• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The compounds of formula I are known for their antiphlogistic properties. The new process makes it possible to obtain them easily on an industrial scale and in the pure state. A compound of formula II is reacted with thallic nitrate in the presence of water or of an alcohol. <IMAGE>
    公开号:SU927109A3
    申请号:SU762375571
    申请日:1976-06-24
    公开日:1982-05-07
    发明作者:Палоши Эндре；Хейа Гергель；Корбонитш Деже；Генци Чаба；Кишш Пал；Себени Рудольф；Молнар Эржебет
    申请人:Хиноин Дьедьсер Еш Ведьесети Термекек Дьяра Р.Т.(Инопредприятие)；
    IPC主号:
    专利说明:

    • The invention relates to an improved method for producing substituted phenylalkane carboxylic acids, which, as having anti-inflammatory properties, can be used in pharmaceutical preparations for medical practice.
    A known method for producing unsubstituted in the phenyl core of phenylalkanoic acids, for example methyl <k, -alkylphenylacetate, by oxidation of phenylalkylacetylenes with thallium nitrate in methyl alcohol during boiling for two hours, followed by filtration and extraction of the target product with chloroform, washing with 5% aqueous solution drying over sodium sulfate with the yield of the target product up to 90% [1].
    However, according to this method, phenylalanoic acids substituted in the phenyl moiety were not obtained.
    The closest technical solution to the proposed one is a method for producing various substituted phenyl2 alkanoic carboxylic acids, for example, meta-phenoxyphenylacetic acid, by oxidation of meta-phenoxyacetophenone with sulfur in the presence of 5 morpholine while boiling for about 20 hours.
    Isolation of the target product is carried out using extraction and purification with activated carbon with the yield of non-Bbiuie85% £ 2j. However, the great complexity of the IQ process, its duration and the need for heating to a boil as a whole complicate the implementation of the process.
    The goal is achieved according to the method of producing substituted phenylalkanecarboxylic acids op general formula _, 20 E-CH-COOR 1
    Q 27 where R = R * is hydrogen, alkyl C <-Cz, '. If R 4 is hydrogen, then R 4 is tert-butyl;
    'if R' is benzoyl or phenoxy, then R is hydrogen ^ £ if R * is fluorophenyl, then R * : phenyl, '.
    if R 8 · is hydrogen or 3 “chlorophenyl, then R 4 is tenoyl or chlorotenoyl, if R 5 is chlorine, then R - tenoyl, 'by reacting (oxidizing) I correspondingly substituted phenylalkylacetylene with thallium nitrate at 5 * 24 C in a medium of the general formula R OH, where R are the indicated values, or in a mixture of alcohol and an organic solvent, followed by isolation of the desired product x).
    B. Diethyl ether or a mixture of ethylene glycol and methyl ether in the presence of aqueous perchloric acid is used as an organic solvent.
    This provides the desired product with a good yield and; purity in mild conditions compared to the known method.
    Derivatives bearing relatively large substituents can be converted under mild conditions with from-; personal exits to phenylalkanecarboxylic acid esters.
    with methyl ether in the presence of aqueous perchloric acid.
    Example 2. Suspend
    48.8 g of THNT in 250 ml of methanol are added in small portions of 20.8 g of (m-phenoxyphenyl) methylacetylene, so that the heat is removed so that the temperature does not rise above 15 ° C.
    'The mixture is stirred for another 3.5 hours at 10-15 ° C and nitrate precipitated; thallium divalent is filtered off, 250 ml of methylene chloride are added to the filtrate, the aqueous phase is separated with two portions of ISIS in 150 ml of methylene chloride.
    ^ The combined organic phase is evaporated. The residue is dissolved in 350 ml of methanol, 20 ml of an aqueous solution are added, 6 g of sodium hydroxide and Ϊ 0 boil the mixture for 3 hours, and then evaporated. The residue is dissolved in 200 ml of water, extracted twice with 150 ml of methylene chloride each and activated carbon is filtered off! 5 after decolorization of the aqueous phase.
