JPH0587063B2 - - Google Patents
Info
- Publication number
- JPH0587063B2 JPH0587063B2 JP5578090A JP5578090A JPH0587063B2 JP H0587063 B2 JPH0587063 B2 JP H0587063B2 JP 5578090 A JP5578090 A JP 5578090A JP 5578090 A JP5578090 A JP 5578090A JP H0587063 B2 JPH0587063 B2 JP H0587063B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- represented
- halogen atom
- aroylthioxime
- 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 - Lifetime
Links
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- -1 aromatic thiocarboxylic acid Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- NEQRDYYMIIIVPW-UHFFFAOYSA-N s-amino benzenecarbothioate Chemical compound NSC(=O)C1=CC=CC=C1 NEQRDYYMIIIVPW-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000026280 response to electrical stimulus Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は、アロイルチオオキシム類およびそれ
らの製造法に関するものである。
〔発明が解決しようとする問題点〕
含硫黄有機化合物の中には医農薬などの生理活
性物質、電気、光等に対して特異な挙動を示す機
能性物質が数多く知られていた。最近、オプトエ
レクトニツクス分野の新素材の開発は目覚まし
く、非線形光学材料について関心が注がれてき、
多くの化合物の中で、芳香族アルデヒドの誘導体
が有望視されている。
〔問題点を解決するための手段〕
本発明は、かかる現状を鑑みてなされたもので
新たな含硫黄有機化合物を合成し、機能性物質を
創出するべく有機硫黄化合物の化学的性質につい
て鋭意検討を重ねたところ、その目的に合致する
新規な化合物、Ｓ−アロイルチオオキシム、およ
びその製造方法を見い出し、本発明を完成するに
至つた。
すなわち、本発明によれば、一般式
[Industrial Application Field] The present invention relates to aroylthioximes and methods for producing them. [Problems to be Solved by the Invention] Many sulfur-containing organic compounds have been known to include physiologically active substances such as medicines and pesticides, and functional substances that exhibit unique behavior in response to electricity, light, and the like. Recently, the development of new materials in the optoelectronics field has been remarkable, and interest has been focused on nonlinear optical materials.
Among many compounds, derivatives of aromatic aldehydes have shown promise. [Means for solving the problems] The present invention was made in view of the current situation, and involves synthesizing new sulfur-containing organic compounds and conducting intensive studies on the chemical properties of organic sulfur compounds in order to create functional substances. As a result of repeated research, the inventors discovered a new compound, S-aroylthioxime, and a method for producing the same, which met the objective, and completed the present invention. That is, according to the present invention, the general formula
【化】
（式中、Arは低級アルキル基、低級アルコキ
シ基及びハロゲン原子の中から選ばれる置換基を
有していてもよいフエニル基を示し、Ｒは低級ア
ルコキシ基、ハロゲン原子及びニトロ基の中から
選ばれる置換基をＰ−位に有していてもよいフエ
ニル基、ピリジル基又はチエニル基を示す）
で表わされるアロイルチオオキシムが提供され
る。
また、本発明によれば、前記一般式（Ｉ）で表
わされるアロイルチオオキシムを製造するため
に、一般式[Formula, Ar represents a phenyl group which may have a substituent selected from a lower alkyl group, a lower alkoxy group, and a halogen atom, and R represents a lower alkoxy group, a halogen atom, and a nitro group. An aroylthioxime represented by a phenyl group, a pyridyl group or a thienyl group which may have a substituent selected from among them at the P-position is provided. Further, according to the present invention, in order to produce the aroylthioxime represented by the general formula (I), the general formula
【化】
（式中、Arは前記と同じ意味を示す）
で表わされるＳ−アロイルスルフエンアミドと、
一般式
Ｒ−CHO （III）
（式中、Ｒは前記と同じ意味を示す）
で表わされるアルデヒドを反応させる方法が提供
される。
本発明において原料として用いる一般式（）
で示されるＳ−アロイルスルフエンアミドは芳香
族チオカルボン酸のアルカリ水溶液に室温以下の
温度でヒドロキシルアミン−Ｏ−スルホン酸水溶
