JP3256259B2 - Method for producing sulfone derivative - Google Patents

Method for producing sulfone derivative

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Publication number
JP3256259B2
JP3256259B2 JP02932792A JP2932792A JP3256259B2 JP 3256259 B2 JP3256259 B2 JP 3256259B2 JP 02932792 A JP02932792 A JP 02932792A JP 2932792 A JP2932792 A JP 2932792A JP 3256259 B2 JP3256259 B2 JP 3256259B2
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JP
Japan
Prior art keywords
compound
formula
reaction
xiii
sulfone derivative
Prior art date
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Expired - Fee Related
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JP02932792A
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Japanese (ja)
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JPH05221955A (en
Inventor
陽二 橘
信二 横山
剛 手島
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Nisshin Seifun Group Inc
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Nisshin Seifun Group Inc
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は植物ホルモンであるブラ
シノライド、あるいは医薬品であるビタミンDおよび活
性型ビタミンD誘導体の合成中間体の製造方法に関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a synthetic intermediate of brassinolide, which is a plant hormone, or vitamin D, which is a pharmaceutical, and an active vitamin D derivative.

【0002】[0002]

【従来の技術】式(I)または(II)で示されるスルホン誘
導体はブラシノライド類の側鎖合成(K. Mori, Tetrahe
dron, 38, 2099(1982), スキームI参照)やビタミンD
の側鎖合成(P.J. Kocienski, J. Chem. Soc., Perkin
1, 1978, 834, スキームII参照)に用いられている。ま
た、P. Ferrabochi らはS−(−)−3−メチル−γ−ブ
チロラクトンより(I)を合成しており(Synth. Commu
n., 13, 1199(1984), スキームIII参照)、Y. Gooni ら
はスルホレン誘導体を用いて本発明の中間体((V)およ
び(VI))(ラセミ体)を得ている(J. Org. Chem., 50, 2
493(1985),スキームIV参照)。また、DeLuca らはキラ
ルなスルフィネートエステルを用いる(I)および(II)の
誘導体の合成を報告している(J. Chem. Soc., Chem. C
ommun., 1989, 1113)。
2. Description of the Related Art A sulfone derivative represented by the formula (I) or (II) is used for side chain synthesis of brassinolides (K. Mori, Tetrahe).
dron, 38 , 2099 (1982), see Scheme I) and vitamin D
Side chain synthesis (PJ Kocienski, J. Chem. Soc., Perkin
1, 1978 , 834, Scheme II). Have synthesized (I) from S-(-)-3-methyl-γ-butyrolactone (Synth. Commu.
n., 13 , 1199 (1984), Scheme III), Y. Gooni et al. obtained the intermediates ((V) and (VI)) (racemic) of the present invention using sulfolene derivatives (J. Org. Chem., 50 , 2
493 (1985), Scheme IV). Also reported the synthesis of derivatives of (I) and (II) using chiral sulfinate esters (J. Chem. Soc., Chem. C.
ommun., 1989 , 1113).

【0003】[0003]

【化7】 Embedded image

【0004】しかしいずれの合成法も特殊な試薬を用い
ており、かつ立体選択性および収率上必ずしも満足でき
るものではない。
[0004] However, all the synthesis methods use special reagents and are not always satisfactory in stereoselectivity and yield.

【0005】[0005]

【発明が解決しようとする課題】本発明は式(I)または
(II)で示されるスルホン誘導体の簡便な合成法を提供す
ることを目的とする。
The present invention relates to a compound of the formula (I)
An object of the present invention is to provide a simple method for synthesizing the sulfone derivative represented by (II).

【0006】[0006]

【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、次の式(I)または(II)
Means for Solving the Problems The present inventors have made intensive studies and found that the following formula (I) or (II)

【化8】 で示されるフェニルスルホン誘導体が以下に記載する方
法によって容易に製造できることを見出した。
Embedded image Have been found to be easily produced by the method described below.