    The filtrate was acidified with 50% sulfuric acid, dried with sodium sulfate, the solvent was evaporated, the residue was distilled in vacuo. Obtain 2.05 g (85%) of m-phenoxyhydrotropic acid boiling at 190-192 ° C (0.4 mm Hg) PD 5 = 1.575 Example 1. 1.94 g of m-phenoxyphenyl ^ cetylene is added to a solution of 8.88 g of thallium nitrate trihydrate (THNT) and a 25 mp mixture of glycol methyl ether in 15 ml of water and 8 ml of 70% HC | Oc. The reaction mixture was stirred at room temperature for 2 hours, after which water was added and the mixture was extracted with benzene. The benzene layer was dried over sodium sulfate, the residue was evaporated, and the residue was recrystallized from a mixture of n-Guxane and ethyl acetate, using activated carbon to discolor the product. 1.9 g (83%) of m-phenoxyphenylacetic acid are obtained, m.p. 84-86 C.
    A distinctive feature is the conduct of 'oxidation' using thallium nitrate of the other parent; substituted phenylalkylacetylenes when
    5-24 ° C in an alcohol medium of the formula R * OH, where R ’are the indicated values, or in a mixture of alcohol and an organic solvent, mainly diethyl ether or an ethylene glycol mixture
    Example 3 · 36.8 g (0.083 mol) of THNT are suspended in 200 ml of methanol 35 and 20.4 g (0.0755 mol) of 1- (m ~ benzoylphenyl) methylacetylene are added. The mixture was stirred at room temperature for 3 hours. The precipitate of divalent thallium nitrate was filtered off, 14 ml of 40% sodium hydroxide was added to the 40 filtrate, and the mixture was refluxed for 6 hours. The solution was decolorized with activated charcoal, boiled for another 5 minutes and filtered.
    45 The filtrate was evaporated in vacuo. The residue was dissolved in 100 ml of water, extracted with 30 ml of methylene chloride and the pH of the aqueous phase was adjusted to two with concentrated 50 hydrochloric acid. The precipitate is a slowly hardening oily substance, which is filtered and washed with water. Receive
    15.8 g (82.3%) of m-benzoylhydrotropic acid, melting at 92 ° C. PRI me R 4. To 16 g of (p-isobutylphenyl) methylacetylene in 225 ml of methanol are added with stirring 5 927 small portions of 47.7 g of thallium nitrate (NT) at 5 ° C. The reaction mixture was stirred at 10 ° C for 3 hours. The precipitate of thallium nitrate was filtered off, and 42 ml of 5 N was added to the methanol filtrate. sodium hydroxide solution, the reaction mixture is refluxed for 10 hours, and then evaporated in vacuo. The residue is taken up in water, extracted with chloroform and the pH of the aqueous solution is adjusted to two using hydrochloric acid. The separated oily product is dissolved in chloroform, and the solution is dried over sodium sulfate. Chloroform is distilled off, the hardened oil is recrystallized from petroleum ether. 13.2 g of (69¾) 4-isobutyl sulphate of hydropropic acid are obtained. Mp 2 4 ° C.
    Example 5 · K 5.6 g of (p-isobutylphenyl) methylacetylene in 75 ml of methanol at 5 ° C are added in small portions with stirring
    15 9 g of thallium nitrate, then the reaction mixture is stirred for another 3 hours at 10 ° C. The precipitate of divalent thallium nitrate is filtered off and washed with methanol. The filtrate was diluted with water, the separated oil was extracted with chloroform. The solution was dried over sodium sulfate and chloroform was distilled off. The remaining oil is dispersed in vacuo. 6 g (84%) of 3 methyl-2- (p-isobutylphenyl) propionate are obtained. Mp 112-118 ° C at 0.7 mm Hg
    Example 6. To 15 g of methyl 2- (p-isobutylphenyl) propionate c. 150 ml of methyl alcohol are added 35 ml 4) 5 n sodium hydroxide, the reaction mixture is refluxed for 6 hours, after which the solution is evaporated in vacuo, the residue is dissolved in water, extracted- 4 . Chloroform and acidify an aqueous solution of 35 ml of 5 N. of hydrochloric acid. Separated'.' the oily product is dissolved in chloroform; the solution exists over sodium sulfate. Chloro- 5) transform is distilled off, and 13 g (92.5¾) of oily 2- (p-isobutylphenyl) propionic acid are obtained.
