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    1466657 Benzophenones and phosphonium iodides ROUSSEL-UCLAF 27 Nov 1975 [28 Nov 1974] 48754/75 Headings C2C and C2P Novel compounds (I) wherein X<SP>1</SP> and X<SP>2</SP>, which may be the same or different, each represent a hydrogen atom, a halogen atom, an alkyl radical having from 1 to 5 carbon atoms, an alkoxy radical having from 1 to 5 carbon atoms, an alkylthio radical having from 1 to 5 carbon atoms, a trifluoromethoxy radical, trifluoromethylthio radical or a trifluoromethyl radical; R<SP>1</SP> represents a hydrogen atom, or an alkyl radical containing from 1 to 5 carbon atoms; R<SP>2</SP> represents an aliphatic hydrocarbyl radical of the formula in which a and b, which may be the same or different, are each integers of from 0 to 16 such that their sum is less than or equal to 16, are made by reacting compounds (II) with to give (I) wherein R<SP>2</SP> is and thereafter effecting reduction to give (I) wherein R<SP>2</SP> is Compounds (II) are obtained by reducing corresponding acid chlorides. 2- Methyl-3- (p - chlorobenzoyl) - phenyl acetic acid chloride is prepared from the free acid. n-Hexyl- and npentyl-triphenylphosphonium iodides are prepared by reacting triphenylphosphine with iodohexane and iodopentane respectively. Pharmaceutical preparations having analgesic action contain (I) as active ingredient. Administration is orally, parenterally, rectally and topically.
    公开号:SU733515A3
    申请号:SU752193205
    申请日:1975-11-27
    公开日:1980-05-05
    发明作者:Дераед Роже；Маршандо Кристиан；Мейе Жан
    申请人:Руссель-Юклаф (Фирма)；
    IPC主号:
    专利说明:

    Rene's nickel, platinum oxide, and in an alkanol environment, such as methanol, ethanol, or isopropanol.
    Preparation of 1, 2-methyl 3- (phlorbenzoyl) benzaldehyde
    The 2-methyl 3- (p-chlorobenzoyl) benzaldehyde used as the starting material is prepared by reduction of 2-methyl 3- (p-chlorobenzoyl) benzoic acid chloride.
    43, g of 2-methyl 3 chloride (p-chlorobenzoyl benzoic acid, 450 ml of xylene, 4.5 g of barium sulphate containing 10% palladium, and 0.4 MP of the solution obtained by heating under reflux with b g of quinoline with 1 g of sulfur for 5 hours, and diluted after cooling to 70 ml with xylene, stirred in a stream of hydrogen for 45 minutes, heated to 130 ° C, stirred at this temperature until the hydrochloric acid release was complete, and then kept in an inert gas, cooled to , the catalyst is separated by filtration, the solvent is distilled off, dissolved isopropyl ether, add sour sodium sulfate and mix for 18 hours. Acid sulfate compound that is cooled, sucked off, washed and then decomposed by stirring for 2 hours 30 minutes, in an inert gas in the presence of dilute sulfuric acid and ether decant the ether, extract the aqueous layer again with ether, combine the ether layers, wash them with water, dry them, and then distill off the ether in vacuo.
    After recrystallization in isopropyl ether, 24.3 g of 2-methyl 3- {p-chlorobenzoyl) benzaldehyde are collected. M.p. 68 68
    Preparation 2: 2-methyl 3- (p-hlobenzoyl) phenylacetaldehyde.
    Phase A: 2-methyl 3- (p-chlorobenzoyl) phenylacetic acid.
    A mixture of 5 g of 2-methyl 3- (p-chlorobenzoyl) benzoic acid and 50 cm of thionyl chloride is heated for 2 hours. Excess thionyl chloride is removed by distillation under reduced pressure. The acid chloride formed is dissolved in 50 cm of blue methylene and the resulting solution is gradually added: to 370 cm of a solution of diazomethane in methylene chloride. After keeping at room temperature for one night, the solvent was removed under reduced pressure. The resulting diazoketbium is dissolved in 30 cm of dioxane and this solution is gradually added at 70 ° C to a mixture of 6 g of silver oxide, 14.5 g of sodium carbonate, 9.6 g of sodium thiosulfate in 70 cm of water After 2 hours at 70 s, filtered and acidify the filtrate with concentrated hydrochloric acid. The precipitate is separated, washed with water and recrystallized from isopropyl ether.
    Get 2-methyl-3 (p-chlorobenzoyl) phenylacetic acid, So, 152 ° C, 5Faza B: 2-methyl chloride
    3- (p-chlorobenzoyl) phenylacetic acid.
