• 专利附录
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    • 专利摘要:
    The method for the preparation of pyrochloric acid oximes of the general formula RA-0-NC R, COOH where R is a hydrogen atom, a cyclohexyl, naphthyl, phenyl, phenoxy-strong residue, and the phenyl moiety may contain one or two substituents. alkyl, lower alkoxy, halogen atom, trifluoromethyl residue, nitro group, R - lower alkyl residue that can be substituted by halogen A - saturated linear or branched lower alkylene residue, unsaturated linear lower alkylene, moreover, RA cannot mean b methyl, ethyl, benzyl or their salts, or amides, about t - -G, in which the compound of the general formula RAY where RiH A has the indicated values Y is chlorine or bromine, is reacted with the compound of the general formula XR, - C - COOH (L / (1. Where X and X (together mean the group -NOH; R has the indicated value, and the target product is isolated in the form of the free acid, or, S if necessary, the latter is converted into the corresponding acid amide or salt. N9
    公开号:SU1217252A3
    申请号:SU823449247
    申请日:1982-06-08
    公开日:1986-03-07
    发明作者:Петер Вольфф Ханс；Хеердт Рут；Хюбнер Манфред；Кюнле Ханс；Хельмут Шмидт Феликс
    申请人:Берингер Маннхайм Гмбх (Фирма)；
    IPC主号:
    专利说明:

      12 The invention concerns a process for the preparation of new 0-substituted Pierce-grape acid oximes from salts and amides, which exhibit a pronounced hypoglycemic effect and differ in their high chemical stability in the physiological environment.
    The proposed method receive oxides of pyruvic acid of the formula
    R
    R-A-0-N-C
    (




    -soon
    where R is a hydrogen atom, cyclohexyl, naphthyl, phenyl, phenoxy is a strong residue, and the phenyl fragment can contain one or two substituents, which can be lower alkyl, lower alkoxy, halogen atom, trifluoromethyl residue, neutro group, chlorphenoxy,
    RI is a lower alkyl residue which may be substituted by halo
    A - saturated linear or branched lower alkylene residue, non-saturated linear lower alkylene, and R-A can not mean methyl, ethyl, benzyl group, as well as the salts of these compounds and their amide.
    The goal of avoidance is to develop a method for producing new pyruvic acid oximes that have a hypoglycemic effect and at the same time high chemical stability in the physiological environment.
    Example 1 Sodium 2- (2-metalloxyimino) propionate.
    To a solution of 13.6 g (0.2 mol) of sodium ztilate in 200 ml of ethanol, 10.3 g (0.1 mol) of pyruvic acid oxime are introduced with stirring. Immediately thereafter, 18.1 g (0.2 mol) of J -methyllchloride is slowly added dropwise to the mixture while heating to its boiling point, and the reaction mixture is kept for 14 hours at the same temperature. Then, 9.0 g (0.1 mol) of metal-methyl chloride and 6.8 g (0.1 mol) of sodium ethylate are again added to the reaction mixture, then heating is continued for 7 hours. After that, the mixture is filtered off in a hot condition. the precipitate formed, the filtrate is evaporated, and after
    52
    evaporation of the residue is recrystallized from ethyl alcohol.
    Output 7.3 g, (61% of the theoretically calculated value), mp. 240 C (dec) ..
    In a similar manner, pyruvic acid oxime and
    a) sodium 2-methoxymethyl bromide; 2- (2-methoxyethyloxyimino) -propionate, m.p. 185 ° C (decomp.);
    c) Sodium 3-phenylpropyl bromide 2- (3-phenylpropylpoxyimino) propionate, m.p. 234 ° C (decomp.) (Ethyl alcohol-water);
    c) Sodium 2-phenoxyethyl bromide 2- (2-phenoxy ethyloxyimino) propionate, m.p. 209 C (decomp.) T ethyl alcohol),
    d) 2- (2-cyclohexylethyloxyimino) sodium propionate, 2-cyclohexylethylbromide, mp; 234-235 C (decomp (ethyl alcohol).