    Mp 74 ^ 0.
    Example 7. 21.1 g of (4-phenyl ~ 3 “fluorophenyl) methylacetylene are mixed with 245 ml of methanol and added in small portions at a temperature of · below 10 ° C with stirring 51.8 g
    109 6
    TGNT. After this, the reaction mixture was stirred for another 3 hours at 10 ° C. The precipitated thallium nitrate is filtered off to the filter.
    > 46 ml of 5 N are added to the rat. sodium hydroxide and the reaction mixture are refluxed for 10 hours, then evaporated in vacuo. The residue was maintained in vacuo CME J Shiva with 2 g of activated charcoal and filtered. Set the pH to two with 5. of hydrochloric acid. The separated oil crystallizes upon friction with a glass rod. D s Polucha- dissolved 19.7 g (80.5%) of 2- (4-phenyl-W-fluorophenyl) propionic acid, melting at 102-109 ° C.
    Example 8. To a mixture of 11.3 g of 4- (2-tenoyl) phenylmethylacetylene and 5 150 ml of methanol are added at a temperature below 10 ° C in small portions of 22.2 g of NT with stirring. The reaction mixture was stirred for another 3 hours. The precipitated thallium nitrate precipitate was filtered off, washed with methanol and the filtrate was diluted with water. The separated oil is extracted with methylene chloride. The solution thus obtained was dried over sodium sulfate), decolorized with activated carbon, filtered off, evaporated in vacuo and then suctioned off. · The resulting methyl ester of 4- (2-thenoyl ~ yl) -gidratropovoy perekris acid; they are thallized from a small amount of diisopropyl ether. Mp 60 S.
    Example 9. To 8.2 g of 4- (2-tenoyl) -hydrotropic acid methyl ester in 100 ml of methyl alcohol), 30 ml of 5 N are added. sodium hydroxide solution, the reaction mixture is refluxed for 7 hours. The mixture is decolorized with activated carbon and evaporated in vacuo. The remainder of the current is dissolved in water, the pH is set to unity with 5 N. hydrochloric acid and the separated oil are dissolved in chloroform. The solution was dried over sodium sulfate and concentrated. The remaining oil is thoroughly triturated with petroleum ether and the resulting product is filtered off. 6.3 g (80%) of 4- (2-tenoyl) hydrotropic acid are obtained. Mp after recrystallization from acetonitrile Rav S at 121-123 ° C.
    Example 10. To a mixture of 5.23 g of (4-) 2-tenoyl (-3chlorophenyl) methylacetylene and 50 ml of methanol was added 927109 8 in small portions at a temperature below 10 ° C with stirring
    8.8 g of THT. The reaction mixture was stirred at 10 ° C for another 3 m. Filter off the precipitated nitrate two- valent thallium 5, to the filtrate was added 8.5 ml of 5N. sodium hydroxide solution, the reaction mixture is refluxed
    h. Methanol is distilled off. The residue was dissolved in water, decolorized with activated carbon, and the pH of the filtrate was adjusted to two with 5 N. hydrochloric acid upon cooling. Other], the oil is extracted with chloroform, dried over sodium sulfate, filtered and evaporated in vacuo. The residual oil crystallized on tschatel'nom Trituration with petroleum ether, was prepared .obrazom 4- (2-thenoyl-3-chloro _) -gidratropovuyu acid, melting at 79 "81 ° C.
