• 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:

    公开号:SU873890A3
    申请号:SU802907605
    申请日:1980-04-11
    公开日:1981-10-15
    发明作者:Вихерт Рудольф；Биттлер Дитер；Керб Ульрих；Прецевовски Клаус；Казальс-Штенцель Йорге；Лозерт Вольфганг
    申请人:Шеринг Аг(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing new derivatives of steroids, namely 6 ft, 7 (b, 15.16-dimethylene-1,4-
    where the 15.16-methylene group may be in the bcL or ft position;
    E - means a group
    The purpose of the invention is the receipt of new steroid compounds with pharmacological activity.
    The goal is achieved in that according to the method for producing compounds of the formula '1, the corresponding 6ft ·, 7 ft, 15.16 dimethylene-4-androsten-3-one is dehydrated in the 1,2-position, preferably with selenium dioxide or 2,3 dichloro-5,5 β-dicyanobenzoquinone and, if desired, the lactone ring is then cleaved, after which the desired products are isolated by known methods.
    . HE
    GT ° A (eig), he
    0 ") or
    OH: x X z-CH - CH z - Cook possessing pharmacological NOSTA.
    A method is known for introducing the D 'double active bond into a steroid of the androstane series using selenium dioxide or 2,3-dichloro-5,5-dicyanobenzoquinone (1J.
    Example 1. 500 mg 6 ft t 7ft, 15ft, 16 ft-dimethylene-4-androsten- [17 (ft-1 1 ) spiro-5 1 J perhydrofuran-2,3-dione, dissolved in 7.5 ml of dioxane, refluxed for 17 h with 500 ml of 2,3-dichloro-5,6-dicyan-p-benzoquinone, after which the reaction mixture was diluted with diethyl ether and washed with saturated bicar-! sodium bonate and water, dried and evaporated. The residue was separated by silica gel chromatography. The result is 330 mg of 6 ^, 79, 15ft, 16 ft-dimethylene-1,4-androstadiene [17 (ft-1 1 ) with pyro-5 1 ] perhydrofuran-2 *, 330 dione with so pl. 250.5-252'0.
    UV: e 2.45 = 12000; € - 9950.
    Example 2. 300 mg 6fl>, 7 (b, 15L, 16L-dimethylene-4-androsten [17 ((b-1 ') spiro-5'] perhydrofuran-2 1 , 3-dione, dissolved in 15 ml tert butanol, stirred with 90 mg of selenium dioxide and 0.5 ml of acetic acid for 20 hours under reflux, then another 90 mg of selenium dioxide was added to the mixture and refluxed for another 24 hours. After evaporation to dryness, the residue was separated by chromatography. on silica gel, 120 mg of 6β> 7 (b, 154, 16ct-dimethylene-1,4-androstadadiβΗ- [17 (& - 1 *) spiro-5 ( ] perhydrofuran ~ 2 3-dione are obtained.
    UV: € ¢ .46 = 11800; E 2d5 = 9800.
    Example 3. 500 mg 6 p,, 1 $, 15 (b, 16 [b-dimethylene-1,4-androstadiene- (17 ((b-1 ') spiro-5'] perhydrofuran-2,3-dione are dissolved in 5 ml of isopropanol, mixed with 1.37 ml of a 1N potassium hydroxide solution in methanol and refluxed for 1 h. After cooling to it • 30 ml of absolute ether are added, placed in an ice bath and stirred for 1 h. The precipitated crystals * ^ are suctioned off, washed well with ether and dried to give 510 mg of potassium salt 3 (17B-oxybp> 7 (ί, 15 (b, 16 (i-dimethylene-3-oxo-1 , 4-androstadien-174-yl) propionic acid.
    UV: E u5 = 11500; E 2 bb = 9600.
    Primer 4. 300 mg 17p> hydroxy-17Λ - (3-hydroxypropyl) -6 ίϊ, 7 P> -dimethylene-4-androsten-3-one dissolved in 9 ml of dioxane, and 300 mg of 2,3-dichloro- 5,6-dicyan-p-benzoquinone was refluxed for 17 hours, after which the reaction mixture was diluted with ether, washed with saturated sodium bicarbonate solution and water, dried and evaporated. The residue was separated by silica gel chromatography. The result is 120 mg of 17 ^ .- hydroxy (0
    -17-4- (3-hydroxypropyl) -6 (%, 7th>, 15p>, 16p-dyethylen-l, 4-androstadiene-3-one as an amorphous substance.
