JPS6141907B2 - - Google Patents
Info
- Publication number
- JPS6141907B2 JPS6141907B2 JP14780383A JP14780383A JPS6141907B2 JP S6141907 B2 JPS6141907 B2 JP S6141907B2 JP 14780383 A JP14780383 A JP 14780383A JP 14780383 A JP14780383 A JP 14780383A JP S6141907 B2 JPS6141907 B2 JP S6141907B2
- Authority
- JP
- Japan
- Prior art keywords
- selenocyanate
- naphthalenyl
- reaction
- present
- general formula
- 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
Links
- BUKBHPHEGMNOBE-UHFFFAOYSA-N naphthalen-1-yl selenocyanate Chemical compound C1=CC=C2C([Se]C#N)=CC=CC2=C1 BUKBHPHEGMNOBE-UHFFFAOYSA-N 0.000 claims description 9
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- CRDYSYOERSZTHZ-UHFFFAOYSA-M selenocyanate Chemical compound [Se-]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000012954 diazonium Substances 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MFJMLBJXQBYZHB-UHFFFAOYSA-N naphthalen-2-yl selenocyanate Chemical compound C1=CC=CC2=CC([Se]C#N)=CC=C21 MFJMLBJXQBYZHB-UHFFFAOYSA-N 0.000 description 3
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VZCFVXZALPZXDN-UHFFFAOYSA-N carbonic acid;dihydrate Chemical compound [OH3+].[OH3+].[O-]C([O-])=O VZCFVXZALPZXDN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規な化合物であるナフタレニルセ
レノシアナートに関するものである。
有機セレン化合物は、生理活性などがあるとい
うことで、最近注目されているが、その化合物は
ごくわずかしか存在しない。本発明者はこれらの
点に着目しより有用な新規な化合物を合成すべく
種々研究を重ねた結果、本発明の化合物を創製す
るに到つた。
本発明の第一の発明は、一般式
で示されるナフタレニルセレノシアナートであ
る。
具体的な化合物名としては、１―ナフタレニル
セレノシアナート、および２―ナフタレニルセレ
ノシアナートである。
本発明の第二の発明は、ナフタレンアミンのジ
アゾニウム塩に一般式MSeCN（こゝでＭはアル
カリ金属を示す）で示されるセレノシアナート金
属塩を反応させることを特徴とする一般式(1)で示
されるナフタレニルセレノシアナートの製造法で
ある。
本発明の反応に用いられるナフタレンアミンと
は１または２―ナフタレンアミンを意味し、１―
ナフタレンアミンからは１―ナフタレニルセレノ
シアナートが、また２―ナフタレンアミンからは
２―ナフタレニルセレノシアナートが製造され
る。また、セレノシアナート金属塩としは、通常
アルカリ金属塩が用いられるが、セレノシアン酸
カリウムが好適に使用される。
本発明の製造法における反応を化合反応式で示
せば、つぎのようになる。
（式中、Ｍはアルカリ金属を示す）
上記反応はナフタレンアミンの塩酸溶液または
懸濁液を冷却下に亜硝酸ナトリウム（NaNO2）に
よりジアゾニウム塩溶液となし、冷却下、酢酸ナ
トリウム（NaOAc）にてPHが3.5ないし5.5の範囲
になるよう調整し、これにセレノシアン酸金属塩
（MSeCN）を加えることにより達成される。ナフ
タレンアミンとセレノシアン酸金属塩の割合は、
モル比で1.5：１、ないし１：1.5がよく、好適に
は１：１が良い。反応終了後は溶媒抽出、再結晶
などにより本発明の化合物が得られる。
本発明のナフタレニルセレノシアナートのSe
は親電子性が強くアルケンに対して付加しやす
い、また、アルケンにCN基を求核的に付加させ
る有効的な試剤であり、ほゞ定量的に反応するこ
とが特徴である。
すなわち、一般式(1)で示されるナフタレニルセ
レノシアナートは、アルケン類にナフタレニルセ
レノ基
The present invention relates to a novel compound, naphthalenyl selenocyanate. Organic selenium compounds have recently attracted attention due to their physiological activity, but only a small number of these compounds exist. The present inventor focused on these points and conducted various studies in order to synthesize more useful new compounds, and as a result, the compound of the present invention was created. The first invention of the present invention is based on the general formula It is naphthalenyl selenocyanate represented by Specific compound names are 1-naphthalenyl selenocyanate and 2-naphthalenyl selenocyanate. The second invention of the present invention is a general formula (1) characterized in that a diazonium salt of naphthalenamine is reacted with a selenocyanate metal salt represented by the general formula MSeCN (where M represents an alkali metal). This is a method for producing naphthalenyl selenocyanate shown in The naphthalene amine used in the reaction of the present invention means 1- or 2-naphthalene amine, and 1-
1-naphthalenyl selenocyanate is produced from naphthalene amine, and 2-naphthalenyl selenocyanate is produced from 2-naphthalen amine. Further, as the selenocyanate metal salt, an alkali metal salt is usually used, and potassium selenocyanate is preferably used. The reaction in the production method of the present invention can be expressed as a chemical reaction formula as follows. (In the formula, M represents an alkali metal.) In the above reaction, a hydrochloric acid solution or suspension of naphthaleneamine is made into a diazonium salt solution with sodium nitrite (NaNO 2 ) under cooling, and then converted into a diazonium salt solution with sodium acetate (NaOAc) under cooling. This is achieved by adjusting the pH to a range of 3.5 to 5.5 and adding metal selenocyanate (MSeCN). The ratio of naphthalenamine and selenocyanate metal salt is
The molar ratio is preferably 1.5:1 to 1:1.5, preferably 1:1. After the reaction is completed, the compound of the present invention can be obtained by solvent extraction, recrystallization, etc. Se of naphthalenyl selenocyanate of the present invention
It has strong electrophilicity and easily adds to alkenes, and is an effective reagent for nucleophilic addition of CN groups to alkenes, and is characterized by its almost quantitative reaction. That is, naphthalenylselenocyanate represented by general formula (1) has a naphthalenylseleno group in the alkene.