    权利要求:
    Claims (2)
    [1]
    where is hydrogen, alkyl C «-Ch,, if R is hydrogen, then tert butyl; - benzoyl or phenoxy, hydrogen; R is fluorofenyl, then R is phenyl, if R is hydrogen or H-chlorine NIL, then R is tenoyl or chloroteno if R is chlorine, then R is thioyl by reacting (oxidizing) the Corresponding substituted phenylalkylacetylene with thallium nitrate at C in an environment of the general formula ROH, where indicated values, or in a mixture of alcohol and organic (solvent, followed by isolation of desired product x). C. As an organic solvent, diethyl ether or a mixture of ethylene glycol and methyl ether in the presence of aqueous perchloric acid is used. This provides the desired product in good yield and purity under mild conditions as compared with the known method. Derivatives bearing relatively large substituents can be converted under mild conditions with excellent yields to phenylalkane carboxylic esters. Example 1. 1.9 g of m-phenoxy phenyl cetylene is added to a solution of 8.88 g of thallium nitrate trihydrate (THNT) and 25 ml of a mixture of glycol methyl ether in 15 ml of hydrogen and 8 ml of HClOij. The reaction mixture is stirred at room temperature for 2 hours, after which water is added and the mixture is extracted with benzene. The benzene layer is dried over sodium sulfate, ocTaTok is evaporated and re-crystallized from a mixture of n-hexane and ethyl acetate, using activated carbon to decolorize the product. 1.9 g (83) m-phenoxyphenylacetic acid, m.p. 84-86 G, are obtained. A distinctive feature is the oxidation by V using thallium nitrate of other original substituted phenylalkyl acetibodies with an alcohol of the formula R OH where R is the indicated or in a mixture of alcohol and organic solvent, mainly diethyl ether, or a mixture of ethylene glycol 94 with methyl ether in the presence of aqueous perchloric acid. Example 2. 8.8 g of THNT are suspended in 250 ml of methanol and 20.8 g of (m-phenoxyphenyl) methylacetylene are added in small portions, thus removing heat so that the temperature does not rise above. The mixture is stirred for another 3f5 h at 10-15 The &lt; / RTI &gt; C and the precipitated bivalent thallium nitrate is filtered off, 250 ml of methylene chloride is added to the filtrate, separated and the aqueous phase is extracted with two 150 ml of methylene chloride. The combined organic phase is evaporated. The residue is dissolved in 350 ml of methanol, 20 ml of an aqueous solution, 6 g of sodium hydroxide are added and the mixture is boiled for 3 hours and then evaporated. The residue is dissolved in 200 ml of water, extracted twice with 150 ml of methylene chloride each time and the activated carbon is filtered off after the aqueous phase has decolorized. The filtrate is cast with sulfuric acid, dried with sodium sulfate, the solvent is evaporated, and the residue is distilled in vacuo. 2.05 g (85%) of m-phenoxyhydrotroic acid are obtained, boiling at 190-192 ° C (0, i mm Hg) or 1.575. Example 3- 36.8 g (O, 083 mol) of THNHT are suspended in 200 ml of methanol and 20.4 g (0.0755 mol) of 1 - {m benzoylphenyl) methylacetylene are added. The mixture is stirred at room temperature for 3 hours. The precipitated bivalent thallium nitrate is filtered, added to the filtrate is And ml of 40; -aq sodium hydroxide and the mixture is heated under reflux for 6 hours. The solution is decolorized with activated carbon, boiled for another 5 minutes and filtered . the filtrate is evaporated in vacuo. The residue is dissolved in 100 ml of water, extracted with 30 ml of methylene chloride and the pH of the aqueous phase is adjusted to two with concentrated hydrochloric acid. The precipitate is a slowly hardening oily substance, which is filtered and washed with water. 