    UV: ¢¢ 44. "11500; E 295 "9600.
    权利要求:
    Claims (3)
    [1]
    UV: e 2.45 12000; e av - 9950. Example 2. 300 mg 61b, 71, 15L, 16A. - dimethylene-4-androstene 17 -1) spiro-5 perhydroFuran-2,3-dio dissolved in 15 ml of tert butanol P1 is mixed with 90 mg of selenium dioxide and 0.5 ml of acetic acid for 20 hours under refluxing. Then, another 90 mg of selenium dioxide is added to the mixture and refluxed for another 24 hours. After evaporation to dryness, the residue is separated by chromatography on silica gel. The result is 120 mg of 6ft, 7 15dl, 16cL-dimethylen-1, 4-andprostadien-17 ((-l) crcro-5J perhydrofuran-2, 3-dione. UV: € 146 11800; Etce 9800. Example 3. 500 mg br, 70, 15ft, 161) -dimethylene-1,4-andprostadien-7 ((-l) spiro-5 perhydrofuran-2, 3-dione is dissolved in 5 ml of isopropanol, mixed with 1.37 ml 1 and. the solution of hydroxide ali in methanol and the mixture is boiled under reflux for 1 h. After cooling, 30 ml of absolute ether are added to it, placed in an ice-water bath and stirred for 1 hour. The crystals that fall out are drained by ether and dried.The result is 5HH) mg potassium th salt of 3 {17E-oxy-bp-, 7ft f 15 (b, 16ft-dimethylene-3-oxo-1,4-androstadiene-17o1-yl) propionic acid. UV: 11500; e2vb 9600. Example 4. 300 mg of 17 (hydroxy-17dL - (3-hydroxypropyl) -b |, 7 P -dimethylene-4-androsten-3-one, dissolved in 9 ml of dioxane, and 300 mg of 2 , 3-dichloro-5, b-dicyan-p-benzoquinone is boiled 17. under reflux, after which the reaction mixture is diluted with ether, washed with saturated sodium bicarbonate solution and water, dried and evaporated. chromatography on silica gel. The result is 120 mg of 17.-hydroxy-17- (1- (3-hydroxypropyl) -6 (%, 71%, 15 (L, 16 | 5 D1 "5 | ethylene-1, 4-androstadiene -3-C) on in the form of an amorphous substance. UV: € “11,500; Ejgj 9600. Invention Formula and 1. A method for preparing 6p), 71b, 15,16-dimethylene-1, 4-androstadiene-3-oy; the general formula G. where the 15,1b-methylene group can be in the d- or | i-position; E means he group A- (iH,), GT f ciHz-COOK characterized in that the corresponding b (J, 7 (i, 15,16-dimethylene-4-androsten-3-one) is dehydrated in the 1,2-position and, if desired, the lactone ring is then cleaved, after which the desired products are isolated,
    [2]
    2. Method according to item 1, about t l and. This is due to the fact that the 1,2-position dehydrogenation is carried out with the help of selenium oxide.
    [3]
    3. The method according to claim 1, about the t and h and y and the fact that the dehydrogenation of the 1,2-position is carried out using 3-dichloro-5,5-dicyanobenzoquinone. . Sources of information taken into account during the examination 1. Jerassi J.steroids reactions. h.5, p. 229, 233.
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    同族专利:
    公开号 | 公开日
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    DK234780A|1980-12-01|
    AU5874580A|1980-12-04|
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    IE49899B1|1986-01-08|
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    CS214712B2|1982-05-28|
    YU41926B|1988-02-29|
    EP0019690A1|1980-12-10|
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    JPS55162799A|1980-12-18|
    CA1134814A|1982-11-02|
    DD151172A5|1981-10-08|
    YU132980A|1983-02-28|
    HU187419B|1986-01-28|
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    ES491916A0|1980-12-16|
    IL60185D0|1980-07-31|
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    引用文献:
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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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