１―ナフタレンアミン28.6ｇ（0.2mol）を濃塩
酸90mlと水100mlの混合液に懸濁し、５℃に冷却
し亜硝酸ナトリウム13.8ｇ（0.2mol）を少量ずつ
加えながら撹拌した。得られた溶液に酢酸ナトリ
ウムをコンゴーレツド試験紙がもはや青変しなく
なるまで加えた。ついではげしくかきまぜながら
セレノシアン酸カリウム28.8ｇ（0.2mol）を少量
ずつ加え、ガスが発生しなくなるまで冷却下に反
応を続けた。反応混合液をエーテルにて抽出し、
水、重炭酸ナトリウム水にて順次洗滌した後、硫
酸マグネシウムにて乾燥した。
シリカゲルカラムをとおし、ついで溶媒を留去
した後、ヘキサン―塩化メチレンで活性炭を加え
て熱時ろ過した後再結晶し生成物の結晶33.9ｇ
（0.146mol）を取得した。収率73％であつた。
得られた生成物の物性値は、融点：73℃、
IRmax（KBr disk）：2150cm-1（νCN）、13C―
NMR：δ101.1PPM（―SeＣＮ）、77Se―NMR：
δ267.4PPMであり、１―ナフタレニルセレノシ
アナートであることを確認した。
〔実施例 ２〕
２ナフタレンアミン28.6ｇを用い、以下は実施
例１と同様の方法で反応後処理を行い、生成物
22.7ｇを取得した。収率49％であつた。
得られた生成物の物性値は、融点：68℃、
IRmax（KBr disk）：2150cm-1（νCN）、13C―
NMR：δ101.4PPM（―SeCN）、77Se―NMR：δ
325.7PPMであり、２―ナフタレニルセレノシア
ナートであることを確認した。
28.6 g (0.2 mol) of 1-naphthaleneamine was suspended in a mixture of 90 ml of concentrated hydrochloric acid and 100 ml of water, cooled to 5°C, and stirred while adding 13.8 g (0.2 mol) of sodium nitrite little by little. Sodium acetate was added to the resulting solution until the Congo Red test paper no longer turned blue. Next, 28.8 g (0.2 mol) of potassium selenocyanate was added little by little while stirring vigorously, and the reaction was continued under cooling until no gas was generated. The reaction mixture was extracted with ether,
After sequentially washing with water and sodium bicarbonate water, it was dried over magnesium sulfate. Passed through a silica gel column, then distilled off the solvent, added activated carbon with hexane-methylene chloride, filtered while hot, and recrystallized to give 33.9 g of crystalline product.
(0.146mol) was obtained. The yield was 73%. The physical properties of the obtained product are: melting point: 73°C;
IRmax (KB r disk): 2150cm -1 (ν CN ), 13 C—
NMR: δ101.1PPM (-Se CN ), 77 Se-NMR:
It was confirmed that it was δ267.4PPM and was 1-naphthalenyl selenocyanate. [Example 2] Using 28.6 g of 2-naphthalene amine, post-reaction treatment was performed in the same manner as in Example 1, and the product was
22.7g was obtained. The yield was 49%. The physical properties of the obtained product are: melting point: 68°C;
IRmax (KB r disk): 2150cm -1 (ν CN ), 13 C—
NMR: δ101.4PPM (-SeCN), 77 Se-NMR: δ
It was confirmed that it was 2-naphthalenyl selenocyanate.
Claims (1)
シアナート金属塩を反応させることを特徴とす
る一般式【式】で示されるナ フタレニルセレノシアナートの製造法。[Claims] 1. Naphthalenyl selenocyanate represented by the general formula [Formula]. A method for producing naphthalenyl selenocyanate represented by the general formula [Formula], which comprises reacting a diazonium salt of naphthalene amine with a selenocyanate metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14780383A JPS6041661A (en) | 1983-08-12 | 1983-08-12 | Naphthalenylselenocyanate and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14780383A JPS6041661A (en) | 1983-08-12 | 1983-08-12 | Naphthalenylselenocyanate and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6041661A JPS6041661A (en) | 1985-03-05 |
| JPS6141907B2 true JPS6141907B2 (en) | 1986-09-18 |
Family
ID=15438563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14780383A Granted JPS6041661A (en) | 1983-08-12 | 1983-08-12 | Naphthalenylselenocyanate and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6041661A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH066713U (en) * | 1990-12-27 | 1994-01-28 | 株式会社竹中工務店 | Clamp with nut |
-
1983
- 1983-08-12 JP JP14780383A patent/JPS6041661A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH066713U (en) * | 1990-12-27 | 1994-01-28 | 株式会社竹中工務店 | Clamp with nut |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6041661A (en) | 1985-03-05 |
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