【0007】すなわち、(R)−または(S)−3−ヒドロ
キシ−メチルプロピオネートより数工程で得られる式(I
II)または(IV)で示される(R)−または(S)−2,3−ジ
メチル−4−フェニルスルホニル−2−ブタノール(Y.
Tachibana, Bull. Chem. Soc. Jpn., 62, 3132(1989))
That is, the formula (I) obtained in several steps from (R)-or (S) -3-hydroxy-methylpropionate
(R)-or (S) -2,3-dimethyl-4-phenylsulfonyl-2-butanol represented by (II) or (IV) (Y.
Tachibana, Bull.Chem.Soc.Jpn., 62 , 3132 (1989))

【化9】 を塩基の存在下メタンスルホニルクロライドと反応させ
て式(V)または(VI)
Embedded image Is reacted with methanesulfonyl chloride in the presence of a base to give a compound of formula (V) or (VI)

【化10】 で示される化合物とし、ついでこの式(V)または(VI)の
化合物に水素添加を行うことによって式(I)または(II)
で示される化合物が容易にかつ高収率で得られることを
見出して本発明を完成した。
Embedded image And then hydrogenating the compound of formula (V) or (VI) to give a compound of formula (I) or (II)
The present invention was completed by finding that the compound represented by the formula (1) can be obtained easily and in a high yield.

【0008】[0008]

【0009】上記した方法による式(III)または式(IV)
の化合物の脱水処理としては、直接例えば硫酸のような
脱水剤と反応させても良いが、一旦水酸基を例えばオキ
シ塩化リンのようなオキシハロゲン化リン、チオニルク
ロライドのようなチオニルハライド等のハロゲン化剤で
ハロゲンに変換するか、あるいはメタンスルホニルクロ
ライド、p−トルエンスルホニルクロライドのような置
換スルホニルハライドで活性エステル化した後に塩基と
反応させることによって脱水することも出来る。通常、
塩基の存在下にハロゲン化剤或いはエステル化剤を反応
させ一工程で実施することが好ましい。式(III)または
式(IV)の化合物とメタンスルホニルクロライドとの反応
は、有機溶媒中塩基としてのピリジン、トリエチルアミ
ンなどの存在下で行うことができる。また、これらの塩
基を溶媒として用いても良い。メタンスルホニルクロラ
イドは式(III)または(IV)の化合物に対して1〜10倍
当量を用いることができる。反応は0°〜室温で容易に
進行する。この反応におけるメタンスルホニルクロライ
ドの代わりにオキシ塩化リン、チオニルクロライドを用
いることもできる。
Formula (III) or formula (IV) according to the method described above
May be directly reacted with, for example, a dehydrating agent such as sulfuric acid, but once the hydroxyl group is halogenated with, for example, phosphorus oxyhalide such as phosphorus oxychloride, thionyl halide such as thionyl chloride, etc. Alternatively, dehydration can be carried out by converting the compound to a halogen with an agent, or by active esterification with a substituted sulfonyl halide such as methanesulfonyl chloride or p-toluenesulfonyl chloride, followed by reaction with a base. Normal,
The reaction is preferably carried out in one step by reacting a halogenating agent or an esterifying agent in the presence of a base. The reaction of the compound of the formula (III) or the formula (IV) with methanesulfonyl chloride can be carried out in an organic solvent in the presence of pyridine, triethylamine or the like as a base. Further, these bases may be used as a solvent. Methanesulfonyl chloride can be used in an amount of 1 to 10 times the equivalent of the compound of the formula (III) or (IV). The reaction proceeds easily from 0 ° to room temperature. Phosphorus oxychloride or thionyl chloride can be used instead of methanesulfonyl chloride in this reaction.

【0010】次に式(V)または(VI)の化合物に水素添加
を行い目的化合物である式(I)および(II)で示されるス
ルホン誘導体を得ることができる。水素添加はパラジウ
ム−炭素、酸化白金等慣用の触媒を式(V)または(VI)の
化合物に対して0.5〜15%(重量比)用いて行うこ
とができる。水素圧は1〜10気圧で反応は進行し、反
応温度は0°〜室温で行うことができる。
Next, the compound of formula (V) or (VI) is hydrogenated to obtain the desired sulfone derivative represented by formula (I) or (II). Hydrogenation can be carried out using a conventional catalyst such as palladium-carbon or platinum oxide in an amount of 0.5 to 15% (weight ratio) with respect to the compound of the formula (V) or (VI). The reaction proceeds at a hydrogen pressure of 1 to 10 atm and the reaction temperature can be from 0 ° to room temperature.