液を滴下することにより容易に、かつ好収率で得
られる。一方、芳香族チオカルボン酸の水溶液は
対応する酸塩化物に硫化ジアルカリ又は水硫化ア
ルカリを作用させることによつて調製できるの
で、Arについてはこれらのチオカルボン酸また
は酸塩化物の中から置換基の種類を選ぶことによ
つて目的とする置換基を導入することができる。
Arは置換基を有していてもよいフエニル基を示
すが、この場合の置換基としては、メチル、エチ
ル、プロピル等の低級アルキル基、メトキシ、エ
トキシ、プロポキシ等の低級アルコキシ基、及び
塩素や臭素等のハロゲン原子が挙げられる。
本発明のもう一方の原料である一般式（）で
示されるアルデヒドは数多くの市販品が知られて
おり、きわめて入手しやすく、Ｒとしては、置換
基をＰ−位に有していてもよいフエニル基の他、
ピリジル基、チエニル基が挙げられる。この場
合、フエニル基に結合することのできる置換基と
しては、低級アルコキシ基、ハロゲン原子、ニト
ロ基が挙げられる。
次に目的物を導く反応経路をＳ−ベンゾイルス
ルフエンアミドおよびｐ−アニスアルデヒドを用
いた場合を例にとれば、下記のような反応式で表
現できる。S-aroylsulfenamide represented by [Chemical formula] (wherein Ar has the same meaning as above),
A method for reacting an aldehyde represented by the general formula R-CHO (III) (wherein R has the same meaning as above) is provided. General formula () used as a raw material in the present invention
The S-aroylsulfenamide represented by can be easily obtained in a good yield by dropping an aqueous hydroxylamine-O-sulfonic acid solution into an aqueous alkaline solution of an aromatic thiocarboxylic acid at a temperature below room temperature. On the other hand, an aqueous solution of an aromatic thiocarboxylic acid can be prepared by reacting the corresponding acid chloride with dialkali sulfide or alkali hydrosulfide. By selecting , the desired substituent can be introduced.
Ar represents a phenyl group which may have a substituent, and the substituents in this case include lower alkyl groups such as methyl, ethyl, and propyl, lower alkoxy groups such as methoxy, ethoxy, and propoxy, and chlorine and Examples include halogen atoms such as bromine. The aldehyde represented by the general formula (), which is the other raw material of the present invention, is known as a large number of commercially available products and is extremely easily available.R may have a substituent at the P-position. In addition to phenyl group,
Examples include pyridyl group and thienyl group. In this case, examples of the substituent that can be bonded to the phenyl group include a lower alkoxy group, a halogen atom, and a nitro group. Next, the reaction route leading to the desired product can be expressed by the following reaction formula, taking as an example the case where S-benzoylsulfenamide and p-anisaldehyde are used.
本発明によつて得られるものは新規化合物であ
るが、特に、Ｓ−（ｐ−置換ベンゾイル）−ｐ−置
換ベンズチオオキシム類の多くのものはSHG活
性を示し、非線形光学材料として有望である。ま
た、これらのアロイルチオオキシムには高い反応
性が保持されており、Ｎ−アシルイミンの等価体
として、各種の試剤との反応で多くの誘導体を与
えるものと考えられ、合成化学的にも利用価値が
高い。
〔実施例〕
次に本発明を実施例に基づきさらに詳細に説明
する。
実施例 １
クロロホルム５mlにＳ−ベンゾイルスルフエン
アミド1.53ｇと1.27ｇのベンズアルデヒドを溶か
す。さらにｐ−トルエンスルホン酸の結晶片（約
１mg程度）を加えて、水浴上で２時間還流した
後、減圧下で溶媒を除き、メタノールで再結晶し
て精製すると、融点91℃のＳ−ベンゾイルベンズ
チオオキシムの白色針状結晶1.93ｇ（収率80％）
を得た。
IR：1670，895cm-1；NMR：8.8ppm；MS：
241，209，105m／ｚ。
C14H11NSOとしての元素分析結果は次のよう
であつた。
計算値（％）：Ｃ，64.45；Ｈ，4.16；Ｎ，11.56
測定値（％）：Ｃ，64.27；Ｈ，4.16；Ｎ，11.58
実施例 ２
クロロホルム５mlに0.01molのＳ−アロイルス
ルフエンアミドと0.012molのアルデヒドをとか
し、さらに、ごく少量のｐ−トルエンスルホン酸
の結晶片を加えて、水浴上で約２時間還流した
後、減圧下で溶媒を除く。得られた粗精製物をメ
タノール、エタノール、アセトニトリルなどの溶
媒で再結晶して精製した。この様にして得られた
各種のＳ−アロイルチオオキシム類の収率、融
点、元素分析の結果などを表にまとめた。