    Dissolve. 5.8 g of 2-methyl 3- (phlorbenzoyl) phenylacetic acid 10 in 25 cm of thionyl chloride and heated under reflux for 1 h 30 min. Excess thionyl chloride is removed and 2-methyl 3- (p-chlorobenzoyl) phenylacetic acid 15-chlorohydride is obtained, m.p. 62-bz ° C,
    Phase B: 2-methyl 3- (p-hlsrbenzoyl) phenylacetaldehyde.
    Acting in the same way as when preparing 1, but starting from 2-methyl 2-methyl 3- (p-chlorobenzoyl) phenylacetic acid 0, 2-methyl 3- (p-chlorobenzoyl) phenylacetaldehyde is obtained as an oil.
    Calculated,%: C, 70.46; H 4.8; CI 13.0,
    i6 -tl 2Found,%: C 70.5; H 4.6; C1 13.6.
    Preparation 3, Iodide n-hexyl triphenylphosphonium,
    28.82 g of triphenylphosphine and 21.2 g of 1-iodhexane are introduced into 200 cm of xylene. The resulting solution was heated under reflux for 5 hours. After cooling, the solvent was decanted and the gummy residue was triturated in ether. Dry at 90-10 ° C under reduced pressure to obtain 44.53 g of n-hexyl triphenylphosphonium iodide, melting at.
    Preparation 4, Iodide n-pentyl triphenylphosphonium.
    Acting in the same way as in preparation 3, but starting from n-pentyl iodide and triphenylphosphine, iodide n-pentyl tryphosphonium, melting at 174 s, is obtained,
    Example 1, 4-chloro-3- (1-ngeptil) -2-methylbenzophenone.
    With and with stirring, a solution containing 9.955 g of n-hexyl triphenylphosphonium iodide, 5.17 g of 2-methyl 3- (p-chlorobenzyl) benzaldehyde and 100 cm 5 of dimethyl sulfoxide-tetrahydrofuran mixture in a suspension containing 880 mg of sodium hydride with 60% is introduced. mineral oil, previously washed with petroleum ether, in a 20 cm mixture of dimethyl sulfoxide-tetrahydrofuran. Incubated with stirring for 10 minutes. at 0 C, and then change at room temperature for 4 hours, 30 minutes. The solvents are distilled off in vacuo. The residue is heated inversely with a 5 REFRIGERATOR with isopropyl ether. Decanted and restarted / process three times under the same conditions. After chromatography on silica in benzene, 5,645 4-chloro 3 (1-heptyl, 2-methylbenzophenone in the form of oil are obtained. Calculated: C 77.16; H 7.09 ; CI 10.85, 24 Found: C 78.2; H 7.5; CI 10.7. Thin-layer chromatography T.X TX: (on SiO2) Coefficient Rj 0.58 (benzene) P m and m p 2. 4-xriopo 3-n-heptyl 2-methylbenzophenone 5.57 g of 4-chloro 3- (1 -heptyl) -2methylbenzophenone are introduced into a suspension containing 60 cm of ethanol and 110 m of platinum oxide. and hold while stirring for 20 minutes, filter and distill dissolve. After chromatography on silica in benzene, 4.87 g of 4-chloro 3 heptyl-2-methylbenzophenone are collected in the form of oil. Calculated: C 76.69; H 7.66 CI 10.78. СЮ Found,% : C 76.5; H 7.7; CI 10.8. Infrared spectrum (CHC) C-iO peak at 1670 (conjugated ketone) aromatic: peaks at 1606 cm 1570 cm, and 1486 For example 4-chloro-3- (4-g-nyl) -2-methylbenzophenone. Acting in the same way as Example 1, but starting from 9.66 g of iodide n-pentyl triphenylphosphonium 5.17 g 2-methyl-3-p-chlorobenzoyl .beandehyde, will receive 5.785 g of 4-chloro-3- (l-hexyl) 2-methylbenzophenone as an oil. Analysis: С H С1О Calculated, .- С 76.78 N 6.77 01 11.33 Found,%: С 77.1 N 6.9 C1 11.2 T.X (SiOj) Coefficient, 62 (CH Example 4 4-chloro 3-n-ge 2-methylbenzofensn Acting as in example 2, but the course of 5.7 g of 4-chloro-3- (l -reKce nile) -2-methylbenzophenone, get 3.73 g of 4- Chloro 3-n-hexyl-2-methy benzophenone as an oil Calculated: C, 76.29; H, 7.36 CI, 11.26. CjpHj was found,%: C, 76.2; H, 7.4; CI 11 , 3.24 Boiling point 150 C nj, 1.566 T.X (on SiO) Coefficient R ,, 0.34 ((petroleum ether) tO4Ka boiling 64-75 C (4: 6). Example 5. 