【0011】化合物(III)および(IV)をメタンスルホニ
ルクロライドと処理した場合5〜10%の式(XIII)
When compounds (III) and (IV) are treated with methanesulfonyl chloride, 5-10% of the compound of formula (XIII)

【化14】 で示されるオレフィンが副生する。しかし式(XIII)の
化合物は反応混合物より選択的に結晶として除くことが
できるし、さらに上記の水素還元条件下では全く還元さ
れないことがわかった。従って式(I)または(II)の化合
物に式(V)および(VI)または(XIII)の化合物が混入して
も水素還元後、反応混合物をm−クロロ過安息香酸(m
−CPBA)等の酸化剤またはオゾンと処理すれば式
(V)および(VI)または(XIII)の化合物はエポキシ化合物
或いはケトン化合物に変換することができる。生成した
エポキシ化合物、ケトン化合物は式(I)または(II)の化
合物と容易に例えばクロマトグラフィー等により分離す
ることができる。すなわち式(I)または(II)の化合物と
式(V)および(VI)または(XIII)の化合物との分離は容易
に達成することができる。
Embedded image The olefin represented by is by-produced. However, it has been found that the compound of the formula (XIII) can be selectively removed as crystals from the reaction mixture, and further, it is not reduced at all under the above-mentioned hydrogen reduction conditions. Therefore, even if the compound of the formula (I) or (II) is mixed with the compound of the formula (V), (VI) or (XIII), after hydrogen reduction, the reaction mixture is treated with m-chloroperbenzoic acid (m
-CPBA) or an oxidizing agent such as ozone
Compounds (V) and (VI) or (XIII) can be converted to epoxy compounds or ketone compounds. The produced epoxy compound and ketone compound can be easily separated from the compound of the formula (I) or (II) by, for example, chromatography. That is, separation of the compound of formula (I) or (II) from the compound of formula (V) and (VI) or (XIII) can be easily achieved.

【0012】上記した反応工程による方法を具体的な反
応試薬を用いる反応によって例示すると次のスキームV
で示される。
The above reaction step is exemplified by a reaction using a specific reaction reagent.
Indicated by

【0013】[0013]

【化15】 Embedded image

【0014】[0014]

【0015】[0015]

【0016】[0016]

【0017】上記した本発明の方法で得られた式(I)
および(II)で示される化合物はブラシノライド類、ビタ
ミンD類(ビタミンD4、ビタミンD7)および活性型ビ
タミンD類の側鎖部合成のための中間体として極めて有
用な化合物である。
Formula (I) obtained by the method of the present invention described above.
The compounds represented by (II) and (II) are extremely useful compounds as intermediates for synthesizing side chains of brassinolides, vitamin Ds (vitamin D 4 and vitamin D 7 ) and active vitamin Ds.

【0018】以下、実施例によって本発明を具体的に記
述することにするが、これらの実施例は本発明を例示す
る目的で記述するものであって、本発明はこれらに限定
されるものではない。
Hereinafter, the present invention will be specifically described by way of examples. However, these examples are described for the purpose of illustrating the present invention, and the present invention is not limited to these examples. Absent.

【0019】実施例1 (S)−2,3−ジメチル−1−フェニルスルホニルブタ
ン(I)の製造 (S)−2,3−ジメチル−4−フェニルスルホニル−2
−ブタノール(III)(4.8g)をピリジン(45ml)に
溶かしジメチルアミノピリジン0.3gおよびメタンス
ルホニルクロライド(4.0g)を加え、室温で20時
間撹拌した。反応液を氷水中に注ぎ酢酸エチルで抽出
し、10%塩酸次いでブラインで洗浄し、乾燥後濃縮し
た。残留物をシリカゲルクロマトグラフィーで精製し
(S)−2,3−ジメチル−4−フェニルスルホニル−2
−ブテン(V)と2,3−ジメチル−1−フェニルスル
ホニル−2−ブテン(XIII)の混合物3.3gを得た。
この混合物をヘキサン−IPEに溶解し冷却すると0.
3gの化合物(XIII)が針状結晶として得られた。母液
からは化合物(V)が3.0g得られた。
Example 1 Preparation of (S) -2,3-dimethyl-1-phenylsulfonylbutane (I) (S) -2,3-dimethyl-4-phenylsulfonyl-2
-Butanol (III) (4.8 g) was dissolved in pyridine (45 ml), dimethylaminopyridine (0.3 g) and methanesulfonyl chloride (4.0 g) were added, and the mixture was stirred at room temperature for 20 hours. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with 10% hydrochloric acid and then with brine, dried and concentrated. The residue is purified by silica gel chromatography.
(S) -2,3-dimethyl-4-phenylsulfonyl-2
3.3 g of a mixture of -butene (V) and 2,3-dimethyl-1-phenylsulfonyl-2-butene (XIII) were obtained.
This mixture was dissolved in hexane-IPE and cooled to 0.2.
3 g of compound (XIII) were obtained as needle crystals. 3.0 g of compound (V) was obtained from the mother liquor.

