stirring. 2- (Pentylhydrazono) - sodium propionate precipitates, it is filtered, sucked off on a filter, and washed first with a small amount of ethanol, and then ether. Yield 1, 9 g (59 from the theoretical); m.p. 225-228 With decomposition. Similarly obtained by the interaction of pyruvic acid; with 2-cyclohexylethylhydrazine sulfate and the subsequent preparation of sodium salt of 2- (2-cyclohexylethylhydrazono) sodium propionate; m.p. 230233 with decomposition; with 3-cyclohexylpropylhydrazine hydrochloride (so pl. 220-225 C), followed by the preparation of sodium salt of 2- (3-cyclohexylpropylhydrazono) sodium sulfonate; m.p. 224-22b C with dilatation. Example 3 Dialogically, as described in Example 1, is obtained by the reaction of pyruvic acid: with 9-decenyl hydrazine hydrochloride (crude product) 2- (9-decenyl hydrao but) propionic acid; m.p. 39 - (recrystallized from hex on); with 2-hexenyl-hydrazino-salsate (mp. lee-ieV C) 2- (2-hexenyl-hydrazo-6o) -propionic acid; butter; with methylhydrazine sulfate 2- (methylhydrazono) -propionic acid; m.p. 89-91 C (recrystallized from isopropanol-isooctane mixture); with 5-methylhexylhydrazine hydrs sormids (mp. 184-188 ° C, crude) 2- (5-methylhexylhydrazono) -propionic acid, oil. Example 4. Amide of 2- (decylhydroc) eono-propionic acid. 6.5 g of decylhydrazine dihydrochloride are dissolved in 30 ml of water and 2.3 g of pyruginic acid amide in 40 ml of water are added to a solution. After adding a dilute solution of sodium hydroxide, the pH of the solution is set to about 3 and the solution is kept in the refrigerator for 16 hours. At the same time, the target product crystallizes, is filtered, sucked off on the filter and recrystallized from iso-octane. Yield 3.3 g (61.6% of theoretical); m.p. 64 C with decomposition. PRI me R 5. Ethyl ester of 2- (heptylhydrazono) -propionic acid. 4.0 g of heptyl hydrazine dihydrochloride is dissolved in 40 ml of ethanol and 2.3 g of ethyl pyruvic acid ester are added. The solution is kept for 20 minutes at room temperature, then 160 ml of water is added to it, and the supernatant oil is extracted with ether. The ether solution is washed several times with 2N first. sodium carbonate solution and then with water / dried sodium sulfate and evaporated. The remaining ether does not crystallize. The output of 3.7 / g (82,4% of theoretical). In a similar manner, they are obtained from nonylhydrazine dihydrochloride and methi-. of pyruvic acid ester: 2- (nonylhydraionic) propionic acid methyl ester as an oil. .. Example 6. Similar to that. As described in Example 1, the reaction of pyruvic acid is obtained: with 4-hexecyl hydrazine hydrochloride, free base; bp 82-89 with (14 mm Hg salt is hydroscopic; 2- (4-hexenylhydrazono) -propionic acid / oil. The compound contains 0.6 mol of water; with octadecylhydrazine dihydrochloride; mp. With decomposition, aglo -. Measurement with 88 ° С, 2- (octadecylhydrazoin6) -propionic acid; mp 80.Ci (recrystallized from isooctane); j with 3-butenylhydrazine hydrochloride (: (crude product) 2- (3-butenylhydrod propionic acid; 5 g oil; with 3,3-dimethylbutylhydrazine hydrochloride (mp. 213-214 ° C) 2- (3,3-dimethylbutylhydrazono) propionic acid; mp (recrystallized from isooctane); with 3-meth elktilgidrazinoksalatom (so pl. with decomposition) 2- (3methyloctylhydrazono) -propionic acid in the form of oil; with H-cyclohexyl-2-propenylhydrazine hydrochloride (so pl, 165C with decomposition) propionic acid in the form of an oil; with dodecylhydrate & zindihydrochloride (t.p. 210c with decomposition) after sintering, starting from) 2 - (dodecylhydrazine but-propionic acid; t, pl. 60-61 ° C (recrystallized from isooctane); with 4-methylhexylhydrazine dihydrochloride (hygroscopic; free base; bp. 86-88 C
    (13 mm Hg) 2- (4-mlheylhexyl gid :: asoHO) -phopionic acid in the form of oil V
    with 17methylgvksilhydraenoxalate
    () 2-imyoTylgoyisylgidroyno) -p1 opionic acid in. types of oil -, -, - ;, - With 2-ethylhexylhydpeline 6l free base; m.p. 56-60 C, (0.1 mmHg) 2- (2-ethylhex: ylhydraeno) propionic acid in the form of oil; with s-gokeyl hydrochloride hydrochloride (mp. 166-167 s) 2- (3-hexenylhydra-eono) propynoic acid as an oil; . ; - -. ,
    with 3-cyclopentyl propyl hydrazine hydrochloride (mp. 197-202 C) 2 - (3-cyclopeyl propyl hydraone) -cropionic acid, oil.