4-chloro 3- ( 3-5-utenyl) -2-methylbenzophenone.I'm acting as in Example 1, but starting from 3 (p-chlorobenzoyl) 2 methyl phenylpropionaldehyde and triphenylmethylphosphonium bromide, get 4-chloro 3 (3-butenyl) 2-methyl-benzophenone. Calculated: C 75.91; H 6.02; CI 12.45; H CU Found: C 76.0; H 6.2; CI 12.5: T.X (on SiOj,) Coefficient Rr 0.38 (CH.CI) petroleum ether (boiling point 6475 0 (6: 4) „„ ni, 1.5900 Example 6. 4-chloro-3-nbutyl-2-methylbenzophenone. Acting as in Example 2, but starting from 9.01 g of 4-chloro-3- (3-butenyl) 2-methylbenzophenone, 7.09 g of 4-chloro 3-n are obtained. -butyl 2-methylbenzophenone. Calculated,%: C 75.38; H 6.68; CI 12.36. C found;% 75.5; H 6.9; CI 12.4 T.X (on SiO), Rp - 0.58 (benzene). Infrared spectrum (CHCIj), peak at 1661 cm- (conjugated ketone) ,. aromatic: peaks at 1590 1573 cm-, 1487 cm Example 7. 4-chloro 3- (2-butenyl) -2-methylbenzophenone. Acting as in Example 1, but starting from 8.065 g of 3- (p-chlorobenzoyl) 2-methylphenylacetaldehyde and 11 g of triphenylethylphosphonium bromide, 2.54 g of 4-chloro-3- (2 butenyl) -2-methyLbenzophenone are obtained as an oil. Calculated,%: C 75.91; H 6.02; CI 12.45. H „CU Found,%: C 76.2; H 6.1; CI 12.4. .S T.X (SiOg) Coefficient 0.5% (cyclohexane-isopropyl ether 8: 2) Example 8. 4-fluoro-3-n-butyl2-methylbenzophenone. Acting as in Examples 1 and 2, but starting from 3- (p-fluorobenzoyl) -2methylbenzaldehyde and n-propyltriphenylphosphonium iodide, 4-fluoro3-n-butyl 2-methylbenzophenone is obtained as an oil. Calculated,%: C 79.97; H 7.08; F 7.03 Ea-4 FO Found%: C 80.3; H7.1; C1 7.0. T.X (SiOjj), Coefficient R 0.6 (), Infrared Spectrum
    /
     peak at 1668 cm (conjugated ketone),
    aromatic: peaks at 1602 cm and 1506 cm
    The method of obtaining benzophenone derivatives of the general formula
    (P
    gda.K.- hydrogen, alkyl radical

    with 1-3 carbon atoms;
    - saturated or unsaturated aliphatic hydrocarbon 1H chain having from 4 to 7 carbon atoms;
    - halogen,
    eight
    characterized in that the compound of the general formula
    S 1
    where X and R are as defined above;
    a is an integer from O to 8, is subjected to condensation with a compound of the general formula W
     G.-, where (G is an integer from O to 8. and in the case of K, equal to - (CH2) d-CH CH- (CH2) (f-H, the reaction mixture is reduced.
    Sources of information taken into account in the examination: 1. A. Serrey Handbook of organic reactions, Goskhimizdat, M., 1962, p.64-65
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of obtaining benzophenone derivatives of the general formula hydrogen, an alkyl radical with 1-3 carbon atoms;
    where R ^ R is a saturated or unsaturated aliphatic hydrocarbon chain having from 4 to 7 carbon atoms;
    X is halogen, characterized in that the compound of the general formula wherein X and R ^ have the above meanings;
    a is an integer from 0 to 8, is subjected to condensation with compound 10 of the General formula Y
    Ch n 5 PtCH * (SI 2 ''<T * n No.> where <T is an integer from 0 to 8. and in the case equal to - (CHg) ^ - CH = CH— (CHg) j - H , the reaction mixture is reduced.
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    引用文献:
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    US2671016A|1951-10-23|1954-03-02|Monsanto Chemicals|Herbicidal compositions|
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    JPS5946205B2|1976-01-01|1984-11-10|Kaken Pharma Co Ltd|
    US4145444A|1976-01-01|1979-03-20|Kaken Chemical Co., Ltd.|Anti-inflammatory agent of benzoyl derivative|
    GB1585962A|1976-10-14|1981-03-11|Lilly Industries Ltd|Benzophenone derivatives|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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