    Example 2. 2- (2-p-tolylethyl-hydroxyimino) -propionic acid.
    Analogously to Example 1, 2-p-tolylethylbromide and pyruvic acid oxime react and after the completion of the reaction, the reaction mixture is evaporated. The residue is dissolved in a small amount of water, the solution is washed with diethyl ether, after which the aqueous solution is acidified. The precipitate formed is filtered and dried.
    Yield 41% of theoretically calculated value, m.p. 106-SW S. I
    In a similar way receive
    from pyruvic acid oxime and a) 2-phenylstilbromid 2- (2-phenylethyloxyimino) -propionic acid,
    m.p. 74 ° C
    c) Hexyl bromide 2-hexyloxy-
    propionic. acid, so pl. ,
    c) octyl bromide 2-octyloxyiminopropionic acid, m.p. 42 ° s
    (naphtha),
    d) 3-phenylpropargyl bromide
    2- (3-phenyl-2-propynyloxyimino) -propionic acid, so pl. 84-85 C.
    With the appropriate choice of source components in the same way can be obtained:
    2- (3-bromocinamyloxyimino) -propionic acid, m.p. 107-109 ° C;
    2- (3-nitrocinnamyloxyimino) prprionic acid, so pl. 131-132 s;
    2- (3-chlorinamineloxyimino) - propionic acid, so pl. 116-118 ° С
    312
    2g. (3-chlorocinnamineloxyimino) -3-fluoropropionic acid, m.p. 9294 s;
    2- (3-chlorocinnamineloxyimino) butyl acid, m.p. 91-93 C,
    2- (o (-methylcinnamineloxyimino) -propionic acid, mp. 56-58 Cj
    2-cyanamyloxyiminopropionic acid, m.p. 89-91 C;
    2- (0-methylcinnamyloxyimino) -propionic acid, so pl. 139 С;
    2- (3-chlorocinnamineloxyimino) -propionic acid, so pl. 99-100 С
    2- (2-chlorocinnamineloxyimino) -propionic acid, so pl. 88-90 C (methyl alcohol - water);
    2- (4-chlorocinnamineloxyimino) -propionic acid, so pl. 114-116 C (ethyl acetate - ligroin)}
    2- (allyloxyimino) -propionic acid, so pl. 38-39 C;
    2- (4-fluorocinnamineloxyimino) -propionic acid, m.p. 98-100 C (ethyl acetate and
    naphtha);
    2- (3-trifluoromethylcinnamineloxyimino) propionic acid, m.p. 103-105 ° C,
    2- (3-methylcinnamyloxyimino) - propionic acid, sodium salt, so pl. (different)
    2- (4-tert-boothin cinnamineloxyimino) - propionic acid, so pl. 114-11b with
    2- (3-methoxycinnamineloxyimino) - propionic acid, so pl. 91-92 ° C;
    2- (2-methoxycinnamineloxyimino) - propionic acid, so pl. 84-8b with;
    2- (5-chloro-2-methylcinnamyloxymino) propionic acid, m.p. 112 ° CJ
    2- (5-chloro-2-methoxycin namyloxyimino) propionic acid, m.p., 125-12b;
    2- 3- (1-naphthyl) -2-propenyloxy-imino-propionic acid, mp 85-
    2- (3,5-dichlorocinamineloxyimino) - propionic acid, so pl. 101-104 C;
    2- (5-chloro-2-methoxy- / 5-methylcinnamyloxyimino) -propionic acid, m.p. 108-110 ° C;
    2- (5-bromo-2-methoxycin namyloxyimino) -propionic acid, m.p. 118-120 ° C;
    2- (5-fluoro-2-methoxy-cinnamyloxyimino) -propionic acid, m.p. 114-116 ° C;
    72524
    2- (2-methoxy-5-trifluoromethyl-. Cinnamyloxyimino) -propionic acid, m.p. 120-123 ° C;
    2- (2,5-dimethoxycinnamine 5 but) -propionic acid, so pl. 747b ° s;
    2- (2-methoxy-5-methylcinnamineloxyimino) -propionic acid, so pl. sodium salt 218 ° C
    2- (cinnamyloxyimino) -3-fluoropropionic acid, m.p. 81-83 °;
    H-chloro-2-cinnamyloxyiminopropionic acid, so pl. 95-98 ° C;
