JPS6023397A - Production of 3',5'-disubstituted-2'-deoxy-5-fluorouridine compound - Google Patents
Production of 3',5'-disubstituted-2'-deoxy-5-fluorouridine compoundInfo
- Publication number
- JPS6023397A JPS6023397A JP58130755A JP13075583A JPS6023397A JP S6023397 A JPS6023397 A JP S6023397A JP 58130755 A JP58130755 A JP 58130755A JP 13075583 A JP13075583 A JP 13075583A JP S6023397 A JPS6023397 A JP S6023397A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- disubstituted
- deoxy
- fluorouridines
- group
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は３’、 ５’−ジ画換−２１−デオキシー５−
フルオロウリジン類の製造法ＫＩＡする。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 3', 5'-di-fractionated-21-deoxy-5-
KIA production method for fluorouridines.
２′−デオキシ−５−フルオロウリジンは代謝拮抗型の
制癌剤であり１強力な制癌活性を有することが知られて
いる。従って２′−デオキシ−５−フルオロウリジンな
らびにその誘導体の制癌作用に関しては多くの報告があ
る〔例えば、 ３−
Ｃａｎｃｅｒ Ｃ１＋ｅｍｏｔｈｅｒ、 Ｐｈａｒｍａ
ｅｏｌ、 ＋ヱ、１９ （１９８］）参照〕。一方、２
’−チオキシ−５−フルオロウリジンの合成に関しても
多くの報告があるが、これらは次の３種類に大別するこ
とが出来る。2'-deoxy-5-fluorouridine is an antimetabolite anticancer agent and is known to have strong anticancer activity. Therefore, there are many reports regarding the anticancer effects of 2'-deoxy-5-fluorouridine and its derivatives [for example, 3-Cancer C1+mother, Pharma
eol, +e, 19 (198])]. On the other hand, 2
There are also many reports regarding the synthesis of '-thioxy-5-fluorouridine, but these can be roughly classified into the following three types.
１）２′−デオキシウリジン類をフッ素化する力木法に
よれば、２′−デオキシウリジン又は保護された２′−
デオキシウリジンをフッ素を用いてフッ素化することに
よって、保護基を有する場合には更に保護基を除去する
ことによって２′−デオキシ−５−フルオロウ’） ）
ｙが得られる。しかしながら水沫は、危険なフッ素ガ
スを使用すること、原料となる２′−デオキシウリジン
が高価であることから、収率 ４−
はよいが実験室的にも工業的にも一般的とは言えない〔
例えば、Ｊ、 Ｐｒａｋｔ、 Ｃｈｅｍ、、 ３１５．
１゜１４９ （１９７３） ： Ｃｏ１１ｅｃｔ、 Ｃ
ｚｅｃｈ、 Ｃｈｅｍ、 Ｃｏｍｙｎｕｎ、＋−リー、
３２１７ （１９８ｆｌ） ）。1) According to the strength tree method of fluorinating 2'-deoxyuridines, 2'-deoxyuridine or protected 2'-
By fluorinating deoxyuridine with fluorine, and if it has a protecting group, by further removing the protecting group, 2'-deoxy-5-fluoro'))
y is obtained. However, since water droplets use dangerous fluorine gas and the raw material 2'-deoxyuridine is expensive, although the yield is good, it is not common in both the laboratory and industry. [
For example, J. Prakt. Chem., 315.
1°149 (1973): Co11ect, C
zech, Chem, Comynun, +-Lee,
3217 (198fl)).
２）５−フルオロウリジンの２′−水酸基を還元的に除
去する方法
ルオロウリジンも高価である〔例えば、Ｃｏ１１ｅｃｔ
、 Ｃｚｅｃｈ、 Ｃｈｅｍ、 Ｃｏｍｍｕｎ、 １４
４．４３９（１９７９）；Ｂｕｌｌ、 Ｃｈｅｍ、 Ｓ
ｏｃ、 Ｊａｐａｎ 、 ５０．２１９７ （１９７７
） ）。2) Method for reductively removing the 2'-hydroxyl group of 5-fluorouridine Fluorouridine is also expensive [for example, Co11ect
, Czech, Chem, Commun, 14
4.439 (1979); Bull, Chem, S.
oc, Japan, 50.2197 (1977
) ).
