JPH09249683A - N-actyl-d-neuraminic acid derivaitive and its production - Google Patents
N-actyl-d-neuraminic acid derivaitive and its productionInfo
- Publication number
- JPH09249683A JPH09249683A JP8069696A JP8069696A JPH09249683A JP H09249683 A JPH09249683 A JP H09249683A JP 8069696 A JP8069696 A JP 8069696A JP 8069696 A JP8069696 A JP 8069696A JP H09249683 A JPH09249683 A JP H09249683A
- Authority
- JP
- Japan
- Prior art keywords
- acetyl
- group
- neuraminic acid
- formula
- neuraminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- Saccharide Compounds (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【0001】[0001]
【発明の属する技術分野】N−アセチル−D−ノイラミ
ン酸は天然の生理活性を示す糖鎖の末端に広く見られ、
これらの化合物は、医薬品、農薬、化粧品、試薬類など
として注目されている。本発明のN−アセチル−D−ノ
イラミン酸エステル誘導体は、これらの化合物を製造す
る際に、重要な合成中間体として使用することができ
る。TECHNICAL FIELD N-Acetyl-D-neuraminic acid is widely found at the end of sugar chains showing natural physiological activity.
These compounds have attracted attention as pharmaceuticals, agricultural chemicals, cosmetics, reagents and the like. The N-acetyl-D-neuraminic acid ester derivative of the present invention can be used as an important synthetic intermediate in the production of these compounds.
【0002】[0002]
【従来の技術】従来知られている無保護のN−アセチル
−D−ノイラミン酸をエステル化する方法としては、メ
チルアルコール中で酸性樹脂を用いて、メチルエステル
基を導入する方法がある。2. Description of the Related Art As a conventionally known method for esterifying unprotected N-acetyl-D-neuraminic acid, there is a method of introducing a methyl ester group using an acidic resin in methyl alcohol.
【0003】[0003]
【発明が解決しようとする課題】従来のアルコール中、
酸性樹脂を用いる無保護のN−アセチル−D−ノイラミ
ン酸のエステル化法では、メタノール以外のアルコール
を用いて、メチル基以外のエステル基を導入することは
困難である。DISCLOSURE OF THE INVENTION In conventional alcohol,
In the esterification method of unprotected N-acetyl-D-neuraminic acid using an acidic resin, it is difficult to introduce an ester group other than a methyl group using an alcohol other than methanol.
【0004】[0004]
【課題を解決するための手段】本発明者らは、N−アセ
チル−D−ノイラミン酸塩とハロゲン化アルキルを反応
させることにより、無保護のN−アセチル−D−ノイラ
ミン酸から1位のカルボキシル基に種々のエステル基が
導入された種々のN−アセチル−D−ノイラミン酸エス
テル誘導体が効率良く得られることを知り本発明に到達
した。以下、本発明を詳細に説明する。Means for Solving the Problems The present inventors have prepared a carboxyl group at the 1-position from unprotected N-acetyl-D-neuraminic acid by reacting N-acetyl-D-neuraminate with an alkyl halide. The present invention has been achieved by knowing that various N-acetyl-D-neuraminic acid ester derivatives in which various ester groups are introduced into the group can be efficiently obtained. Hereinafter, the present invention will be described in detail.
【0005】まず、N−アセチル−D−ノイラミン酸塩
は、水溶液中、N−アセチル−D−ノイラミン酸と当量
の無機塩基とを反応させ、濃縮、乾燥して得ることがで
きる。無機塩基としては周知のものを使用することがで
きる。例えば、炭酸水素リチウム、炭酸水素ナトリウ
ム、炭酸水素カリウム、炭酸セシウム、炭酸リチウム、
炭酸バリウム、炭酸マグネシウム、炭酸ナトリウム、炭
酸カリウム、炭酸ルビジウム、水酸化カリウム、水酸化
リチウム、水酸化ナトリウム、水酸化ルビジウム、水酸
化バリウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ
化カリウム、ヨウ化ルビジウム、フッ化リチウム、フッ
化ナトリウム、フッ化カリウム及び塩基性樹脂が挙げら
れる。反応温度は室温、反応時間は数分で十分である。First, N-acetyl-D-neuraminic acid salt can be obtained by reacting N-acetyl-D-neuraminic acid with an equivalent amount of an inorganic base in an aqueous solution, concentrating and drying. Well-known inorganic bases can be used. For example, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, lithium carbonate,
Barium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, potassium hydroxide, lithium hydroxide, sodium hydroxide, rubidium hydroxide, barium hydroxide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide , Lithium fluoride, sodium fluoride, potassium fluoride and basic resins. A reaction temperature of room temperature and a reaction time of several minutes are sufficient.