    . EXAMPLE 7. In a manner similar to that described in Example 2, the pyruvic acid is obtained by the interaction of: -, ..,;, ;; . . -. ,. ,,, .-.
    with 3-cycle ogexyl-2-methyl-2-11.yo I1 Lihydrazine hydrochloride 6m (oil) with SheleyUyadiM obtaining sodium 2 (3-cycle, pohexyl-2-methyl-2-propenylgydrazono) -yrbpion, t sodium t. square 2bb-2b8 With decomposition (recrystallized from ethanol).
    权利要求:
    Claims (2)
    [1]
    1. A process for the preparation of 2-hydrazonopropionic acid derivatives of the general formula
     -. - -snz .. /. -
    ; RXHN-NC. ..., ...,:
    -: - ...: - - V
    V.,;:. ;. .;:. CORV V: -, v:
     yo |; a-zvetv; te1Gn 1aly rGzveT-; 1 etched, nailed, and nonbasic alkyl group with 1-18 carbon atoms or unbranched & , saturated or unsaturated cycloalkyl group with 5-7 carbon atoms J
    X is a simple bond or unbranched or branched, saturation or an unsaturated alkyl group with l4 carbon atoms, and if X is a simple bond, then R cannot mean a cyclohexyl group
    R - OXI-, lower alkoxy or
    amine group,
    or ihshly, about tl and h and y y and i, hydrazine total
    with
    R-X-NH-NH,
    g
    where R and X have a sheuk: zannye meaning
    Q or its salt is reacted with a propionic acid derivative of the formula
    , CH -CCRjR. ) -COR,
    where R has the above values,. . /. .
    RjH R halogen, alkoxy together means oxygen in a polar solvent, followed by isolation of the desired product in free form or as a salt. 0 - -. .-. ,;
    [2]
    2 .. The method according to p. 1, about tl and h ayush and with the fact that as a solvent using water or lower, alcohol, or acetic acid.
    Source of information
    taken into account in the examination
    1. Weigand-Hilgetag. Methods of ex .. periment in organic chemistry, Himi, M., 1968, p. 474.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU725555A1|1980-03-30|Method of preparing 2-hydrazonopropionic acid derivatives or their salts
    SU439983A1|1974-08-15|Method for preparing ethylenebenzoyl derivatives
    SU1217252A3|1986-03-07|Method of producing oximes of pyruvic acid,or their salts or amides
    DK149586B|1986-08-04|PROCEDURE FOR PREPARING 1-AMINO-CYCLOPROPAN-CARBOXYLIC ACID AND DERIVATIVES THEREOF
    EP0179254A1|1986-04-30|4,5-Dihydro-4-oxo-2- [|amino]-3-furancarboxylic acids and derivatives thereof
    SU856382A3|1981-08-15|Method of preparing cynnolin-3-yl-carboxalic acids or their salts
    US4575557A|1986-03-11|Preparation of substituted benzamides
    US2641601A|1953-06-09|Furans and method of preparation
    SU936806A3|1982-06-15|Process for producing 3-|-phenyl esters of carbonyl acid
    US5663365A|1997-09-02|Process for the preparation of pyrazolones
    CA1086329A|1980-09-23|Unsaturated carboxylic acids
    SU439978A1|1974-08-15|The method of obtaining sulfamoylpyrimidine or its salt
    SU505358A3|1976-02-28|The method of producing piperazine derivatives
    SU474143A3|1975-06-14|Method for preparing dibenzofuran or carbazole derivatives
    US4517130A|1985-05-14|Substituted amino acid process
    SU719493A3|1980-02-29|Method of preparing 2-|-propionic acid or its derivatives
    US4656309A|1987-04-07|Preparation of alpha-pivaloyl-substituted acetic acid esters
    US3950381A|1976-04-13|Preparation of aroyl acidic esters