３）２−デオキシリメフラノシルハライド類と５−フル
オロウリンル類との縮合
５−
不法目、一般にα体とβ体の２種類の生成物がほぼ等訃
生成し目的とするβ体の収率は１０〜６０％である〔例
えば、Ｊ ６Ｍｅ ｄ −Ｃｈ ｅ ｍ 、＋１、５６
６ （１９６６） ；スイス特許、第５００２０３号。3) Condensation of 2-deoxylimefuranosyl halides and 5-fluorourinyl 5-Illegal products, generally two types of products, α-form and β-form, are produced almost equally, and it is difficult to obtain the desired β-form. The rate is 10-60% [e.g. J6Med-Chem, +1,56
6 (1966); Swiss Patent No. 500203.
Ｊ、 Ｏｒｇ、 Ｃｈｅｍ、 、土９．３６５４ （１
９７４） ）。J, Org, Chem, , Sat 9.3654 (1
974) ).
本発明者等は、前記の方法３）が比較的工程も短く危険
性も少ないことに着目し、縮合反応の条件を種々検討し
た。The present inventors focused on the fact that method 3) described above involves relatively short steps and little risk, and studied various conditions for the condensation reaction.
既Ｋ Ｍ、 Ｐ、 Ｋｏｔｉｃｋ等が、３，５−ジ置換
−２−デオキシ−α−Ｄ−リボフラノシルハライドと５
−フルオロウラシル誘導体を緩和が条件下でＳＮ、型の
縮合反応を行えば、目的とするβ体の収率が向上するこ
とを示唆している（ Ｊ、 Ｏｒｇ。KM, P., Kotick et al. reported that 3,5-disubstituted-2-deoxy-α-D-ribofuranosyl halides and 5
It has been suggested that if the SN-type condensation reaction is carried out under conditions where the -fluorouracil derivative is relaxed, the yield of the desired β-isomer can be improved (J, Org.
Ｃｈｅｍ−ｒ土４．３８０６ （１９６９） 〕。そこ
で１本発明 ６−
者らけ、効率よ（ＳＮ、型反応を進行させるためには核
試薬５−Ｆｕ誘導体を活性化することが必要と考え、種
々の添加剤の存在下でＦ記の縮合反応を行った結果、本
発明に到達したものである。Chem-r soil 4.3806 (1969)]. Therefore, we believe that it is necessary to activate the nuclear reagent 5-Fu derivative in order to promote the efficiency (SN, type reaction), and in the presence of various additives, we The present invention was achieved as a result of conducting a condensation reaction.
すなわち、本発明は下記式（Ｔ）
で表わされる３、５−−）＠換−２−デオギシリボフラ
ノシルハライドと、
下記式（Ｔｌ）
〔式中、Ｒ２は有機シリル基を表わす〕で表わされる５
−フルオロピリミジン誘導体をフッ化物の存在下に縮合
反応させることからなる。That is, the present invention relates to a 3,5--)@substituted-2-deogysilibofuranosyl halide represented by the following formula (T), and a 3,5--)@substituted-2-deogysilibofuranosyl halide represented by the following formula (Tl) [wherein R2 represents an organic silyl group]. 5 represented
- It consists of subjecting a fluoropyrimidine derivative to a condensation reaction in the presence of fluoride.
〔式中、Ｒ１は前記定義と同じ〕
で表わされる３’、５’−ジ置換−２−チオキシ−５＝
フルオロウリジン類の製造法である。[In the formula, R1 is the same as defined above] 3',5'-disubstituted-2-thioxy-5=
This is a method for producing fluorouridines.
