JPS6365076B2 - - Google Patents
Info
- Publication number
- JPS6365076B2 JPS6365076B2 JP9970881A JP9970881A JPS6365076B2 JP S6365076 B2 JPS6365076 B2 JP S6365076B2 JP 9970881 A JP9970881 A JP 9970881A JP 9970881 A JP9970881 A JP 9970881A JP S6365076 B2 JPS6365076 B2 JP S6365076B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- nitrophenyl
- hydrogen atom
- substituent
- 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.)
- Expired
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- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- LHBLJWULWKQRON-UHFFFAOYSA-N (2-nitrophenyl) selenocyanate Chemical compound [O-][N+](=O)C1=CC=CC=C1[Se]C#N LHBLJWULWKQRON-UHFFFAOYSA-N 0.000 claims description 5
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003230 pyrimidines Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000003835 nucleoside group Chemical group 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003212 purines Chemical class 0.000 description 3
- 239000002126 C01EB10 - Adenosine Substances 0.000 description 2
- IQFYYKKMVGJFEH-XLPZGREQSA-N Thymidine Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 IQFYYKKMVGJFEH-XLPZGREQSA-N 0.000 description 2
- DRTQHJPVMGBUCF-XVFCMESISA-N Uridine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-XVFCMESISA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229960005305 adenosine Drugs 0.000 description 2
- 150000003838 adenosines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000002777 nucleoside Substances 0.000 description 2
- 150000003833 nucleoside derivatives Chemical class 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- -1 2-nitrophenylseleno group Chemical group 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- DWRXFEITVBNRMK-UHFFFAOYSA-N Beta-D-1-Arabinofuranosylthymine Natural products O=C1NC(=O)C(C)=CN1C1C(O)C(O)C(CO)O1 DWRXFEITVBNRMK-UHFFFAOYSA-N 0.000 description 1
- UZSSGAOAYPICBZ-SOCHQFKDSA-N Decoyinine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@]1(CO)OC(=C)[C@@H](O)[C@H]1O UZSSGAOAYPICBZ-SOCHQFKDSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- UZSSGAOAYPICBZ-UHFFFAOYSA-N angustmycin A Natural products C1=NC=2C(N)=NC=NC=2N1C1(CO)OC(=C)C(O)C1O UZSSGAOAYPICBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- IQFYYKKMVGJFEH-UHFFFAOYSA-N beta-L-thymidine Natural products O=C1NC(=O)C(C)=CN1C1OC(CO)C(O)C1 IQFYYKKMVGJFEH-UHFFFAOYSA-N 0.000 description 1
- DRTQHJPVMGBUCF-PSQAKQOGSA-N beta-L-uridine Natural products O[C@H]1[C@@H](O)[C@H](CO)O[C@@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-PSQAKQOGSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940104230 thymidine Drugs 0.000 description 1
- DRTQHJPVMGBUCF-UHFFFAOYSA-N uracil arabinoside Natural products OC1C(O)C(CO)OC1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-UHFFFAOYSA-N 0.000 description 1
- 229940045145 uridine Drugs 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Description
本発明は5′−Se−（２−ニトロフエニル）セレ
ノヌクレオシドに関する。更に詳しくは
一般式
（式中、Ｒは水素原子または水酸基を示し、Ｂは
The present invention relates to 5'-Se-(2-nitrophenyl)selenonucleosides. For more details, see General formula (In the formula, R represents a hydrogen atom or a hydroxyl group, and B represents
【式】で表わされる２−、６−、８
−位に置換基を有することもあるプリン核、また
はA purine nucleus that may have substituents at the 2-, 6-, or 8-positions, or
【式】で表わされる２−、５−、６−位
に置換基を有することもあるピリミジン核を示
す）
で表わされる5′−Se−（２−ニトロフエニル）セ
レノヌクレオシドおよびその合成法に関するもの
である。
本発明による一般式（）で示される新規な
5′−Se−（２−ニトロフエニル）セレノヌクレオ
シドは4′，5′−不飽和ヌクレオシドに対し有用な
試薬となることを見出した。例えば4′，5′−不飽
和アデノシンはnucleocidineやAngustmycinAの
重要な合成中間体でありこれら化合物は強力なト
リパノゾーマ剤、抗菌作用、抗微生物性を有する
ことが既に知られている。また4′，5′−不飽和ア
デノシンはI.D.Jenkins、J.P.H.Verheyden、J.G.
Moffat；J.Amer.Chem.Soc.、93、4323（1971）；
E.J.Prisbe、J.Smejkal、J.P.H.Verheyden、J.G.