【0020】化合物V:1H NMR(CDCl3):δ 1.20(3H,
d, J=6.8Hz)、 1.62(3H, s)、 2.77(1H, m)、 3.05(1H, d
d, J=14.2Hzおよび7.9Hz)、 3.23(1H, dd, J=14.2Hzおよ
び4.9Hz)、 4.70(1H, s)、 4.71(1H, s)、 7.53-7.93(5H,
m)。
Compound V: 1 H NMR (CDCl 3 ): δ 1.20 (3H,
d, J = 6.8Hz), 1.62 (3H, s), 2.77 (1H, m), 3.05 (1H, d
d, J = 14.2Hz and 7.9Hz), 3.23 (1H, dd, J = 14.2Hz and 4.9Hz), 4.70 (1H, s), 4.71 (1H, s), 7.53-7.93 (5H,
m).

【0021】化合物XIII:融点97〜98℃;1H NMR(C
DCl3):δ 1.28(3H, s)、 1.63(3H,s)、 1.78(3H, s)、 3.
87(3H, s)、 7.52-7.90(5H, m)。
Compound XIII: melting point 97-98 ° C .; 1 H NMR (C
DCl 3 ): δ 1.28 (3H, s), 1.63 (3H, s), 1.78 (3H, s), 3.
87 (3H, s), 7.52-7.90 (5H, m).

【0022】化合物(V)(3.0g)をエタノール(1
50ml)に溶かしパラジウム−炭素0.3gを加え常圧
で接触水素添加を18時間行った。触媒を濾過して除き
エタノールを留去し、残留物(2.7g)を塩化メチレ
ン(30ml)に溶解し、m−CPBA(1.0g)を加
え室温で24時間反応させた。炭酸カリウム水溶液に次
いでブラインで洗浄した後溶媒を留去した。残留物をシ
リカゲルクロマトグラフィーで精製し化合物(I)を2.
3g得た。
Compound (V) (3.0 g) was added to ethanol (1
50 g), and 0.3 g of palladium-carbon was added thereto, followed by catalytic hydrogenation at normal pressure for 18 hours. The catalyst was removed by filtration, and ethanol was distilled off. The residue (2.7 g) was dissolved in methylene chloride (30 ml), m-CPBA (1.0 g) was added, and the mixture was reacted at room temperature for 24 hours. After washing with an aqueous potassium carbonate solution and brine, the solvent was distilled off. The residue was purified by silica gel chromatography to give compound (I) in 2.
3 g were obtained.

【0023】〔α〕20 D +19.1°(c=1.0,クロ
ロホルム)1 H NMR(CDCl3):δ 0.77(3H, d, J=6.8Hz)、 0.82(3H,
d, J=6.8Hz)、 1.02(3H,d, J=7.3Hz)、 1.68(1H, m)、 2.0
3(1H, m)、 2.88(1H, dd, J=14.2Hzおよび8.8Hz)、 3.09
(1H, dd, J=13.7Hzおよび2.9Hz)、 7.56-7.93(5H, m)。
[Α] 20 D + 19.1 ° (c = 1.0, chloroform) 1 H NMR (CDCl 3 ): δ 0.77 (3H, d, J = 6.8 Hz), 0.82 (3H,
d, J = 6.8Hz), 1.02 (3H, d, J = 7.3Hz), 1.68 (1H, m), 2.0
3 (1H, m), 2.88 (1H, dd, J = 14.2Hz and 8.8Hz), 3.09
(1H, dd, J = 13.7 Hz and 2.9 Hz), 7.56-7.93 (5H, m).

【0024】実施例2 (R)−2,3−ジメチル−1−フェニルスルホニルブタ
ン(II)の製造 (R)−2,3−ジメチル−4−フェニルスルホニル−2
−ブタノール(IV)(5.0g)をピリジン(50ml)に
溶かし、氷冷下オキシ塩化リン(2.0ml)を加え、0
〜5℃で6時間撹拌した。10%塩酸を加え酸性にした
後酢酸エチルで抽出した。NaHCO水溶液に次いで
ブラインで洗浄した後濃縮した。残留物をシリカゲルク
ロマトグラフィーを行い、化合物(VI)(約7%の化合物
(XIII)を含む)を3.7g得た。
Example 2 Preparation of (R) -2,3-dimethyl-1-phenylsulfonylbutane (II) (R) -2,3-dimethyl-4-phenylsulfonyl-2
-Butanol (IV) (5.0 g) was dissolved in pyridine (50 ml), and phosphorus oxychloride (2.0 ml) was added thereto under ice-cooling.
Stirred at 55 ° C. for 6 hours. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate. The extract was washed with an aqueous solution of NaHCO 3 and then with brine, and then concentrated. The residue was subjected to silica gel chromatography to give compound (VI) (about 7% of compound
(Including (XIII)).