本発明において用いられる前記式（１）で表わされる３
、５−ジ置換−２−デオキシリボフラノシルハライドは
、いかなる方法で製造してもかまわないが１例えば、Ｄ
−リボースより３工程で２−デオキシ−３，５−ジー０
−（パルクロルベンゾイル）−α−Ｄ−リボフラノシル
クロライドを製造することができる（ Ｊ、 Ｏｒｇ、
Ｃｈｅｍ、。3 represented by the above formula (1) used in the present invention
, 5-disubstituted-2-deoxyribofuranosyl halide may be produced by any method; for example, D
- 2-deoxy-3,5-di0 in 3 steps from ribose
-(parchlorobenzoyl)-α-D-ribofuranosyl chloride can be produced (J, Org,
Chem.
３４ 、３８０６ （１９６９）参照〕。34, 3806 (1969)].
本発明において用いられる前記式（Ｔｒ）で表わされる
５−フルオロウラシル誘導体は、いかなる方法で製造し
てもかまわないが、例えば５−フルオロウラシルとへキ
サメチルジシラザン、あるいは５−フルオロウラシルと
トリメチルクロルシラ／及びトリエチルアミンの反応に
より容易に製造することが出来る（ Ｃｈｅｍ 、 Ｐ
Ｉ＋ａｒｍ 。The 5-fluorouracil derivative represented by the formula (Tr) used in the present invention may be produced by any method, but for example, 5-fluorouracil and hexamethyldisilazane, or 5-fluorouracil and trimethylchlorosila/ and triethylamine (Chem, P
I+arm.
Ｂｕｌｌ、 、 ２６．２９９０ （１９７ｆｌ）参照
〕。See Bull, 26.2990 (197fl)].
前記式日〕中、Ｒ１はアルコールの保護基を表わす。保
護基と１７ては通常用いられているいかなるものでもか
まわないが１例えばアセチル基。In the formula above, R1 represents an alcohol protecting group. The protecting group 17 may be any commonly used group, such as an acetyl group.
グロビオニル基、ブタノイル基等の脂肪族アシル基、ヘ
ンジイル基、ｐ−ニトロベンゾイル基。Aliphatic acyl groups such as globionyl group and butanoyl group, hendiyl group, p-nitrobenzoyl group.
ｐ−メトキシベンゾイル基、ｐ−クロルベンゾイル基、
Ｐ−ブロモペンソイル基、ｏ−クロロベンゾイル基＋ｍ
−クロロベンゾイル基等の置換又は非置換の芳香族アシ
ル基、ベンジル基。p-methoxybenzoyl group, p-chlorobenzoyl group,
P-bromopenzoyl group, o-chlorobenzoyl group +m
- Substituted or unsubstituted aromatic acyl group such as chlorobenzoyl group, benzyl group.
、−クロルベンジル基、トリチル基、モノメトキシトリ
チル基搾のアラルキル基を挙げるこλが出来るが、これ
に限定されるものではない。, -chlorobenzyl group, trityl group, monomethoxytrityl group, and other aralkyl groups can be mentioned, but the present invention is not limited thereto.
前記式（１）中、Ｘはハロゲン原子を表わし。In the formula (1), X represents a halogen atom.
具体的にけフッ素原子、塩素原子、臭素原子等を表わす
。Specifically, it represents a fluorine atom, a chlorine atom, a bromine atom, etc.
前記式［Ｔｒ）中、Ｒ″は有機シリル基を表わす。In the formula [Tr), R'' represents an organic silyl group.
有機シリル基としては通常アルコール等の保護 ９ −
基として用いられるものならばいかなるものでもかまわ
ないが、例えば、トリメチルシリル基。The organic silyl group may be any group that is normally used as a protective 9- group in alcohols, for example, a trimethylsilyl group.
ｔ−ブチルジメチルシリル基等を挙げることが出来る。Examples include t-butyldimethylsilyl group.
