• 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:
    A process for preparing 1-(3-benzyloxyphenyl)-1,1-dimethylheptane by reacting 1-(3-benzyloxyphenyl)-1-chloro-1-methylheptane in a solvent at -50 DEG to 10 DEG C with from 1 to 3 molar equivalents of trimethylaluminum. Also included are the novel intermediates 1-(3-benzyloxyphenyl)-1-chloro-1-methylheptane and 1-(3-benzyloxyphenyl)-1-methylheptan-1-ol and their preparation. The title compound is a valuable intermediate in the synthesis of certain analgesic agents.
    公开号:SU1250168A3
    申请号:SU823507548
    申请日:1982-11-01
    公开日:1986-08-07
    发明作者:Шерман Мелвин Лоренс (младший)
    申请人:Пфайзер,Инк (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to an improved process for the preparation of 1 - (3-benzyl syphenyl) -1,1-dimethyl-heptane.
    p9
    C-SbNy
    which is used as a precursor for the synthesis of 2- (substituted) -4- (1/1 -dimethylgöptil) -phenols.
    The purpose of the invention is to increase the yield of the target product.
    Example 1. (a) 86%. 3- -Benzyloxyacetophenone.
    A mixture of 1 kg (7.35 mol) of 3-oxyacetophenone, 1.035 mg (7.5 mol) of anhydrous potassium carbonate, and 0.945 kg of benzyl chloride is boiled under reflux for 24 hours with mechanical stirring. in 4 liters of acetone, after which 0.1035 kg (0.75 mol of potassium carbonate and 0.0945 kg (0.75 mol of benzyl chloride) are added and continue to boil under reflux. This addition is repeated after 72 h of refluxing and continue boiling for up to 96 h. The reaction mixture is cooled, filtered, and the filtrate is concentrated on a rotary evaporator. Then the filtrate is treated with 0.202 kg (2.0 mol) of triethylamine and stirred overnight. The reaction mixture is diluted with 1 L of ether and filtered. The filtrate is evaporated and the residue is distilled to give 1.429 kg (86%) of 3-benzyloxyacetophenone as an oil. BP 160. C / 0.3 mm Hg
    J-spectrum (CHCl1), cm: 1695.1605, 1595, 1493 and 1443.
    PMR (CDClI), 2.52 (s, CH3), 5.03 (s, CHj) and 7, .0-7.7 (m, Ph).
    Example 2. 1- (3-Benzyloxy-phenyl) -1-methylheptan-1-ol.
    To a paste of 186 g (7.65 mol) of magnesium in 3.5 l of tetrahydrofuran was added 1.023 l (7.29 mol) of 1-brpmhexane over 2 hours. The resulting Grignard solution was allowed to cool to 25 ° C. A solution of 1.098 kg is added.
    501682
    (4.86 mol) of 3-bezyloxyacetofenone in 1 liter of tetrahydrofuran to a Grignard solution for 3 hours. Podzer. The reaction temperature at 125–18 ° C lives with the help of an ice bath. After the addition is complete, the reaction mixture is stirred overnight at 25 ° C. A solution of 61.5 g (3.42 mol) of water is added to the reaction mixture.
    10 in 120 ml of tetrahydrofuran. Within 15 minutes and after stirring for 20 minutes, another 0.440 l (1.1 mol) of 2.5 M hexyl-magnesium bromide in ether is added. Stir
    15 The reaction mixture was further 20 hours, and then quenched by slowly adding to the mixture 6 liters of water and ice and 75 O l (14.2 mol) of ammonium chloride. The organic extract is removed and the aqueous extract
    20 extrahexant in 1 liter of ether. The combined organic extract is washed with 1 L of sodium chloride chloride, dried over magnesium sulfate and evaporated, yielding 1.424 kg
    25 (94%) 1- (3-benzyloxyfensch1) -1-methylheptan-1-ol as an oil.
    PMR (CDClI),: 0.83 (m, CHj), 1.20 (m, CH); 1.51 (s, CH3); B72 (s, HE); 1.8 (m, CHj); 5.02 (s,
    30 CHj). and 6.7-7.6 (m, PhH).
    Example 3. 1- (3-Benzyloxy-. Phenyl) -1,1-dimethylheptane.
    A mixture of 660 g (2.11 mol) of 1- (3-benzyloxy-phenyl) -1-methylheptan-1-ol and 1.70 l of concentrated hydrochloric acid is intensively stirred for 40 minutes. The reaction mixture is diluted with 600 ml of tbxane and the layers are separated. The organic extract was washed with 500 ml of saturated sodium bicarbonate solution, 500 ml of saturated sodium chloride solution, dried over magnesium sulfate and evaporated, yielding 664 g (95%) of intermediate 45
    1- (3-benz1-oxyphenyl) -1-chloro--1-methylheptane.