    cinnamyloxyiminoacetic acid, 5 so pl. 85-88 ° C;
    2-cinnamyloxyiminobutyric acid, m.p. 75-77 ° C;
    2-cinnamyloxyimino-3-methylbutyric acid, m.p. sodium salt, 0 220 ° С (decomp.);
    2-cinnamyloxyimino valeric acid, m.p. 53-55 C,
    2-cinnamyloxyimino-4-methylvaleric acid, m.p. 60-62 ° C, 2-cinnamyloxyimino-3-metsh1-valeric acid, so pl. 57-59 ° CJ
    2-cinnamyloxyimino-octane acid, m.p. 56-58 С,
    2-cinnamyloxyimino-3-phenylpropionic acid; m.p. 84-86 C;
    2-cinnamyloxyimino succinic acid, so pl. 124-126 ° C;
    2-cinnamyloxyaminoglutaric acid, so pl. 121-123 C, 5 2- (4-phenylbutoxyimino) propionate sodium, m.p. 215-215 ° C;
    2- (5-phenylpentoxyimino) sodium propionate, m.p. 209-212 s;
    2- (2-phenoxypropoxyimino) -propio-0 no sodium, m.p. 204-206 ° C,
    2- (3-phenoxypropoxyimino) -propionic acid, so pl. 86-88,
    (4-chlorophenoxy) -propoxy-HoJ-propionic acid, m.p. 70-5 73 ° C;
    2-cinnamyloxyimopropionic acid, so pl. 89-91 ° C
    methyl ester 2-cinnamyloxyiminopropionic acid, so pl. 89-91 ° CJ 0 2- (3-fluorocinnamineloxyimino) -pyrovic acid, m.p. 88-.
    Example 3. 2- (Zinnamyloxyimino) propionic acid 5 ethyl ester.
    A mixture consisting of 2.2 g (10 mmol) of 2- (cinnamyloxyimino) - propionic acid, 16 ml of chlorophore, 1.78 g (15 MMonti) of ionyl chloride and 2 drops of dimethylformamide is heated for 2 hours at boiling point. the reaction mixture. Immediately thereafter, loroform and an excess amount of loric thionyl are distilled off from the reaction mixture in vacuum. The remaining massed product is mixed with 20 ml of ethyl alcohol and the mixture is kept at room temperature for 12 hours. Thereafter, ethyl alcohol is distilled off in vacuo and the resulting residue is dissolved in diethyl ether. The solution is washed twice with saturated sodium hydrogen carbonate, dried and evaporated in vacuo. The residue obtained after evaporation is dissolved in ligroine, the solution is decolorized with coal and again evaporated. 2.4 g (97% of the theoretically calculated value) of 2- (cinnamyloxyimino) propionic acid ethyl ester, which is a colorless oily substance, i.p. °. 1,5390 is obtained as a residue.
    Example 4. Amide of 2- (cinnamyloxyimino) -propionic acid.
    From 4.38 g (20 mmol) of 2- (cinnamyl-oxyimino) -propionic acid and 3.57 g (30 mmol) of thionyl chloride are obtained by analogy with the described 2- (cinnamyloxyimino) -propionyl chloride. The crude acid chloride is dissolved in 20 ml of chloroform and, with stirring, the prepared solution is added dropwise to an ice-cooled solution of ammonia in 40 ml of chloroform. The reaction mixture was incubated overnight at room temperature, after which 100 ml of water was extracted. Immediately after this, the organic phase is washed first with 0.5N. solution of hydrochloric acid, then with a saturated solution of sodium hydrogen carbonate, dried over sodium sulfate and evaporated in vacuo. The residue obtained is recrystallized from a mixture of ethyl ester of acetic acid and ligroin. As a result, 2.9 g (66% of the theoretically calculated value) of the amide of 2- (cinnamyl-oxyimino) -propionic acid, m.p. 120-12l c.