【0025】化合物(VI)(3.7g)をエタノール(2
00ml)に溶かし、パラジウム−炭素(0.3g)を加
え常圧で接触水素添加を20時間行った。触媒を濾過し
て除き触媒を留去し、残留物(3.4g)を塩化メチレ
ン(50ml)に溶かし、m−CPBA(1.0g)を加
え室温で20時間撹拌した。炭酸カリウム水溶液に次い
でブラインで洗浄した後溶媒を留去し、残留物をシリカ
ゲルクロマトグラフィーで精製し化合物(II)を2.5g
得た。
Compound (VI) (3.7 g) was added to ethanol (2
00 ml), palladium-carbon (0.3 g) was added, and catalytic hydrogenation was performed at normal pressure for 20 hours. The catalyst was removed by filtration, and the catalyst was distilled off. The residue (3.4 g) was dissolved in methylene chloride (50 ml), m-CPBA (1.0 g) was added, and the mixture was stirred at room temperature for 20 hours. After washing with an aqueous potassium carbonate solution and brine, the solvent is distilled off, and the residue is purified by silica gel chromatography to obtain 2.5 g of compound (II).
Obtained.

【0026】〔α〕20 D −19.6°(c=1,クロロ
ホルム)1 H NMR(CDCl3):δ 0.77(3H, d, J=6.8Hz)、 0.82(3H,
d, J=6.8Hz)、 1.02(3H,d, J=7.1Hz)、 1.67(1H, m)、 2.0
3(1H, m)、 2.91(1H, dd, J=14.2Hzおよび8.8Hz)、 3.10
(1H, dd, J=13.8Hzおよび3.0Hz)、 7.55-8.00(5H, m)。
[Α] 20 D -19.6 ° (c = 1, chloroform) 1 H NMR (CDCl 3 ): δ 0.77 (3H, d, J = 6.8 Hz), 0.82 (3H,
d, J = 6.8Hz), 1.02 (3H, d, J = 7.1Hz), 1.67 (1H, m), 2.0
3 (1H, m), 2.91 (1H, dd, J = 14.2Hz and 8.8Hz), 3.10
(1H, dd, J = 13.8 Hz and 3.0 Hz), 7.55-8.00 (5H, m).

【0027】[0027]

【0028】[0028]

【0029】[0029]

【0030】[0030]

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C07C 317/00 C07C 315/00 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07C 317/00 C07C 315/00 CA (STN) REGISTRY (STN)

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 次の式(I)または(II) 【化1】 で示されるフェニルスルホン誘導体を製造するにあた
り、次の式(III)または(IV) 【化2】 で示されるフェニルスルホニルアルコール誘導体を塩基
の存在下にメタンスルホニルクロライド、オキシ塩化リ
ンまたはチオニルクロライドと処理して次の式(V)また
は(VI) 【化3】 で示される化合物とし次いで水素添加を行うことによ
る、上記化合物(I)および(II)の製造方法。
(1) The following formula (I) or (II): In producing the phenylsulfone derivative represented by the following formula (III) or (IV): Is treated with methanesulfonyl chloride, phosphorus oxychloride or thionyl chloride in the presence of a base to give the following formula (V) or (VI): A method for producing the compounds (I) and (II) by subjecting the compound to the compound represented by the formula (1) and then performing hydrogenation.
JP02932792A 1992-02-17 1992-02-17 Method for producing sulfone derivative Expired - Fee Related JP3256259B2 (en)

Priority Applications (1)

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JP02932792A JP3256259B2 (en) 1992-02-17 1992-02-17 Method for producing sulfone derivative

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JP02932792A JP3256259B2 (en) 1992-02-17 1992-02-17 Method for producing sulfone derivative

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JPH05221955A JPH05221955A (en) 1993-08-31
JP3256259B2 true JP3256259B2 (en) 2002-02-12

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