本発明において添加剤として用いられるフッ化物は、前
記式（ＩＩ）で表わされる５−フルオロピリミジン誘導
体を活性化し、前記式〔１）で表わされる３、５−ジ置
換−２−デオキシリボフラノシルハライドと緩和な条件
下でＳＮ２型の反応を促進させるために加えられる。添
加剤として加えるフッ化物の具体例を挙げると、例えば
。The fluoride used as an additive in the present invention activates the 5-fluoropyrimidine derivative represented by the above formula (II), and activates the 3,5-disubstituted-2-deoxyribofuranosyl halide represented by the above formula [1]. is added to promote the SN2 type reaction under mild conditions. Specific examples of fluorides added as additives include:
フッ化リチウム、フッ化すｌ・リウム、フッ化カリウム
、フッ化セシウム等のフッ化アルカリ金！Ｒ，フフ化マ
グネシウム、フッ化カルシウム。Alkali gold fluorides such as lithium fluoride, sulfur fluoride, potassium fluoride, and cesium fluoride! R, magnesium fluoride, calcium fluoride.
フッ化パリリウム、フッ化バリウム等のフッ化アルカリ
土類金属、フッ化第１銅、フッ化第２銅、フッ化ニッケ
ル、フッ化コバルト、フッ化銀等のフッ化遷移金属、フ
ッ化テトラブチルアンモニウム、フッ化ピリジニウム、
フッ化アンモニウム等のフッ化アンモニウム類がある。Alkaline earth metal fluorides such as paryllium fluoride and barium fluoride, transition metal fluorides such as cuprous fluoride, cupric fluoride, nickel fluoride, cobalt fluoride, and silver fluoride, tetrabutyl fluoride ammonium, pyridinium fluoride,
There are ammonium fluorides such as ammonium fluoride.
ｌＯ−
本発明において用いられる溶媒は、反応に影響を力えな
いことが望ましく１例えば、ヘキサン、ベンゼン、トル
エン、四塩化炭素、クロロホルム、ジクロルメタン、ジ
クロルエタン、テトラクロルエタン、アセトニトリル、
酢２エチル、アセトン、テトラヒドロフラン、ジオキ
サン、ジメトキシエタンが挙げられる。It is desirable that the solvent used in the present invention does not affect the reaction. Examples include hexane, benzene, toluene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, tetrachloroethane, acetonitrile,
Examples include diethyl acetate, acetone, tetrahydrofuran, dioxane, and dimethoxyethane.
反応温度は、用いる添加剤により異なるが、−７８”Ｃ
から１５０℃の間で行なわれ、特ＫＯ℃〜８０℃にて行
なうことが好ましい。反応時間は条件によって異なるが
１通常４８時間以内に終了する。添加剤として加えるフ
ッ化物の量は０．０１〜３０当量、さらＫｆｆましくは
０．】〜１０当量程度である。また、前記式（１）で表
わされる３、５−ジ置換−２−デオキシリボフラノシル
ハライドと前記式〔■（〕で表わされる５−フルオロピ
リミジン誘導体のモル比は通常約１：１で反応を行うが
、適宜１ ： ０．７から１ ： １．５程度で反応し
てもかまわ々い。The reaction temperature varies depending on the additives used, but is -78"C
to 150°C, and preferably at KO to 80°C. The reaction time varies depending on the conditions, but it is usually completed within 48 hours. The amount of fluoride added as an additive is 0.01 to 30 equivalents, preferably Kff or 0.01 to 30 equivalents. ] ~10 equivalents. Further, the molar ratio of the 3,5-disubstituted-2-deoxyribofuranosyl halide represented by the above formula (1) and the 5-fluoropyrimidine derivative represented by the above formula [■(]) is usually about 1:1 for the reaction. However, the reaction may be carried out at a ratio of about 1:0.7 to 1:1.5 as appropriate.
かくして得られた前記式（ｎｔ）で表わされる３、’
、５’−ジ置換−２′−デオキシ−５−フルオロウリジ
ン類は、通常の単離操作、すなわち抽出。The thus obtained 3,' expressed by the above formula (nt)
, 5'-disubstituted-2'-deoxy-5-fluorouridines can be obtained by conventional isolation procedures, namely extraction.