    In a similar way, it is obtained from 2- (cinnamyloxyimino) -propionyl chloride and ethanolamine, M- (2-hydroxyethylamide) -2- (cinnamyloxymino) propionic acid, m.p. 74-76 S. Example 9 (cinnamyloxyimino) propionyl -1-methyl piperazine.
    To a solution of 20 g (20 mmol) of 1-methylpiperzine in 40 ml of dry pyridine at 0 ° C and stirring, 4.8 g (20 mmol) of 2- (cinnamyloxyimino) propionyl chloride are added dropwise. The mixture is further stirred for 1 h at 0 ° C and then poured onto ice. The mixture is extracted with diethyl ether, the ether extract is dried over sodium sulfate and evaporated.
    Yield 4.3 g (71% of theoretically calculated value). colorless oily product. M.p. hydrochloride of this compound 162-164 C
    (isopropyl alcohol).
    In a similar way, ethyl ester is obtained from ethyl α-alanine hydrochloride and 2- (cinnamyloxyimino) propionyl chloride.
    3- 2- (cinnamyloxyimino) -propionyl-amino-propionic acid.
    13.7 g (43 mmol) of the crude ester are dissolved in 250 ml of methyl alcohol and the solution prepared is mixed with 90 ml of 1N. potassium hydroxide solution. The mixture is heated with stirring for 2 hours at 40 ° C, after which methyl alcohol is distilled off in vacuo. The aqueous residue is decolorized with coal and neutralized by the addition of 90 ml of 1N. hydrochloric acid. The crystalline product which precipitates out is filtered off and recrystallized from a mixture of ethyl acetate of acetic acid and ligroin. 7.3 g are obtained (58% of the theoretically calculated value)
    3-12- (cinnamyloxyimino) -propionyl1.
    amidesu-propionic acid,
    m.p. 111-113 0.
    The synthesized compounds are tested for pharmacodynamic activity.
    Test method for determining the dose limit.
    as an experimental model for determining the limiting
    doses of blood glucose lowering, the test substances are used by the guinea pig (on an empty stomach). The animals used for the study 16 hours before the start of the experiment did not have Tummy. Animals remained without food during the whole experiment, but had free access to drinking water.
    The experiments were carried out by injecting a substance into the peritoneum as a solution of salt K at pH 7.4.
    The control group receives a 0.9% NaCl solution.
    Blood to determine the concentration of glucose is taken immediately prior to the administration of the substance, as well as at intervals of one hour to the 4th hour after giving the substance. For (THIS, the ear vein is gently punctured using cannula no. 18, and the outgoing drop of blood is collected using a 10 ml capillary.
    Determination of glucose concentration in the blood is performed by a specific method with hexokinase in hemolysate. To do this, 10 ml of a blood sample is pipetted into a stabilizer solution, which contains digitonin as an accelerator, hemolysis, and malein imide as a glucose inhibitor. From the hemolysate obtained in this way, the amount to be removed without residue is determined and determined according to the principle of the hexokinase method on LKB 8600.
    As a dose limit, take such that, given the number of experimental animals per group
    2- (2 Phenoxyethyloxyimino) - sodium propionate
    2- (3-Fenilpropyloxyimino) - sodium propionate
    2- (4-Chlorocinamineloxyimino) propionic acid

    (N 4) causes a significant decrease in fasting blood sugar (p 0.05).