Moffat；J.Org.Chem.、41、1836（1976）等で公
知である。しかしこれらの方法ではアデノシンの
塩基および糖部を保護する必要があり副反応とし
て環化反応などが起こりその収率も好ましくな
い。このことは他の4′，5′−不飽和ヌクレオシド
においても同様な問題を包含しておりそれ故、こ
れらの解決法が要望されていた。
これに対し本発明の一般式（）で示される
5′−Se−（２−ニトロフエニル）セレノヌクレオ
シドを原料とする新合成法は、上記の欠点を解消
し容易に高収率で4′，5′−不飽和ヌクレオシドを
得ることができる。すなわち5′−Se−（２−ニト
ロフエニル）セレノヌクレオシドに過酸化水素水
を作用させ、得られたセレノオキシド誘導体を第
三アミンと反応させることによる4′，5′−不飽和
ヌクレオシドの合成法である。本発明は上記の
4′，5′−不飽和ヌクレオシドのすぐれた出発試薬
である一般式（）で示される5′−Se−（２−ニ
トロフエニル）セレノヌクレオシドおよびその合
成法の提供である。
本発明の5′−Se−（２−ニトロフエニル）セレ
ノヌクレオシド（）はヌクレオシドの5′−水酸
基に選択的に２−ニトロフエニルセレノ基を導入
する方法により得られる。すなわち、下記の反応
式により示される。
（式中、ＲおよびＢは前記定義と同様である）
ヌクレオシドに対し好ましくは３当量の２−ニ
トロフエニルセレノシアニド（O2NPhSeCN）
（）と６当量のｎ−ブチルホスフイン（ｎ−
Bu3P）をピリミジン中で反応するとほぼ定量的
収率で目的生成物（）を得ることができる。こ
の反応はO2NPhSeCNとｎ−Bu3Pの量を減少さ
せると収率は低下するし、またO2NPhSeCNのか
わりに（O2NPhSe）2または（PhSe）2を用いて反
応しても目的とする生成物（）は得られない。
目的生成物（）は反応終了後、ピリジンを留去
し、残渣を例えばシリカカラムクトマトグラフイ
ーで処理して純粋な化合物として得ることができ
る。
上記一般式（）および（）の化合物で使用
される置換基Ｂは5′-Se-(2-nitrophenyl)selenonucleoside represented by [Formula] (representing a pyrimidine nucleus that may have substituents at the 2-, 5-, and 6-positions) and its synthesis method. be. A new novel compound represented by the general formula () according to the present invention
We have found that 5'-Se-(2-nitrophenyl)selenonucleosides are useful reagents for 4',5'-unsaturated nucleosides. For example, 4',5'-unsaturated adenosine is an important synthetic intermediate for nucleocidine and Angustmycin A, and these compounds are already known to have potent trypanosomal, antibacterial, and antimicrobial properties. Also, 4′,5′-unsaturated adenosine is produced by ID Jenkins, J.P. Verheyden, J.G.
Moffat; J.Amer.Chem.Soc., 93 , 4323 (1971);
E.J.Prisbe, J.Smejkal, J.P.Verheyden, J.G.
Moffat; J.Org.Chem., 41 , 1836 (1976), etc. However, in these methods, it is necessary to protect the base and sugar moieties of adenosine, and cyclization reactions occur as side reactions, resulting in unfavorable yields. This includes similar problems with other 4',5'-unsaturated nucleosides, and a solution to these problems has therefore been desired. In contrast, the general formula () of the present invention
A new synthetic method using 5'-Se-(2-nitrophenyl)selenonucleoside as a raw material overcomes the above-mentioned drawbacks and allows 4',5'-unsaturated nucleosides to be easily obtained in high yield. That is, a method for synthesizing 4',5'-unsaturated nucleosides by reacting 5'-Se-(2-nitrophenyl)selenonucleoside with hydrogen peroxide and reacting the obtained selenooxide derivative with a tertiary amine. be. The present invention is based on the above
The present invention provides 5'-Se-(2-nitrophenyl)selenonucleoside represented by the general formula (), which is an excellent starting reagent for 4',5'-unsaturated nucleosides, and a method for synthesizing the same. The 5'-Se-(2-nitrophenyl)selenonucleoside () of the present invention is obtained by a method of selectively introducing a 2-nitrophenylseleno group into the 5'-hydroxyl group of a nucleoside. That is, it is shown by the following reaction formula. (wherein R and B are as defined above) 2-nitrophenylselenocyanide (O 2 NPhSeCN), preferably 3 equivalents relative to the nucleoside
() and 6 equivalents of n-butylphosphine (n-
When Bu 3 P) is reacted in pyrimidine, the desired product () can be obtained in almost quantitative yield. In this reaction, the yield decreases when the amounts of O 2 NPhSeCN and n-Bu 3 P are reduced, and even if (O 2 NPhSe) 2 or (PhSe) 2 is used instead of O 2 NPhSeCN, the reaction yield decreases. The desired product () cannot be obtained.