再結晶、カラムクロマトグラフィー、高速液体クロマド
グ２フイー等を適宜組み合せて実施することにより嚇離
することか出来る。The separation can be achieved by appropriately combining recrystallization, column chromatography, high performance liquid chromatography, etc.
以下、実施例を挙げて本発明を詳述する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
３．５−ビス−〇−（ｐ−クロロベンゾイル）−２′−
デオキシ−α−Ｄ−リボフラノシルクロライド２，１３
９ （５，０ｍｍｏｌｅ ）と、２．４−ビストリメチ
ルシリルオキシ−５−フルオロピリミジ７１．５１１
（５，５ｍｍｏｌｅ）を、２５ｍ１の塩化メチレンに懸
濁し、フッ化セシウム２３ＣＩＩ＆（１，５ｍｍｏｌｅ
）を加え室温で２０時間攪拌した。これに水と塩化メ
チレンを加えて生成物を抽出した。Example 1 3.5-bis-〇-(p-chlorobenzoyl)-2'-
Deoxy-α-D-ribofuranosyl chloride 2,13
9 (5,0 mmole) and 2,4-bistrimethylsilyloxy-5-fluoropyrimidine 71.511
(5,5 mmole) was suspended in 25 ml of methylene chloride, and cesium fluoride 23CII&(1,5 mmole) was suspended in 25 ml of methylene chloride.
) and stirred at room temperature for 20 hours. Water and methylene chloride were added to this to extract the product.
有機層を水洗後、無水硫酸マグネシウムにて乾燥し、濃
縮した。得られた粗結晶を酢酸にて再結晶して、 ３’
、 ５’−ビス−ｏ−（ｐ−クロロベンゾイル）−５−
フルオロ−２′−デオキシ−β−ウリジン１．８１１７
を得た。収率は６９．２％であった。The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated. The obtained crude crystals were recrystallized from acetic acid to obtain 3'
, 5'-bis-o-(p-chlorobenzoyl)-5-
Fluoro-2'-deoxy-β-uridine 1.8117
I got it. The yield was 69.2%.
融点 ２０４〜５℃
実施例２〜１４
実施例１と同様の反応スケールにて、添加剤の種類と反
応条件を変えて検討した結果を第１表にまとめて示した
。Melting point: 204-5°C Examples 2-14 Table 1 summarizes the results of studies conducted on the same reaction scale as in Example 1, with different types of additives and reaction conditions.
１３− 第 １ 表 特許出願人 帝人株式会社 １４−13- Table 1 Patent applicant Teijin Ltd. 14-
Claims (1)
シルハライドと。 下記式（ＩＴ） 〔式中、Ｒ２は有機シリル基を表わす〕で表わされる５
−フルオロピリミジン誘導体をフッ化物の存在下に縮合
反応させることからなる、 〔式中、Ｒ１は前記定義と同じ〕 で表わされる３’、 ５’−ジ置換−２′−デオキシ−
５−フルオロウリジン類の製造法。 ２、前記式（Ｔ）中Ｒ１がアシル基である。特許請求の
範囲第１項記載の３１． ｓｌ−ジ置換−２′−デオキ
シ−５−フルオロウリジン類の製造法。 ３、アシル基が置換又は非置換のベンゾイル基である。 ＠許請求の範囲第２項記載の３’、５’ −ジ置換−２
′−デオキシ−５−フルオロウリジン類の製造法。 ４、前記式（ｎ）中、Ｒ２がトリメチルシリル基である
。特許請求の範囲第１項記載の３’、 ５’−ジｆｉｆ
ｆ、 換−２’−デオキシ−５−フルオロウリジン類の
製造法。 ５、フッ化物がアルカリ金属イオン、アルカリ土類金属
イオン、遷移金属イオン、アンモニウムイオンとフッ素
イオンの塩である１％許悄求の範囲第１項記載の３’、
５’−ジ置換−２′−デオキシ−５−フルオロウリジ
ン類の製造法。 ６、フッ化物がフッ化リチウム、フッ化ナトリウム、フ
ッ化カリウム、フッ化セシウム、フッ化カルシウム、フ
ッ化第二銅、フッ化テトラプ千ルアンモニウム、フッ化
ピリジニウムのいずれかである、特許請求の範囲第５項
記載の３１．５１−ジ置換−２′−デオキシ−５−フル
オロウリジン類の製造法。[Claims] 1. A 3,5-disubstituted-2-deoxyribofuranosyl halide represented by the following formula (I): A 3,5-disubstituted-2-deoxyribofuranosyl halide represented by the following formula (IT) [wherein R2 represents an organic silyl group] 5
3', 5'-disubstituted-2'-deoxy-, which is obtained by subjecting a fluoropyrimidine derivative to a condensation reaction in the presence of a fluoride, [wherein R1 is the same as defined above]
Method for producing 5-fluorouridines. 2. In the above formula (T), R1 is an acyl group. 31. of claim 1. A method for producing sl-disubstituted-2'-deoxy-5-fluorouridines. 3. The acyl group is a substituted or unsubstituted benzoyl group. @3',5'-disubstituted-2 according to claim 2