    5 Test method for determining the inhibitory-brain suction effect.
     To test the effect of glucose absorption, glucose is administered through the mouth. For this one of the marine
    10 pigs in the group of 10 animals, on an empty stomach, give the test substance in the form of salt K, inside the peritoneum. At the same time, animals receive 1 g of glucose, in the form of 20%
    15 solution with throat probe through the mouth.
    After the preliminary value of the animals in the fine-gridded raster (from 20 to 200 min) is dropped, blood is taken to determine the glucose concentration.
    In parallel, the control group also receives 1 g of glucose orally and the corresponding
    25 the amount of 0.9% NaCf solution inside the peritoneum.
    The determination of the glucose concentration in the blood is carried out using the method with hexokinase in hemolysate.
    30 The area under the concentration-time curve is calculated as the measurement value for glucose absorption. The percentage difference in the area of the control group and the group with the substance, expressed in percent, is indicated as a measure to inhibit glucose absorption. Test results
    50 is weak
    40
    25
    25-50
    20 .
    39
    25-50
    20
    ten
    2- (2-Chlorocinamineloxyimino) propionic acid
    2- (3-Chlorocinnaminoxyimino) propionic acid
    2- (Allyloxyimino) -propionova
    acid
    2- (3-Phenyl-2-propynyloxyimino) propionic acid
    2- O-Me / hydroxycinamyloxyimino) - propionic acid
    2- (3-trifluoromethylcinnaminoxy propionic acid
    2- (5-Chloro-2-methylcinnamyloxy propionic acid
    2- (Zinnamyloxyimino) -3-fluoropropionic acid
    (Cinnamyloxyimino) propionyl -1-methylpiperazine
    2-Cinnamyloxyiminopropionov
    acid
    2- (2-Phenylethyloxyimino) propionic acid
    2- (| 3 -methylcinnamineloxyimino) - propionic acid
    2-Cinnamyloxymino oil
    acid
    2-z-Cyclohexyl-2-propenyloxyimino-propionic acid
    2- (3-Nitrocinnaminoxyimino) propionic acid
    (4-Chlorophenoxy) - propoxyiminoZ-propionic acid
    Table continuation


    41
    55
    37
    65
    36
    34
    33
    26
    44
    33
    33
    40
    69 40
    40 32
    Compounds for Comparing 0-Cinnamyl Hydroxylamine Hydrochloride
    Sodium 2- (2-methoxyimino) - propionate
    Editor I. Derbak
    Compiled by L.Ioffe Tehred 3.Paly
    Order 1007/62 Circulation 379Subscription
    VNIIPI State Committee for Inventions and Discoveries 113035, Moscow, Zh-35, Raushsk nab. 4/5
    Branch PSh1 Patent, Uzhgorod, st. Project, 4
    Table continuation
    50
    40
    50
    40
    sixteen
    Proofreader L. Patay
    权利要求:
    Claims (1)
    [1]
    The method of producing oxime pyruvic acid of the General formula
    R-A-O-N-C / R, ^ COOH where R is a hydrogen atom, cyclohexyl, naphthyl, phenyl, phenoxy residue, and the phenyl fragment may contain one or two substituents, which may be lower alkyl, lower alkoxyl, halogen atom, trifluoromethyl residue, nitro group,
    R, is a lower alkyl residue which may be substituted by halogen
    A is a saturated linear or branched lower alkylene residue, an unsaturated linear lower alkylene, and R-A cannot mean methyl, ethyl, benzyl group or their salts or amides, about t - <
    characterized in that the compound of the general formula
    R-A-Y where D; and A have the indicated meanings) g Y, chlorine or bromine, is reacted with a compound of the general formula
    X
    R ( - C - COOH I x <
    where X and X ( together mean a group ·, -NOH;
    R ( has the indicated meaning, and the target product is isolated in the form of a free acid, or, if necessary, the latter is converted into the corresponding acid amide or salt.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    法律状态:
    优先权:
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    DE19803036281|DE3036281A1|1980-09-26|1980-09-26|0-SUBSTITUTED PETROLEUM ACID OXIMES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS|
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