After the reaction is complete, the desired product () can be obtained as a pure compound by distilling off the pyridine and treating the residue with, for example, silica column chromatography. The substituent B used in the compounds of the above general formulas () and () is
【式】で表わされ
る２−、６−８−位に置換基を有することもある
プリン核、またはA purine nucleus that may have substituents at the 2-, 6-8-positions, or
【式】で表わされる２
−、５−、６−位に置換基を有することもあるピ
リミジン核をそれぞれ示すが、プリン核での２
−、６−位置換基は水素原子、アルキル基または
アシル基で置換されることもあるアミノ基、また
はケト基を示し、８−位は水素原子またはハロゲ
ン原子で置換される。ピリミジン核での２−、６
−位置換基はアルキル基またはアシル基で置換さ
れることもあるアミノ基、またはケト基を示し、
５−位置換基は水素原子、アルキル基、ハロゲン
原子またはシアノ基を示す。ここでアルキル基と
は炭素数１〜３の結合鎖を表わす。
次に本発明の代表的な合成法および得られた該
化合物による4′，5′−不飽和ヌクレオシドの合成
法を実施例により詳述する。
実施例 １
アデノシン（524mg、２ｍＭ）と２−ニトロフ
エニルセレノシアニド（1.13ｇ、６ｍＭ）をピリ
ジン（７ml）に加えたのち、冷却下、ｎ−ブチル
ホスフイン（2.42ml、12ｍＭ）を加え室温で24時
間撹拌する。反応終了後、水（１ml）を加え30分
室温に放置したのち、減圧濃縮する。残渣をシリ
カカラムクロマトグラフイーで処理して5′−Se−
（２−ニトロフエニル）セレノアデノシンを884mg
（収率98％）得た。
mp.127〜129℃
UV：λMeOH nax256nｍ
NMR（DMSO−d6）：δ 3.66（ｍ、2H、C′5−
Ｈ）、
4.20（ｍ、1H、C′4−Ｈ）、 4.40（ｍ、1H、C′3
−Ｈ）、
4.89（ｔ、1H、J1′、2′＝６Hz、J2′、3′６Hz、C
′2−
Ｈ
5.52（ｄ、1H、J2′、3′＝６Hz、3′−OH）、
5.69（ｄ、1H、J1′、2′６Hz、C′1−Ｈ）
7.31（br−ｓ、2H、NH2）
7.42〜8.38（ｍ、6H、Ar、C2−Ｈ、C8−Ｈ）
分析：（C16H16H6O5Se、H2O）
Ｃ：40.55（40.94）
Ｈ： 3.63（ 3.86）
Ｎ：17.76（17.79）
（ ）外は実測値、（ ）内は計算値を示す。
以下同様
実施例 ２
チミジン（727mg、３ｍＭ）と２−ニトロフエ
ニルセレノシアニド（1.02ｇ 4.5ｍＭ）をピリ
ジン（30mg）にとかし、冷却下ｎ−ブチルホスフ
イン（1.22ml、５ｍＭ）を加え室温にもどし１時
間撹拌したのち、減圧濃縮し、残渣を塩化メチレ
ンにとかし、水洗浄する。塩化メチレンを留去
し、残渣をシリカゲルカラムクロマトグラフイー
で処理して5′−Se−（２−ニトロフエニル）セレ
ノチミジンを1.15mg（収率90％）得た。
mp.166〜168℃
UV：λMeOH nax256nｍ、272（Sh）ｎｍ．
分析：（C16H17N6O6Se）
Ｃ：45.16（45.07）
Ｈ： 4.06（ 4.03）
Ｎ：9.84（9.86）
実施例 ３
ウリジン（542ｍＭ、2.22ｍＭ）と２−ニトロ
フエニルセレノシアニド（756mg、3.33ｍＭ）を
ピリジン（22ml）に溶かし、冷却下ｎ−ブチルホ
スフイン（0.902ml、3.7ｍＭ）を加え室温にもど
し、30分撹拌する。反応溶液を減圧濃縮し、残渣
をシリカゲルカラムクロマトグラフイーで処理し
て5′−Se−（２−ニトロフエニル）セレノウリジ
ンを834mg（収率89％）得た。
mp.132〜134℃
UV：λMeOH nax254nｍ
分析：（C15H5N3O7Se）
Ｃ：42.01（42.06）
Ｈ： 3.61（ 3.54）
Ｎ：9.73（9.81）
参考例
5′−Se−（２−ニトロフエニル）セレノアデノ
シン（902mg、２ｍＭ）をテトラヒドロラフン
（50ml）に加え、冷却下、30％過酸化水素水（20
ｍＭ）を加えたのち、室温に戻して２時間撹拌す
る。反応後、溶媒を完全に留去し、残渣をピリジ
ン（10ml）にとかし、トリエチルアミン（2.8ml、
20ｍＭ）を加え50℃で12時間反応させたのち、ピ
リジンを留去し、残渣をイオン交換樹脂で処理し
て純粋な4′，5′−不飽和アデノシン〔９−（5′−デ
オキシ−β−Ｄ−エリソーペント−４−エノフラ
ノシル）アデニン〕を483mg（収率97％）得た。
mp.184〜185℃
UV：λMeOH nax259nｍ（ε＝14300）
分析：（C10H11N5O3）
Ｃ：48.41（48.19）
Ｈ： 4.43（ 4.45）
Ｎ：28.03（28.10）[Formula] shows the pyrimidine nucleus which may have substituents at the 2-, 5-, and 6-positions, but the pyrimidine nucleus in the purine nucleus is
The - and 6-position substituents represent a hydrogen atom, an amino group which may be substituted with an alkyl group or an acyl group, or a keto group, and the 8-position is substituted with a hydrogen atom or a halogen atom. 2-, 6 in the pyrimidine nucleus
The -position substituent represents an amino group or a keto group which may be substituted with an alkyl group or an acyl group,