【0006】N−アセチル−D−ノイラミン酸塩をジメ
チルホルムアミド等の溶媒中、ハロゲン化アルキルと反
応させると収率良く目的の化合物であるN−アセチル−
D−ノイラミン酸エステルを容易に得ることができる。When N-acetyl-D-neuraminate is reacted with an alkyl halide in a solvent such as dimethylformamide, the desired compound, N-acetyl-, is obtained in good yield.
D-neuraminic acid ester can be easily obtained.
【0007】本発明の原料の一つとして利用されるハロ
ゲン化アルキルには、周知のハロゲン化アルキルを使用
することができる。例えば、臭化メチル、臭化エチル、
臭化プロピル、臭化オクチル、臭化アリル、臭化ベンジ
ル、及び臭化p−メトキシベンジル、ヨウ化メチル、ヨ
ウ化エチル、ヨウ化プロピル、ヨウ化オクチル、ヨウ化
アリル、ヨウ化ベンジル、及びヨウ化p−メトキシベン
ジル、塩化ベンジル、塩化p−メトキシベンジル、塩化
オクチル、塩化アリル等を挙げることができる。ハロゲ
ン化アルキル基の当量数は、当量から大過剰までの範囲
である。Well-known alkyl halides can be used as the alkyl halide used as one of the starting materials of the present invention. For example, methyl bromide, ethyl bromide,
Propyl bromide, octyl bromide, allyl bromide, benzyl bromide, and p-methoxybenzyl bromide, methyl iodide, ethyl iodide, propyl iodide, octyl iodide, allyl iodide, benzyl iodide, and iodo P-methoxybenzyl chloride, benzyl chloride, p-methoxybenzyl chloride, octyl chloride, allyl chloride and the like. The number of equivalents of the halogenated alkyl group ranges from the equivalent to a large excess.
【0008】有機溶媒は、ジメチルホルムアミド以外に
周知のものを使用することができる。例えば、塩化メチ
レン、クロロホルム、ベンゼン、トルエン、酢酸エチ
ル、ヘキサメチレンホスホリックトリアミド、アセトニ
トリル等を挙げることができる。As the organic solvent, known ones other than dimethylformamide can be used. For example, methylene chloride, chloroform, benzene, toluene, ethyl acetate, hexamethylenephosphoric triamide, acetonitrile and the like can be mentioned.
【0009】反応温度は特に制限はなく、通常0℃〜1
50℃、好ましくは、50℃〜120℃の範囲である。
反応時間も、数十分から数十時間、好ましくは1〜5時
間の範囲で、特に制限はない。また、N−アセチル−D
−ノイラミン酸塩とハロゲン化アルキルを反応させる際
に、18−クラウン−6等のクラウンエーテルを系内に
添加して反応を行うことができるのは言うまでもない。The reaction temperature is not particularly limited and is usually from 0 ° C to 1 ° C.
It is in the range of 50 ° C, preferably 50 ° C to 120 ° C.
The reaction time is also in the range of several tens of minutes to several tens of hours, preferably 1 to 5 hours, and there is no particular limitation. Also, N-acetyl-D
Needless to say, when the neuraminate and the alkyl halide are reacted, a crown ether such as 18-crown-6 can be added to the system to carry out the reaction.