    SU545250A3|1977-01-30|Method for preparing substituted biphenylyl butyric acid or its esters or its salts
    EP0220025A1|1987-04-29|3-perfluoroalkyl-5-hydroxyisoxazoles
    SU446506A1|1974-10-15|Method for preparing 4-aminoquinazoline derivatives
    US4385004A|1983-05-24|Esters of ortho-allylphenol useful for the preparation of arylacetic acid derivatives
    RU2624226C2|2017-07-03|Method of producing n-arylamides of arolylpiroinburgate acids
    SU1313856A1|1987-05-30|Method for producing derivatives of cis- or trans-diaminodibenzoyl-dibenzo-18-crown-6
    US2524799A|1950-10-10|Hydroxybenzenesulfonamidoimidazoles and preparation of the same
    同族专利:
    公开号 | 公开日
    EP0001144B1|1981-06-17|
    CA1109077A|1981-09-15|
    ZA784969B|1979-09-26|
    AR216531A1|1979-12-28|
    AU3923378A|1980-02-28|
    CS199744B2|1980-07-31|
    PL209256A1|1979-06-04|
    FI66843C|1984-12-10|
    IT7827078D0|1978-08-28|
    AT363454B|1981-08-10|
    FI782574A|1979-03-02|
    IE47260B1|1984-02-08|
    YU204778A|1982-10-31|
    US4206231A|1980-06-03|
    PT68483A|1978-09-01|
    DD138652A5|1979-11-14|
    FI66843B|1984-08-31|
    ATA627478A|1981-01-15|
    HU177956B|1982-02-28|
    DK147197C|1984-10-29|
    IT1098384B|1985-09-07|
    DK147197B|1984-05-14|
    SU725555A3|1980-03-30|
    AU516223B2|1981-05-21|
    IL55427A|1981-12-31|
    ES472749A1|1979-02-16|
    DK373478A|1979-03-02|
    JPS5452028A|1979-04-24|
    IE781756L|1979-03-01|
    JPS6218545B2|1987-04-23|
    EP0001144A1|1979-03-21|
    PL111073B1|1980-08-30|
    DE2860777D1|1981-09-24|
    DE2739380A1|1979-03-08|
    IL55427D0|1978-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2643303A1|1976-09-25|1978-03-30|Haeckel Rainer|HYPOGLYKAEMICALLY ACTIVE DRUG|
    CA1106389A|1976-09-25|1981-08-04|Rainer Haeckel|2--propionic acid derivatives and the preparation thereof|DE3031842A1|1980-08-23|1982-04-08|Boehringer Mannheim Gmbh, 6800 Mannheim|N-SUBSTITUTED BRYTHE ACID HYDRAZONE, METHOD FOR THE PRODUCTION THEREOF, AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS|
    DE3036281A1|1980-09-26|1982-05-13|Boehringer Mannheim Gmbh, 6800 Mannheim|0-SUBSTITUTED PETROLEUM ACID OXIMES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS|
    EP0298955A1|1984-07-17|1989-01-18|Roche Diagnostics GmbH|UTILIZATION OF $g-CETOCARBONIC ACID HYDRAZONES AND OXINES FOR TREATING CARDIAC OR CIRCULATORY DISEASES|
    EP1663954A2|2003-08-08|2006-06-07|La Jolla Pharmaceutical Co.|Inhibitors of semicarbazide-sensitive amine oxidaseand vap-1 mediated adhesion useful for treatment of diseases|
    WO2006041922A2|2004-10-08|2006-04-20|Dara Biosciences, Inc.|Agents and methods for administration to the central nervous system|
    US20090012067A1|2005-02-14|2009-01-08|Luciano Rossetti|Modulation of Hypothalamic Atp-Sensitive Potassium Channels|
    US8242058B2|2006-07-21|2012-08-14|Wisconsin Alumni Research Foundation|Reagents and methods for appending functional groups to proteins|
    US9047945B2|2012-10-15|2015-06-02|Marvell World Trade Ltd.|Systems and methods for reading resistive random access memorycells|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772739380|DE2739380A1|1977-09-01|1977-09-01|N-SUBSTITUTED 2-HYDRAZONO-PROPIONIC ACID DERIVATIVES, METHOD FOR PRODUCING THE SAME AND MEDICINAL PRODUCTS CONTAINING THE SAME|
    [返回顶部]