The 5-position substituent represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. Here, the alkyl group represents a bonded chain having 1 to 3 carbon atoms. Next, representative synthetic methods of the present invention and methods for synthesizing 4',5'-unsaturated nucleosides using the obtained compounds will be described in detail with reference to Examples. Example 1 Adenosine (524 mg, 2mM) and 2-nitrophenylselenocyanide (1.13g, 6mM) were added to pyridine (7ml), and then n-butylphosphine (2.42ml, 12mM) was added under cooling. Stir at room temperature for 24 hours. After the reaction was completed, water (1 ml) was added and the mixture was allowed to stand at room temperature for 30 minutes, and then concentrated under reduced pressure. The residue was treated with silica column chromatography to obtain 5'-Se-
(2-nitrophenyl)selenoadenosine 884mg
(yield 98%). mp.127～129℃ UV: λ MeOH nax 256nm NMR (DMSO−d 6 ): δ 3.66 (m, 2H, C′ 5 −
H), 4.20 (m, 1H, C′ 4 −H), 4.40 (m, 1H, C′ 3
−H), 4.89(t, 1H, J 1 ′, 2 ′ = 6Hz, J 2 ′, 3 ′6Hz, C
′ 2 −
H 5.52 (d, 1H, J 2 ′, 3 ′ = 6Hz, 3′-OH), 5.69 (d, 1H, J 1 ′, 2 ′6Hz, C′ 1 −H) 7.31 (br-s, 2H, NH2 ) 7.42-8.38 (m, 6H, Ar, C2 - H, C8 - H) Analysis: (C16H16H6O5Se, H2O ) C : 40.55 (40.94) H: 3.63 ( 3.86) N: 17.76 (17.79) Values outside parentheses are actually measured values, and values inside parentheses are calculated values. Example 2: Thymidine (727mg, 3mM) and 2-nitrophenylselenocyanide (1.02g 4.5mM) were dissolved in pyridine (30mg), and n-butylphosphine (1.22ml, 5mM) was added under cooling at room temperature. After stirring for 1 hour, the mixture was concentrated under reduced pressure, and the residue was dissolved in methylene chloride and washed with water. Methylene chloride was distilled off, and the residue was treated with silica gel column chromatography to obtain 1.15 mg (yield 90%) of 5'-Se-(2-nitrophenyl)selenothymidine. mp.166-168℃ UV: λ MeOH nax 256nm, 272(Sh)nm. Analysis: ( C16H17N6O6Se ) C: 45.16 ( 45.07 ) H: 4.06 (4.03) N: 9.84 (9.86) Example 3 Uridine ( 542mM, 2.22mM) and 2 - nitrophenylselenocyanide (756 mg, 3.33 mM) was dissolved in pyridine (22 ml), and while cooling, n-butylphosphine (0.902 ml, 3.7 mM) was added, the temperature was returned to room temperature, and the mixture was stirred for 30 minutes. The reaction solution was concentrated under reduced pressure, and the residue was treated with silica gel column chromatography to obtain 834 mg (yield: 89%) of 5'-Se-(2-nitrophenyl)selenouridine. mp.132-134℃ UV: λ MeOH nax 254nm Analysis: (C 15 H 5 N 3 O 7 Se) C: 42.01 (42.06) H: 3.61 ( 3.54) N: 9.73 (9.81) Reference example 5'-Se- (2-Nitrophenyl)selenoadenosine (902mg, 2mM) was added to tetrahydrolafun (50ml), and under cooling, 30% hydrogen peroxide solution (20%