【0010】以下に実施例を挙げて本発明を更に具体的
に説明するが、以下の実施例により何等制限を受けるも
のではない。Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
【0011】[0011]
【実施例1】N−アセチル−D−ノイラミン酸0.50
0g(1.6mmol)を水5mlとメタノール3ml
に溶解させ、炭酸セシウム0.260g(0.80mm
ol)を加え、室温で数分反応させた後に、溶媒を減圧
下、留去して固形物質を得た。これにジメチルホルムア
ミド8mlと臭化メチル0.10ml(1.7mmo
l)を加え、40℃で2時間30分反応させた後に、酸
性樹脂IRA−120を加えて、30分撹拌させた。濾
過後、有機溶媒を減圧下、留去させて油状物質を得た。
この化合物の構造確認のため、得られた油状物質に無水
酢酸15.8mlと60%過塩素酸0.12mlで調製
した混合溶液を1.6ml加え、室温で2時間30分反
応させた後に、この混合物を氷水にあけ、クロロホルム
で抽出を行い、有機層を飽和の塩化アンモニウム、塩化
ナトリウム水溶液で洗浄を行った。有機溶媒を無水硫酸
ナトリウムで乾燥させ、無機物をろ過後、有機溶媒を減
圧下、留去して得られる油状物質をシリカゲルカラムク
ロマトグラフィーで精製を行いメチル5−アセトアミド
−4,7,8,9−テトラ−O−アセチル−3,5−ジ
デオキシ−D−グリセロ−D−ガラクト−2−ノヌロピ
ラノースが0.460g(収率58%)得られた。1H
−NMR=3.85(3H,OCH3)Example 1 N-acetyl-D-neuraminic acid 0.50
0 g (1.6 mmol) of water 5 ml and methanol 3 ml
Dissolved in 0.260 g (0.80 mm) of cesium carbonate
ol) was added and the mixture was reacted at room temperature for several minutes, and then the solvent was distilled off under reduced pressure to obtain a solid substance. Add 8 ml of dimethylformamide and 0.10 ml of methyl bromide (1.7 mmo
1) was added and reacted at 40 ° C. for 2 hours and 30 minutes, then acidic resin IRA-120 was added and the mixture was stirred for 30 minutes. After filtration, the organic solvent was distilled off under reduced pressure to obtain an oily substance.
To confirm the structure of this compound, 1.6 ml of a mixed solution prepared with 15.8 ml of acetic anhydride and 0.12 ml of 60% perchloric acid was added to the obtained oily substance, and after reacting at room temperature for 2 hours and 30 minutes, The mixture was poured into ice water, extracted with chloroform, and the organic layer was washed with saturated aqueous ammonium chloride and sodium chloride solutions. The organic solvent is dried over anhydrous sodium sulfate, the inorganic matter is filtered off, the organic solvent is distilled off under reduced pressure, and the oily substance obtained is purified by silica gel column chromatography to obtain methyl 5-acetamide-4,7,8,9. 0.460 g (yield 58%) of -tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonuropyranose was obtained. 1 H
-NMR = 3.85 (3H, OCH 3 )
【0012】[0012]
【実施例2】N−アセチル−D−ノイラミン酸1.55
g(5.0mmol)を水15mlに溶解させ、炭酸セ
シウム0.816g(2.5mmol)を加え、室温で
数分反応させた後に、溶媒を減圧下、留去して固形物質
を得た。これにジメチルホルムアミド20mlと臭化ア
リル0.520ml(6.0mmol)を加え、60℃
で2時間30分反応させた後に、酸性樹脂IRA−12
0を加えて、30分撹拌させた。ろ過後、有機溶媒を減
圧下、留去させて油状物質を得た。この化合物の構造確
認のため、得られた油状物質に無水酢酸49.5mlと
60%過塩素酸水溶液0.37mlで調製した混合溶液
5.0mlを加え、室温で2時間30分反応させた後
に、この混合物を氷水にあけ、クロロホルムで抽出を行
い、有機層を飽和の塩化アンモニウム、塩化ナトリウム
水溶液で洗浄を行った。有機溶媒を無水硫酸ナトリウム
で乾燥させ、無機物をろ過後、有機溶媒を減圧下、留去
して得られる油状物質をシリカゲルカラムクロマトグラ
フィーで精製を行い、アリル5−アセトアミド−4,
7,8,9−テトラ−O−アセチル−3,5−ジデオキ
シ−D−グリセロ−D−ガラクト−2−ノヌロピラノー
スが1.475g(収率57%)得られた。1H−NM
R=2.021,2.025,2.098,2.142
(CH3COα),2.032,2.039,2.08
1,2.093(CH3COβ),5.886−5.9
84(1H、m),5.855(NHα),6.262
(NHβ),13C−NMR=35.94(C−3β),
36.06(C−3α),62.69(C−9α),6
3.63(C−9β),94.68(C−2β),9
4.93(C−2β)Example 2 N-acetyl-D-neuraminic acid 1.55
g (5.0 mmol) was dissolved in 15 ml of water, 0.816 g (2.5 mmol) of cesium carbonate was added, and after reacting at room temperature for several minutes, the solvent was distilled off under reduced pressure to obtain a solid substance. To this, 20 ml of dimethylformamide and 0.520 ml (6.0 mmol) of allyl bromide were added, and the mixture was heated at 60 ° C.