The compounds obtained by the present invention are new compounds, and in particular, many S-(p-substituted benzoyl)-p-substituted benzthioximes exhibit SHG activity and are promising as nonlinear optical materials. . In addition, these aroylthioximes maintain high reactivity, and are thought to give many derivatives as N-acylimine equivalents by reaction with various reagents, and have utility value in synthetic chemistry. is high. [Examples] Next, the present invention will be explained in more detail based on Examples. Example 1 Dissolve 1.53 g of S-benzoylsulfenamide and 1.27 g of benzaldehyde in 5 ml of chloroform. Further, p-toluenesulfonic acid crystal pieces (approximately 1 mg) were added, and after refluxing on a water bath for 2 hours, the solvent was removed under reduced pressure, and purified by recrystallization with methanol. 1.93 g of white needle-like crystals of benzthioxime (yield 80%)
I got it. IR: 1670, 895cm -1 ; NMR: 8.8ppm; MS:
241, 209, 105m/z. The elemental analysis results for C 14 H 11 NSO were as follows. Calculated value (%): C, 64.45; H, 4.16; N, 11.56 Measured value (%): C, 64.27; H, 4.16; N, 11.58 Example 2 0.01 mol of S-aroylsulfenamide and 5 ml of chloroform Dissolve 0.012 mol of aldehyde, add a very small amount of p-toluenesulfonic acid crystal pieces, reflux on a water bath for about 2 hours, and then remove the solvent under reduced pressure. The obtained crude product was purified by recrystallization with a solvent such as methanol, ethanol, or acetonitrile. The yield, melting point, elemental analysis results, etc. of the various S-aroylthioximes thus obtained are summarized in a table.
【表】
° カツコ内の値は計算値を示す。
[Table] ° Values in brackets indicate calculated values.
Claims (1)
シ基及びハロゲン原子の中から選ばれる置換基を
有していてもよいフエニル基を示し、Ｒは低級ア
ルコキシ基、ハロゲン原子及びニトロ基の中から
選ばれる置換基をＰ−位に有していてもよいフエ
ニル基、ピリジル基又はチエニル基を示す） で表わされるアロイルチオオキシム。 ２ 一般式 【化】 （式中、Arは低級アルキル基、低級アルコキ
シ基及びハロゲン原子の中から選ばれる置換基を
有していてもよいフエニル基を示し、Ｒは低級ア
ルコキシ基、ハロゲン原子及びニトロ基の中から
選ばれる置換基をＰ−位に有していてもよいフエ
ニル基、ピリジル基又はチエニル基を示す） で表わされるアロイルチオオキシムを製造するた
めに、一般式 【化】 （式中、Arは前記と同じ意味を示す） で表わされるＳ−アロイルスルフエンアミドと、
一般式 Ｒ−CHO （III） （式中、Ｒは前記と同じ意味を示す） で表わされるアルデヒドを反応させる方法。[Scope of Claims] 1 General formula An aroylthioxime represented by a phenyl group, a pyridyl group, or a thienyl group which may have a substituent selected from an alkoxy group, a halogen atom, and a nitro group at the P-position. 2 General formula: (wherein, Ar represents a phenyl group which may have a substituent selected from a lower alkyl group, a lower alkoxy group and a halogen atom, and R represents a lower alkoxy group, a halogen atom and In order to produce an aroylthioxime represented by the general formula (wherein, Ar has the same meaning as above) S-aroylsulfenamide represented by
A method of reacting an aldehyde represented by the general formula R-CHO (III) (wherein R has the same meaning as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5578090A JPH03258762A (en) | 1990-03-07 | 1990-03-07 | Aroylthiooxime and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5578090A JPH03258762A (en) | 1990-03-07 | 1990-03-07 | Aroylthiooxime and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258762A JPH03258762A (en) | 1991-11-19 |
| JPH0587063B2 true JPH0587063B2 (en) | 1993-12-15 |
Family
ID=13008409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5578090A Granted JPH03258762A (en) | 1990-03-07 | 1990-03-07 | Aroylthiooxime and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03258762A (en) |
-
1990
- 1990-03-07 JP JP5578090A patent/JPH03258762A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03258762A (en) | 1991-11-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |