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    • 专利摘要:
    The headlamp shines over its total frontal area, yet is very shallow due to the absence of a parabolic reflector. There is a bulb (4) held in a socket (3) mounted vertically inside the headlamp. Behind the bulb is a transparent optical dish which has concentric circles of Fresnel prism section. These are designed so that any rays which reach them from the lamp are refracted forwards and all the refracted rays are parallel (as with a parabolic reflector). The front can be covered by a transparent protection disc.
    公开号:SU799647A3
    申请号:SU752112651
    申请日:1975-02-06
    公开日:1981-01-23
    发明作者:Телон Жан-Мари
    申请人:Эксашими (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing new derivatives of indan, which can be used as physiologically active substances.
    A known method of producing indane derivatives of General formula 1 of the Lewis catalyst and hydrochloric acid, the resulting ketone of formula III sn 3
    where R is a hydrogen atom, an alkali metal or a group of the formula CHMN or - CH 2 6W 2 n (ness. alk) m £ 1].
    The purpose of the invention is the expansion of the range of physiologically active compounds.
    This goal is achieved in that the indan of the formula I I
    subjected to recovery, the resulting alcohol of formula IV
    halogenating !, the resulting halogen derivative is reacted with an alkaline cyanide, the resulting nitrile
    react with acetic anhydride in the presence of acidic
    subjected to hydrolysis, followed by isolation of the target product in free form or in the form of ether.
    It is preferable to use A1C1 B as an acidic Lewis catalyst.
    It is advisable to carry out the reduction of the ketone of formula ill with potassium borohydride, and the halogenation of thionyl chloride.
    PRI me R 1. (Isopropyl-2 / indanyl-5) methyl ketone.
    A solution of 100 g of isopropyl-2-indane and 65 ml of acetic anhydride in 400 mp methylene chloride is added over 1 h to a suspension of 190 g of aluminum chloride in 400 ml of methylene chloride under cooling so that the temperature of the reaction mixture remains below 10 ° C. Then, the mixture was stirred for 5 hours at room temperature, then it was poured onto 2 kg of ice and acidified to pH 3 with hydrochloric acid. The methylene chloride phase is separated, and the stock solutions are extracted with methylene chloride. The methylene chloride phases are collected, washed with water and dried over sodium sulfate. After evaporation of the solvent, the residue in 137 g is subjected to vacuum distillation and thus, 10 105.5 g (isopropyl-2 / indanyl-5) of methyl ketone is obtained in the form of white crystals with a melting point below 40 ° C. T. bale. 1.5 mmHg St. = " 0 121-125 ° C.
    PRI me R 2. (Isopropyl-2 / indanyl-5) with / ethanol.
    To a solution of 105.5 g (isopropyl-2 / indanyl-5) methyl ketone in 600 ml of methanol __ 25.6 g of potassium borohydride was added. After 3 hours of magnetic stirring at room temperature, the reaction mixture was concentrated. in vacuo, ice is added and the organic products are extracted with 60 ether. After washing with water and drying over sodium chloride, ether is evaporated. Thus, 106 g of (isopropyl-2 / -indanyl-5) cC-ethanol are obtained, which are used in crude form for subsequent operations.
    Example 3. (Isopropyl-2 / indanyl-5) c ^ - chloroethyl.
    To a solution of 106 g of (isopropyl-jq-3 / indanyl-5) οό-ethanol in 500 ml of benzene, 70 ml of thionyl chloride are added over 2 hours with magnetic stirring. After stirring for 15 minutes at room temperature, the reaction mixture was poured onto ice. The benzoic phase is separated and the mother liquors are extracted with ether. The collected organic phases are washed with water, then with a 5% bicarbonate solution, then again with water and finally dried over sodium sulfate. The organic solvents were evaporated in vacuo, the resulting residue was subjected to vacuum distillation. Obtain 104.1 g (isopropyl-2 / indanyl
    -5) cc-chloroethyl as an oil. T. bale. 1.5 mmHg Art. = 132-136 ^ 0.
    Example 4. (Isopropyl-2 / indanyl-5) methyl-2-acetonitrile.
    To a solution of 24.3 g of sodium cyanide in 210 ml of dimethyl sulfoxide is added dropwise a solution of
    104.1 g of (isopropyl-2 / indanyl) αί-chloroethyl in 70 ml of dimethyl sulfoxide.
    Upon completion of the addition, the reaction mixture was brought to 70-80 ° C for 4 hours 30 minutes. Then the reaction mixture is cooled, diluted with water and ice and extracted with ether. The ether extracts are washed thoroughly with water and dried over sodium sulfate. After evaporation of the ether, the residue was subjected to vacuum distillation, and thus, 74.1 g of (isopropyl-2 / in ^ anil-5) methyl-2-acetonitrile were obtained as an oil. T. bale. 1.5 mmHg Art. = 135-150 ° C.
    PRI me R 5. Methyl-2 (isopropyl-2 / indanyl-5) acetic acid.
    The solution is refluxed for 12 hours from
    74.1 g (isopropyl-2 / indanyl-5) methyl-2-acetonitrile in 185 ml of ethanol containing 185 ml of water and 74 g of potash.
    The reaction mixture was diluted with water and ice and the neutral products were extracted with ether.
    After acidification in the cold of the mother liquor, the acid is extracted with ether. The ether phase is washed and dried over sodium sulfate.
    After evaporation of the ether and recrystallization in petroleum ether, 50.6 g of methyl-2- (isopropyl-2 / indanyl-5) acetic acid are obtained in the form of white crystals, mp. 81-83 ^ 0.
    PRI me R 6. Methyl-2 (isopropyl-2 / indanyl-5) acetic acid hydrochloride dimethylaminoethyl ester.
    To a solution of 3.6 g of dimethylaluminoethanol in 80 ml of anhydrous benzene containing 9 ml of triethylamine is added dropwise a solution of 10 g of methyl-2 (isopropyl-2 / indanyl-5) acetic acid chloride in 50 ml of anhydrous benzene at 0 ° C. mixtures. Upon completion of the addition, the reaction mixture was stirred for 2 hours at room temperature, and then left overnight. The benzoic phase is separated, and the mother liquors are extracted with ether. The collected organic phases are washed thoroughly with water, then dried over sodium carbonate. After concentration in vacuo, the residue was diluted with acetone-ether, then ethyl chloride was added to a neutral pH. The resulting crystals are dehydrated, washed with ether, then crystallized in acetone. Thus, 11.4 g of methyl-2 (ieopropyl-2 / indanyl-5) acetic acid dimethylaminoethyl ester hydrochloride are obtained in the form of white crystals. T. pl. 123-124 R C.
    Example 10. The sodium salt of methyl-2 (isopropyl-2 / indanyl-5) acetic acid. R 4 = Na.
    25.5 g of methyl-2 (isopropyl-2 / -indanyl-5) acetic acid is treated with a solution of sodium methylate obtained from 2.5 g of sodium dissolved in 40 ml of ethanol. After evaporation of the solvent, the residue was diluted with ether to give 23 g of the sodium-containing * 0 salt of methyl-2 (isopropyl-2 / indanyl-5) acetic acid as a white powder, soluble in water.
    Example 11. Maleate of pyrrolidinoethyl ester methyl-2 (isopropyl-15 -2 / indanyl-5). Acetic acid. R = CH 2 —CH ^ —NO
    A solution of 11 g of sodium-containing salt of 20 methyl-2 (isopropyl-2 / indanyl-5) acetic acid and 6.9 g of β-chloroethylpyrrolidine in 100 ml of xylene is subjected to heating under reflux for 7 hours. After cooling the reaction mixture, the organic phase is washed with water and dried __ over sodium carbonate. After evaporation of the solvent, a residue of 14.3 g is obtained, to which a solution of 5 g of maleic acid in acetone is added. So get
    17.4 g of pyrrolidinoethyl maleate 30 methyl ester of 2 (isopropyl-2 / indanyl-5) acetic acid in the form of white crystals. T. pl. 114-11b ° C.
    权利要求:
    Claims (4)
    [1]
    It is desirable to use AlClj as the Lewis acid catalyst. The reduction of the ketone of the formula ill is advisable to conduct with potassium borohydride, and the haloiding with thionyl chloride. Example. {Isopropyl-2 / indanyl-5) methyl ketone. A solution of 100 g of isopropyl-2-indane and 65 ml of acetic anhydride in 400 ml of methylene chloride is added over 1 hour to a suspension of 190 g of aluminum chloride in 400 ml of methylene chloride while cooling so that the temperature of the reaction mixture remains below 10 ° C. The mixture is then stirred for 5 hours at room temperature, then diluted with 2 kg of ice and acidified to pH 3 with hydrochloric acid. ; The methylene chloride phase is separated, and the mother liquors are extracted with methylene chloride. The methylene chloride phases are collected, washed with water and dried over sodium sulfate. After evaporation of the solvent, the residue is 137 g of vacuum distillation and thus 105.5 g (isopropyl -2 / indanyl-5) of methyl ketone are obtained in the form of white crystals with a melting point of less than 40 s. T. Kip. 1.5 mmHg from 121-125c. PRI mme R 2. (Isopropyl-2 / indyl-5) o-ethanol. To a solution of 105.5 g (isopropyl -2 / indanyl-5) methyl ketone in 600 ml of methanol was added 25.6 g of borohydride and potassium. After 3 hours of magnetic stirring at room temperature, the reaction mixture is concentrated, under vacuum, ice is added and the organic products are extracted with ether. After washing with water and drying over sodium chloride, the ether is evaporated. Thus, 106 g (isopropyl-2 / -indanyl-5) o (; -ethanol, which in its crude form is used for subsequent operations, are obtained. Frozen (Isopropyl-2 / indyl-5) o-chloroethyl. To a solution from 106 g of {isopropyl-3 / indanyl-5) o-ethanol in 500 ml of benzene are added over 2 hours to 70 ml of thionyl chloride with magnetic stirring. After stirring for 15 minutes at room temperature, the reaction mixture is poured onto ice. The benzoic phase is separated and the mother solutions are extracted with ether. The collected organic phases are washed with water, then with a 5% bicarbonate solution, then again with water, and finally dried over sodium sulfate. The organic solvents are evaporated off in vacuo, the residue thus obtained is subjected to vacuum distillation. 104.1 g (isopropyl-2 / indanyl-5) with -chloroethyl are obtained in the form of an oil. T. Kip. 1.5 mmHg Art. 132-136 C. Example 4. (Isopropyl-2 / indanyl-5) methyl-2-acetonitrile. To a solution of 24.3 g of sodium cyanide in 210 ml of dimethyl sulfoxide a solution of 104.1 g of (isopropyl-2 / indanyl) og-chloroethyl in 70 ml of dimethyl sulfoxide is added dropwise. At the end of the addition, the reaction mixture is adjusted to 70-80 ° C over 4 hours and 30 minutes. The reaction mixture is then cooled, diluted with water and ice, and extracted with ether. The ether extracts are washed thoroughly with water and dried over sodium sulfate. After evaporation of the ether, the residue is subjected to vacuum distillation and thus 74.4 g (isopropyl-2 / in (anil-5) methyl-2-acetonitrile are obtained in the form of oil. T. boil 1.5 mm Hg. 135-150 ° C Example 5: Methyl-2 {isopropyl-2 / indanyl-5) acetic acid. The solution from 74.1 g (isopropyl-2 / indanyl-5) methyl-2-acetonitrile in 185 ml of ethanol containing 185 ml of water and 74 g of potash is heated under reflux for 12 hours. The reaction mixture is diluted with water and ice and the neutral products are extracted with ether. After acidifying in the cold of the mother liquors, the acid is extracted with ether. The ether phase is washed and dried over sodium sulfate. After evaporation of the ether and recrystallization in petroleum ether, 50.6 g of methyl 2- (isopropyl-2 / indanyl-5) acetic acid are obtained in the form of white crystals, m.p. 81-83c. Example 6. Methyl-2 (isopropyl-2 / indanyl-5) acetic acid dimethylaminoethyl ester hydrochloride. To a solution of 3.6 g of dimethylaluminoethanol in 80 ml of anhydrous benzene with a content of 9 ml of triethylamine is added dropwise a solution of 10 g of methyl 2-chloride (isopropyl-2 / indanyl-5) acetic acid in 50 ml of anhydrous benzene with the whole mixture . After the addition is complete, the reaction mixture is stirred at room temperature for 2 hours and then left overnight. The benzoic phase is separated, and the mother liquors are extracted with ether. The collected organic phases are washed thoroughly with water, then dried over sodium carbonate. After concentration in vacuo, the residue is diluted with acetone-ether, then added chlo | pure ethyl to neutral pH. The resulting crystals are dehydrated, washed with ether, then crystallized in acetone. Thus, 11.4 g of methyl dimethylaminoethyl methyl 2-ester (isopropyl-2 / icdanyl-5) acetic acid are obtained in the form of white crystals, m.p. 123-124s. Example 10. Sodium salt of methyl 2 (isopropyl 2 / indanyl 5) acetic acid. Cd Na. 25.5 g methyl-2 (isopropyl-2 / -indanyl-5) acetic acid is treated with sodium methoxide solution prepared from 2.5 g sodium dissolved in 40 ml of ethanol. After evaporation of the solvent, the residue is diluted with ether and 23 g of sodium salt of methyl 2 (isopropyl 2 / indanyl 5) acetic acid are obtained in the form of a white powder, soluble in water. Example 11. Methyl-2 pyrrolidinoethyl ester maleate (isopropyl-2 / indanyl-5). Acetic acid. R CH, j, -CH2. -N-Cl A 7-gram solution of methyl sodium 2 (. Isopropyl-2 / indanyl-5) acetic acid and 6.9 g /) is heated under reflux for 7 hours. chloroethylpyrrolidine in 100 ml of xylene. After cooling the reaction mixture, the organic phase is washed with water and dried over sodium carbonate. After evaporation of the solvent, a residue of 14.3 g is obtained, to which a solution of 5 g of maleic acid in acetone is added. Thus, 17.4 g of pyrrolidinoethyl maleate are obtained; Vfera methyl 2 (isopropyl 2 / indanyl 5) acetic acid as white crystals. T. pl. 114-11bS. Claims of the invention 1. A method of obtaining derivatives ind on general formula 1 where R is a hydrogen atom, an alkali metal or a group of the formula CHgCHa v J or lower. alk), in order to expand the range of physiologically active compounds, indane of formula II is subjected to interaction with acetic anhydride in the presence of Lewis acid catalyst and hydrochloric acid, the resulting ketone of formula III is reduced, the resulting alcohol of formula IV halogenate, the resulting hschoid derivative is reacted with an alkaline cyanide, the resulting nitrile of the formula V 1-HF-III is subjected to hydrolysis followed by isolation of the desired product in free form or as oli or as ether.
    [2]
    2. A method according to claim 1, characterized in that A1 C} J, is used as the acid catalyst of Lewis.
    [3]
    3. A process according to claim 1, characterized in that the reduction of the ketone of formula III is carried out with potassium borohydride.
    [4]
    4. A method according to claim 1, characterized in that the halogenation is carried out with thionyl chloride. Sources of information taken into account in the examination 1. Bksher K. Pearson D. Organic syntheses. M., Mir, 1973, p. 128,129 (1), 222-226 (1), 380 (2), 431 (2), 228 (2).
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    同族专利:
    公开号 | 公开日
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    FR2291062A1|1976-06-11|
    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:
    申请号 | 申请日 | 专利标题
    FR7437220A|FR2291062B3|1974-08-23|1974-08-23|
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