After reacting for 2 hours and 30 minutes, the acidic resin IRA-12
0 was added and the mixture was stirred for 30 minutes. After filtration, the organic solvent was distilled off under reduced pressure to obtain an oily substance. To confirm the structure of this compound, 5.0 ml of a mixed solution prepared by acetic anhydride 49.5 ml and 60% perchloric acid aqueous solution 0.37 ml was added to the obtained oily substance, and the mixture was reacted at room temperature for 2 hours and 30 minutes. The mixture was poured into ice water, extracted with chloroform, and the organic layer was washed with saturated ammonium chloride and sodium chloride aqueous solution. The organic solvent is dried over anhydrous sodium sulfate, the inorganic matter is filtered off, the organic solvent is evaporated under reduced pressure, and the oily substance obtained is purified by silica gel column chromatography to obtain allyl 5-acetamido-4,
1,475 g (yield 57%) of 7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonuropyranose was obtained. 1 H-NM
R = 2.021, 2.025, 2.098, 2.142
(CH 3 COα), 2.032, 2.039, 2.08
1,2.093 (CH 3 COβ), 5.886-5.9
84 ( 1 H, m), 5.855 (NHα), 6.262
(NHβ), 13 C-NMR = 35.94 (C-3β),
36.06 (C-3α), 62.69 (C-9α), 6
3.63 (C-9β), 94.68 (C-2β), 9
4.93 (C-2β)
【0013】[0013]
【実施例3】N−アセチル−D−ノイラミン酸1.54
g(5.0mmol)を水15mlに溶解させ、炭酸セ
シウム0.819g(2.5mmol)を加え、室温で
数分反応させた後に、溶媒を減圧下、留去して固形物質
を得た。これにジメチルホルムアミド20mlと臭化ベ
ンジル0.720ml(6.0mol)を加え、80℃
で2時間30分反応させた後に、酸性樹脂IRA−12
0を加えて、30分撹拌させた。ろ過後、有機溶媒を減
圧下、留去させて油状物質を得た。この化合物の構造確
認のため、得られた油状物質に無水酢酸53.2mlと
60%過塩素酸水溶液0.37mlで調製した混合溶液
5.4mlを加え、室温で2時間30分反応させた後
に、この混合物を氷水にあけ、クロロホルムで抽出を行
い、有機層を飽和の塩化アンモニウム、塩化ナトリウム
水溶液で洗浄を行った。有機溶媒を無水硫酸ナトリウム
で乾燥させ、無機物をろ過後、有機溶媒を減圧下、留去
して得られる油状物質をシリカゲルカラムクロマトグラ
フィーで精製を行い、ベンジル 5−アセトアミド−
4,7,8,9−テトラ−O−アセチル−3,5−ジデ
オキシ−D−グリセロ−D−ガラクト−2−ノヌロピラ
ノースが1.362g(収率48%)得られた。1H−
NMR=1.890,1.971,2.002,2.0
14,2.021,2.045,2.063,2.06
7,2.069,2.135(CH3COα及びβ),
6.100,6.376(NHα及びβ),13C−NM
R=35.90(C−3β),36.06(C−3
α),62.60(C−9α),63.55(C−9
β),94.77(C−2β),95.02(C−2
α)Example 3 N-Acetyl-D-neuraminic acid 1.54
g (5.0 mmol) was dissolved in 15 ml of water, 0.819 g (2.5 mmol) of cesium carbonate was added, and after reacting at room temperature for several minutes, the solvent was distilled off under reduced pressure to obtain a solid substance. To this, 20 ml of dimethylformamide and 0.720 ml (6.0 mol) of benzyl bromide were added, and the temperature was adjusted to 80 ° C.
After reacting for 2 hours and 30 minutes, the acidic resin IRA-12
0 was added and the mixture was stirred for 30 minutes. After filtration, the organic solvent was distilled off under reduced pressure to obtain an oily substance. To confirm the structure of this compound, to the obtained oily substance was added 53.2 ml of acetic anhydride and 5.4 ml of a mixed solution of 0.37 ml of 60% aqueous perchloric acid, and the mixture was reacted at room temperature for 2 hours and 30 minutes. The mixture was poured into ice water, extracted with chloroform, and the organic layer was washed with saturated ammonium chloride and sodium chloride aqueous solution. The organic solvent is dried over anhydrous sodium sulfate, the inorganic matter is filtered off, the organic solvent is evaporated under reduced pressure, and the resulting oily substance is purified by silica gel column chromatography to obtain benzyl 5-acetamide-
1.362 g (yield 48%) of 4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranose was obtained. 1 H-
NMR = 1.890, 1.971, 2.002, 2.0
14, 2.021, 2.045, 2.063, 2.06
7, 2.069, 2.135 (CH 3 CO α and β),
6.100, 6.376 (NH α and β), 13 C-NM
R = 35.90 (C-3β), 36.06 (C-3
α), 62.60 (C-9α), 63.55 (C-9
β), 94.77 (C-2β), 95.02 (C-2
α)
【0014】[0014]
【発明の効果】以上のように、本発明によれば無保護の
N−アセチル−D−ノイラミン酸から容易にN−アセチ
ル−D−ノイラミン酸エステル誘導体を製造することが
できる。これらエステル誘導体は、医薬品、農薬、化粧
品、試薬類で重要な合成中間体となる。As described above, according to the present invention, an N-acetyl-D-neuraminic acid ester derivative can be easily produced from unprotected N-acetyl-D-neuraminic acid. These ester derivatives are important synthetic intermediates in pharmaceuticals, agricultural chemicals, cosmetics and reagents.