15.8 g (82.3) m-benzoylhydrotroic acid, melting at 92 ° C. is obtained. Example 4. To 16 g of (p-isobutylphenyl) methylacetmylene in 225 ml of methanol, 7.7 g are added with stirring to the NII thallium nitrate (NT) at. The reaction mixture was stirred at 10 ° C for 3 hours. A precipitate of bivalent thallium nitrate was filtered off, 42 ml of 5 N were added to the methanol filtrate. sodium hydroxide solution, the reaction mixture is refluxed for 10 hours and then evaporated in vacuo. The residue is treated with water, extracted with chloroform, and the pH of the aqueous solution is adjusted to two with hydrochloric acid. The separated oily product is dissolved in chloroform, solution s. Sat over sodium sulfate. Chloroform is distilled off, the hardened oil is recrystallized from petroleum ether. Obtain 13.2 g of (69) "-isobutylhydratropic acid. M.p. 74 ° C. . Approx er 5- K 5.6 g of (p-isobutylphenyl) methylacetylene in 79 ml of methanol at 5 ° C. Smaller Thallium thallium is added in small portions of stirring while stirring, then the reaction mixture is stirred for 3 more hours at JV. The precipitated bivalent thallium nitrate is filtered off and washed with methanol. The filtrate is diluted with water, and the separated oil is extracted with chloroform. The solution was dried over sodium sulfate and chloroform was distilled off. The oil which has settled down is dissolved in a vacuum. 6 g (8k%} methyl 2- {p-isobutylphenyl) propionate, m.p. P2-118 C at 0.7 mm Hg Example 6: K15g methyl 2- (p-isobutylphenyl) propionate in 150% methanol was added 35 ml of 5N sodium hydroxide, the reaction mixture was heated under reflux for 6 hours. Then the solution was evaporated in vacuo, the residue in water, extracted with chloroform and acidified with an aqueous solution of 35 ml of 5N. hydrochloric acid. Separated. the oily product is dissolved in chloroform, the solution is dissolved over sodium sulfate. Chloroform is distilled off to obtain 13 g of (92.5) oleaginous 2- (p-isobutylphenyl) - propionic acid. M.p. . Example 7. 21.1 g of (A-phenyl-3 fluorophenyl) methylacetylene are mixed with ml of methanol and 51.8 g of THNT are added in small portions at a temperature below 10 ° C with stirring. After that, the reaction mixture is stirred for another 3 h at 10 ° C. The precipitated precipitate of divalent thallium citrate is filtered off, to filter. rata is added 46 ml of 5 n. The sodium hydroxide and the reaction mixture are refluxed for 10 hours, then evaporated in vacuo. The residue is kept under vacuum, mixed with 2 g of activated carbon and filtered. The pH is set to two using Z.N. hydrochloric acid. The separated oil crystallizes upon rubbing with a glass rod. 19.7 g of (80.5-U 2- (α-phenyl-3-fluorophenyl) propionic acid, melting at 102-109 ° C. are obtained. Example 8: A mixture of 11.3 g of 4- (2-thenoyl) phenylmethylacetylenes and 150 ml of methanol are added at a temperature below 10 ° C in small portions of 22.2 g of NT with stirring. The reaction mixture is stirred for an additional 3 hours. The precipitated mixture of divalent thallium nitrate is filtered, washed with methanol and diluted with a filgrate with water. The separated oil is extracted with methylene chloride The solution thus obtained is dried over sodium sulfate, decolorized with activated charcoal, ltrovyvayut, evaporated in vacuo and then the resultant was aspirated metilovyy- ether -. {2-thenoyl) -gidratropovoy acid was recrystallized from a small amount of diisopropyl ether. M.p. 60 C. Example 9-K8.2g of methyl ester of - (2-thenoyl) -hydrotropic acid in 100 ml of methyl alcohol is added 30 ml of 5N. sodium hydroxide solution, the reaction mixture is