Method for producing '-deoxy-5-fluorouridines. 4. In the above formula (n), R2 is a trimethylsilyl group. 3', 5'-di fif according to claim 1
f. Method for producing substituted-2'-deoxy-5-fluorouridines. 5. 3' according to item 1, in which the fluoride is a salt of an alkali metal ion, an alkaline earth metal ion, a transition metal ion, an ammonium ion and a fluorine ion, within the range of 1% tolerance;
A method for producing 5'-disubstituted-2'-deoxy-5-fluorouridines. 6. A patent claim in which the fluoride is any of lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, calcium fluoride, cupric fluoride, tetrachlorammonium fluoride, and pyridinium fluoride. A process for producing 31.51-disubstituted-2'-deoxy-5-fluorouridines according to Scope 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58130755A JPS6023397A (en) | 1983-07-20 | 1983-07-20 | Production of 3',5'-disubstituted-2'-deoxy-5-fluorouridine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58130755A JPS6023397A (en) | 1983-07-20 | 1983-07-20 | Production of 3',5'-disubstituted-2'-deoxy-5-fluorouridine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6023397A true JPS6023397A (en) | 1985-02-05 |
| JPH027595B2 JPH027595B2 (en) | 1990-02-19 |
Family
ID=15041870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58130755A Granted JPS6023397A (en) | 1983-07-20 | 1983-07-20 | Production of 3',5'-disubstituted-2'-deoxy-5-fluorouridine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6023397A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6371463A (en) * | 1986-09-16 | 1988-03-31 | Mk Seiko Co Ltd | Car washing machine |
| US5532349A (en) * | 1993-07-20 | 1996-07-02 | Mitsui Toatsu Chemicals, Inc. | Process for producing 1-(2'-deoxy-β-D-erythro-pentofuranosyl)-5-trifluoromethyluracil derivatives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54151987A (en) * | 1978-05-17 | 1979-11-29 | Toyama Chem Co Ltd | Preparation of 3',5'-disubstituted-2'-deoxy-beta-uridines and 2'-deoxy-beta-urdines |
-
1983
- 1983-07-20 JP JP58130755A patent/JPS6023397A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54151987A (en) * | 1978-05-17 | 1979-11-29 | Toyama Chem Co Ltd | Preparation of 3',5'-disubstituted-2'-deoxy-beta-uridines and 2'-deoxy-beta-urdines |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6371463A (en) * | 1986-09-16 | 1988-03-31 | Mk Seiko Co Ltd | Car washing machine |
| JPH0510260B2 (en) * | 1986-09-16 | 1993-02-09 | Mk Seiko Co Ltd | |
| US5532349A (en) * | 1993-07-20 | 1996-07-02 | Mitsui Toatsu Chemicals, Inc. | Process for producing 1-(2'-deoxy-β-D-erythro-pentofuranosyl)-5-trifluoromethyluracil derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH027595B2 (en) | 1990-02-19 |
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