(mM), then warmed to room temperature and stirred for 2 hours. After the reaction, the solvent was completely distilled off, the residue was dissolved in pyridine (10 ml), and triethylamine (2.8 ml,
After reacting at 50°C for 12 hours, pyridine was distilled off and the residue was treated with an ion exchange resin to obtain pure 4',5'-unsaturated adenosine [9-(5'-deoxy-β)]. -D-erythopent-4-enofuranosyl)adenine] was obtained (483 mg (yield 97%)). mp.184-185℃ UV: λ MeOH nax 259nm (ε=14300) Analysis: (C 10 H 11 N 5 O 3 ) C: 48.41 (48.19) H: 4.43 (4.45) N: 28.03 (28.10)
Claims (1)
【式】で表わされる２−、６−、８ −位に置換基を有することもあるプリン核、また
は【式】で表わされる２−、５−、６−位 に置換基を有することもあるピリミジン核を示
す）で表わされる5′−Se−（２−ニトロフエニル）
−セレノヌクレオシド。 ２ ２−ニトロフエニルセレノシアニドとｎ−ブ
チルホスフインと 一般式 （式中、Ｒは水素原子または水酸基を示し、Ｂは
【式】で表わされる２−、６−、８ −位に置換基を有することもあるプリン核、また
は【式】で表わされる２−、５−、６−位 に置換基を有することもあるピリミジン核を示
す） で表わされるヌクレオシドとを反応させることを
特徴とする 一般式 （式中、Ｒは水素原子または水酸基を示し、Ｂは
【式】で表わされる２−、６−、８ −位に置換基を有することもあるプリン核、また
は【式】で表わされる２−、５−、６−位 に置換基を有することもあるピリミジン核を示
す）で表わされる5′−Se−（２−ニトロフエニル）
−セレノヌクレオシドの合成法。[Claims] 1. General formula (In the formula, R represents a hydrogen atom or a hydroxyl group, and B represents a purine nucleus represented by [Formula] that may have a substituent at the 2-, 6-, or 8-position, or a 2- , 5'-Se-(2-nitrophenyl)
-Selenonucleosides. 2 2-Nitrophenylselenocyanide and n-butylphosphine General formula (In the formula, R represents a hydrogen atom or a hydroxyl group, and B represents a purine nucleus represented by [Formula] that may have a substituent at the 2-, 6-, or 8-position, or a 2- , a pyrimidine nucleus which may have substituents at the 5- and 6-positions) (In the formula, R represents a hydrogen atom or a hydroxyl group, and B represents a purine nucleus represented by [Formula] that may have a substituent at the 2-, 6-, or 8-position, or a 2- , 5'-Se-(2-nitrophenyl)
- A method for synthesizing selenonucleosides.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9970881A JPS584797A (en) | 1981-06-29 | 1981-06-29 | 5'-se-(2-nitrophenyl)selenonucleoside and its synthesis |
| US06/393,254 US4552955A (en) | 1981-06-29 | 1982-06-29 | Process for the synthesis of 4',5'-unsaturated nucleosides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9970881A JPS584797A (en) | 1981-06-29 | 1981-06-29 | 5'-se-(2-nitrophenyl)selenonucleoside and its synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS584797A JPS584797A (en) | 1983-01-11 |
| JPS6365076B2 true JPS6365076B2 (en) | 1988-12-14 |
Family
ID=14254562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9970881A Granted JPS584797A (en) | 1981-06-29 | 1981-06-29 | 5'-se-(2-nitrophenyl)selenonucleoside and its synthesis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS584797A (en) |
-
1981
- 1981-06-29 JP JP9970881A patent/JPS584797A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS584797A (en) | 1983-01-11 |
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