boiled under reflux for 7 hours. The mixture is decolorized with activated charcoal and evaporated in vacuo. The residue is dissolved in water, the pH is set to unity with help of 5N. hydrochloric acid and the separated oil are dissolved in chloroform. The solution is dried over sodium sulfate and concentrated. The remaining oil is thoroughly triturated with petroleum ether and the product obtained is filtered off. 6.3 g (80%) of 4- (2-tenoyl) -hydrotrope acid are obtained. M.p. after recrystallization from acetonitride, it is equal to 121-123 ° С. Example 10. To a mixture of 5, -23 g of (-) 2-thioyl (-3 chlorophenyl) methylacetylene and 50 ml of methanol was added in 7 portions at a low temperature of 10 ° C with stirring, g of TGNT. The reaction mixture was stirred at a further 3 hours. The precipitated two-valent thallium nitrate was filtered off, and 8.5 ml of 5 N was added to the filtrate. sodium hydrokibi solution, the reaction mixture is heated under reflux for 10 hours. Methanol is distilled off. The residue is dissolved in water, decolorized with activated charcoal, the pH of the filtrate is set to two with 5N hydrochloric acid upon cooling. The separated oil is extracted with chloroform, dried over sodium sulfate, filtered and evaporated in vacuo. The residual oil crystallizes by careful trituration with petroleum ether, is thus obtained (2-thooyl-3-chloro) -hydratropic acid, melting at. Claim 1. Method for producing substituted phenyl-alkanecarboxylic acids of general formula E-CH-COOB alkyl C-C, hydrogen, then R is tert-hydrogen, butyl, fr is phenoxy-or benzoethyl is hydrogen, .. or R is fluorophenyl, then R if phenyl, J or 3-chlorophenyl, if hydrogen or 3-chlorop. phenyl, then R is tenoyl or slateonyl, if R is chlorine, then R is tenoyl using oxidation, characterized in that, in order to simplify the process, phenylacetylene of the general formula R, R has the indicated values, is subjected to oxidation with thallium nitrate at 5- 24 C in the environment of alkyl alcohol With -Ch or its mixture with an organic solvent, followed by separation of the target product in the form of acid or ether and, if desired, the conversion of the latter into acid. 2. Method pop. 1, characterized in that diethyl ether or a mixture of ethylene glycol with methyl ether in the presence of aqueous perchloric acid is used as an organic solvent. Sources of information taken into account in the examination 1.Alexander Mcklttop et al. Thallium in organic synthesis. J, Am. Chem. Sos; 95,1296-1301,1973.
    [2]
    2. US patent number 3 600 37, class. 260-520, pub. 1971 (prototype)
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    同族专利:
    公开号 | 公开日
    SE7607167L|1976-12-25|
    HU173576B|1979-06-28|
    FI761833A|1976-12-25|
    FI66833C|1984-12-10|
    SE432588B|1984-04-09|
    CH613936A5|1979-10-31|
    NL7606830A|1976-12-28|
    DK281576A|1976-12-25|
    JPS5236642A|1977-03-22|
    ES449023A1|1977-12-01|
    FI66833B|1984-08-31|
    GB1552202A|1979-09-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    YU39220B|1976-10-18|1984-08-31|Lek Tovarna Farmacevtskih|Process for preparing 2--propionic acid|
    JPS5535056A|1978-09-04|1980-03-11|Hamari Yakuhin Kogyo Kk|3-substituted acetophenone and its preparation|
    JPS5561132A|1978-10-31|1980-05-08|Nippon Technical Co Ltd|Channel selector of electronic tuning receiver|
    US4528114A|1981-12-18|1985-07-09|Hoffmann-La Roche Inc.|Acetylenes|
    DE3802619C1|1988-01-29|1989-09-07|Hoechst Ag, 6230 Frankfurt, De|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU75CI1595A|HU173576B|1975-06-24|1975-06-24|Process for preparing substituted phenyl-alkyl-carboxylic acids|
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