Claims (7)
アルケニル基、アラルキル基、R2は水素、アシル基を
示す。)で表わされるN−アセチル−D−ノイラミン酸
エステル誘導体。[Claim 1] Formula 1 (wherein R 1 is an alkyl group having 2 to 10 carbon atoms,
An alkenyl group, an aralkyl group and R 2 represent hydrogen and an acyl group. ) N-acetyl-D-neuraminic acid ester derivative represented by
ル基を示す。)で表わされる請求項1記載のN−アセチ
ル−D−ノイラミン酸エステル誘導体。## STR2 ## The N-acetyl-D-neuraminic acid ester derivative according to claim 1, which is represented by Formula 2 (wherein All represents an allyl group and R represents hydrogen or an acetyl group).
ル基を示す。)で表わされる請求項1記載のN−アセチ
ル−D−ノイラミン酸エステル誘導体。(3) The N-acetyl-D-neuraminic acid ester derivative according to claim 1, which is represented by Formula 3 (wherein Bn represents a benzyl group, R represents hydrogen or an acetyl group).
で表わされるN−アセチル−D−ノイラミン酸塩とハロ
ゲン化アルキルとを反応させることを特徴とする、一般
式化1(式中R1は炭素数2〜10のアルキル基、アル
ケニル基、アラルキル基、R2は水素、アシル基を示
す。)で表わされるN−アセチル−D−ノイラミン酸エ
ステル誘導体の製造法。(4) Formula 4 in which a hydroxyl group is free (wherein X represents a metal ion)
Wherein N-acetyl-D-neuraminate represented by the formula and an alkyl halide are reacted, wherein R 1 is an alkyl group having 2 to 10 carbon atoms, an alkenyl group or an aralkyl group. , R 2 represents hydrogen or an acyl group), and a method for producing an N-acetyl-D-neuraminic acid ester derivative.
を特徴とする請求項4記載の製造法。5. The method according to claim 4, wherein the reaction is carried out in dimethylformamide.
項4記載の製造法。6. The method according to claim 4, wherein the reaction is performed by heating.
て、セシウム塩を用いることを特徴とする請求項4記載
の製造法。7. The method according to claim 4, wherein a cesium salt is used as the N-acetyl-D-neuraminate.
Priority Applications (1)
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JP8069696A JPH09249683A (en) | 1996-03-09 | 1996-03-09 | N-actyl-d-neuraminic acid derivaitive and its production |
Applications Claiming Priority (1)
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JP8069696A JPH09249683A (en) | 1996-03-09 | 1996-03-09 | N-actyl-d-neuraminic acid derivaitive and its production |
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Family
ID=13725502
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180591B1 (en) * | 1996-09-30 | 2001-01-30 | Clariant Gmbh | Use of N-(3-dialkylamino) propyl-N-polyhydroxyalkylcarboxamides and their acid adducts as thickeners for liquid aqueous surfactant systems |
US6437150B1 (en) | 1998-04-20 | 2002-08-20 | Givaudan Sa | Compounds having protected hydroxy groups |
US6479682B1 (en) | 1998-04-20 | 2002-11-12 | Givaudan Sa | Compounds having protected hydroxy groups |
-
1996
- 1996-03-09 JP JP8069696A patent/JPH09249683A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180591B1 (en) * | 1996-09-30 | 2001-01-30 | Clariant Gmbh | Use of N-(3-dialkylamino) propyl-N-polyhydroxyalkylcarboxamides and their acid adducts as thickeners for liquid aqueous surfactant systems |
US6437150B1 (en) | 1998-04-20 | 2002-08-20 | Givaudan Sa | Compounds having protected hydroxy groups |
US6479682B1 (en) | 1998-04-20 | 2002-11-12 | Givaudan Sa | Compounds having protected hydroxy groups |
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