    I
    A solution of the said chloride compound in 660 ml of methylene chloride is added to a solution of 947 ml
    25% aluminum methyl (3.28 M) in hexane, dissolved in 1.9 l of methylene chloride. The addition is completed after 1.5 hours, while maintaining the temperature from -18 to
    -20 C. The reaction mixture is stirred for 1 hour at -15 ° C and overnight at -8 ° C. Then the reaction mixture is quenched by slowly adding 2 liters.
    31250168 4
    ice simultaneously with the slow pre-IR spectrum (CHClj), 1604 and
    The addition of 540 ml of concentrated 1581.
    hydrochloric acid. Organizable XPMS (m / e): 310, 2351 (M, high layer and water layer extract for C "H 0: 310.2289), 225,
    500 ml of methylene chloride. 5 1304, (Mf.-Cg, calculated for
    Combined organic extract (jH 0: 225.1275).
    washed with 500 ml of saturated rast-tu f (CDClj), f .0.82 (m, CHj) 1.17
    thief sodium bicarbonate, dried over (m, CH); 1.23 (s, CHj) i 1.5 (m,
    magnesium sulfate and evaporated to CHj); 5.00 (s, CH) and 6.6-7.5 (//,
    oils. The crude product is distilled, Ph-10 each).
    525 g (80%) of the desired product. The proposed method allows
    in the form of oil. Bp 168-17b C / get the target product with the output
    / 0.3 mmHg The total yield of 62% .80% versus 35% in the known method.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 1- (3-BENZYloxyphenyl) -1,1-DIMETHYLHEPTANE by reacting 1- (3-benzyloxyphenyl) -1-methyl-1-chloroalkane with an organometallic compound in an inert organic solvent, characterized in that, in order to increase yield of the target product, 1- (3-benzyloxyphenyl) -1-chloro-1-methylheptane is used as 1- (3-benzyloxyphenyl) -1-methyl-1-chloroalkane, trimethylaluminium is used as an organometallic compound, and as an inert organic solvent - methylene chloride, and the process is carried out at a molar ratio Reagents and respectively 1: 1.64 at a temperature between (-) 20 to (+) 10 ° C.
    类似技术:
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    同族专利:
    公开号 | 公开日
    AU535034B2|1984-03-01|
    GT198277940A|1984-04-21|
    ES8401006A1|1983-12-01|
    PH18275A|1985-05-14|
    DK483782A|1983-05-03|
    PL238735A1|1983-06-06|
    AU9004482A|1983-05-12|
    NO823618L|1983-05-03|
    FI823721L|1983-05-03|
    FI823721A0|1982-11-01|
    US4360700A|1982-11-23|
    IE54030B1|1989-05-24|
    IN158311B|1986-10-18|
    HU187796B|1986-02-28|
    PT75771A|1982-11-01|
    AR231966A1|1985-04-30|
    JPS5888335A|1983-05-26|
    JPS6212773B2|1987-03-20|
    IL67144A|1985-10-31|
    IL67144D0|1983-03-31|
    KR840002340A|1984-06-25|
    CS770482A2|1985-06-13|
    YU242882A|1985-03-20|
    CS241129B2|1986-03-13|
    DE3260609D1|1984-09-27|
    PL137947B1|1986-08-30|
    NO156008B|1987-03-30|
    PT75771B|1985-12-09|
    KR850001471B1|1985-10-10|
    IE822609L|1983-05-02|
    GR77726B|1984-09-25|
    NO156008C|1987-07-08|
    EP0079168B1|1984-08-22|
    EP0079168A1|1983-05-18|
    DD208606A5|1984-04-04|
    ES517002A0|1983-12-01|
    AT9088T|1984-09-15|
    ZA826792B|1983-07-27|
    NZ202321A|1984-11-09|
    CA1198450A|1985-12-24|
    引用文献:
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    US4284829A|1977-09-13|1981-08-18|Pfizer Inc.|Hydroxyalkyl and oxoalkyl substituted phenols as analgesics and sedatives|
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    DE3617183A1|1985-11-16|1987-05-27|Bayer Ag|SUBSTITUTED BENZYL ETHERS|
    DE3644798A1|1986-12-31|1988-07-14|Hoechst Ag|NEW NITROHALOALCOXYBENZOLS, METHOD FOR THEIR PRODUCTION AND THEIR USE|
    KR101057546B1|2007-06-05|2011-08-17|주식회사 엘지화학|Optically anisotropic compound and resin composition containing same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/317,223|US4360700A|1981-11-02|1981-11-02|Intermediates for making 1--1,1-dimethylheptane|
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