JPS6411630B2 - - Google Patents
Info
- Publication number
- JPS6411630B2 JPS6411630B2 JP1080578A JP1080578A JPS6411630B2 JP S6411630 B2 JPS6411630 B2 JP S6411630B2 JP 1080578 A JP1080578 A JP 1080578A JP 1080578 A JP1080578 A JP 1080578A JP S6411630 B2 JPS6411630 B2 JP S6411630B2
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- tetrahydrobenzimidazoline
- aminocyclohexanone
- formula
- 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
Links
- 125000000217 alkyl 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
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- KAWYASGZISVRAL-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1h-benzimidazole Chemical compound C1CCCC2=C1N=CN2 KAWYASGZISVRAL-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 description 10
- JKCWEUIGTMTRMK-UHFFFAOYSA-N 1,3,4,5,6,7-hexahydrobenzimidazole-2-thione Chemical class C1CCCC2=C1N=C(S)N2 JKCWEUIGTMTRMK-UHFFFAOYSA-N 0.000 description 6
- -1 N-substituted-2-aminocyclohexanone Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CHPSWOWDEYXTFU-UHFFFAOYSA-N n-(2-aminocyclohexylidene)hydroxylamine Chemical compound NC1CCCCC1=NO CHPSWOWDEYXTFU-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002540 isothiocyanates Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KMLPEYHLAKSCGX-UHFFFAOYSA-N 2-aminocyclohexan-1-one Chemical compound NC1CCCCC1=O KMLPEYHLAKSCGX-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FVPVTJRHVHMQQZ-UHFFFAOYSA-N 1,3,3a,4,5,6-hexahydrobenzimidazole-2-thione Chemical class C1CCC=C2NC(=S)NC21 FVPVTJRHVHMQQZ-UHFFFAOYSA-N 0.000 description 1
- ZHKJHQBOAJQXQR-UHFFFAOYSA-N 1H-azirine Chemical compound N1C=C1 ZHKJHQBOAJQXQR-UHFFFAOYSA-N 0.000 description 1
- OJHWPOJTJKJBLA-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1h-benzimidazole Chemical class C1C=CC=C2NCNC21 OJHWPOJTJKJBLA-UHFFFAOYSA-N 0.000 description 1
- HGHZKLDCXNJLJK-UHFFFAOYSA-N 2-aminocyclohexan-1-one;hydrochloride Chemical compound Cl.NC1CCCCC1=O HGHZKLDCXNJLJK-UHFFFAOYSA-N 0.000 description 1
- BOWUOGIPSRVRSJ-UHFFFAOYSA-N 2-aminohexano-6-lactam Chemical compound NC1CCCCNC1=O BOWUOGIPSRVRSJ-UHFFFAOYSA-N 0.000 description 1
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical class [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical class S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【発明の詳細な説明】 本発明は、一般式[Detailed description of the invention] The present invention is based on the general formula
【式】（式中R1
は水素、アルキル基、フエニル基、フエニルアル
キル基、R2はアルキル基、フエニル基、フエニ
ルアルキル基を示す。）で表わされる新規な４，
５，６，７−テトラヒドロベンズイミダゾリン−
２−チオン誘導体に関する。
本発明でいう４，５，６，７−テトラヒドロベ
ンズイミダゾリン−２−チオン誘導体は一般式A novel 4, represented by [Formula] (wherein R 1 represents hydrogen, an alkyl group, a phenyl group, or a phenylalkyl group, and R 2 represents an alkyl group, a phenyl group, or a phenylalkyl group).
5,6,7-Tetrahydrobenzimidazoline-
This invention relates to 2-thione derivatives. The 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivative referred to in the present invention has the general formula
【式】（式中R1、R2は前記と同じ。）
で表わされる化学構造式から容易に推察出来ると
おりR1が水素の場合には対応する２−メルカプ
ト−４，５，６，７−テトラヒドロベンズイミダ
ゾール誘導体と互変可能な異性体であり、両者の
存在比率は製造方法、雰囲気、置換基の種類など
によ
つても異なる場合もあるが、両者は化学的には実
質的に同一の化合物とみなせる。したがつて、本
発明においては両者を含めて、４，５，６，７−
テトラヒドロベンズイミダゾリン−２−チオン誘
導体と称する。一般にイミダゾリン−２−チオン
類は医薬品中間体、工業用ゴム薬品またはその中
間体および防錆剤などとして重要な物質であり、
その製造方法や利用方法に関して、すでに数多く
の提案がなされているのみならず、さらに新規な
誘導体の製造が望まれている。ところで、一般式As can be easily inferred from the chemical structural formula represented by [Formula] (in which R 1 and R 2 are the same as above), when R 1 is hydrogen, the corresponding 2-mercapto-4,5,6,7 - It is an isomer that can be tautomerized with the tetrahydrobenzimidazole derivative, and the abundance ratio of both depends on the manufacturing method, atmosphere, type of substituent, etc. Although they may be different, chemically they can be considered to be essentially the same compound. Therefore, in the present invention, including both, 4,5,6,7-
It is called a tetrahydrobenzimidazoline-2-thione derivative. In general, imidazoline-2-thiones are important substances as pharmaceutical intermediates, industrial rubber chemicals or their intermediates, and rust preventive agents.
Not only have many proposals already been made regarding methods of producing and utilizing them, but there is also a desire to produce even newer derivatives. By the way, the general formula
【式】（式中R1、R2は前記と同じ。）
で表わされる４，５，６，７−テトラヒドロベン
ズイミダゾリン−２−チオン誘導体に関しては、
ほとんど知られておらず、わずかにR1およびR2
が水素の場合のみ合成されているにすぎない。
〔J.Am.Chem.Soc.、795710（1957）〕
この公知例の合成方法は２−アミノシクロヘキ
サノンの塩酸塩とチオシアン酸カリウムを水中で
加熱する方法である。
また、原料である２−アミノシクロヘキサノン
の塩酸塩の製造方法としては、下記の方法を採用
している。〔J.Am.Chem.Soc.、76−4561（1954）〕
この公知例の方法はクロルアミンをナトリウム
メトキシドにより処理する方法で、アジリンRegarding the 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivative represented by [Formula] (wherein R 1 and R 2 are the same as above),
Little known, only R 1 and R 2
It is only synthesized when is hydrogen.
[J.Am.Chem.Soc., 79 5710 (1957)] The synthesis method of this known example is a method of heating 2-aminocyclohexanone hydrochloride and potassium thiocyanate in water. Moreover, the following method is adopted as a method for producing the hydrochloride of 2-aminocyclohexanone, which is a raw material. [J.Am.Chem.Soc., 76-4561 (1954)] This known method is a method in which chloramine is treated with sodium methoxide, and azirine is
【式】およびメトキシエチルイミン[Formula] and methoxyethylimine
【式】中間体を経由するアミノ基の転位
反応を含むため、この方法ではＮ−置換−２−ア
ミノシクロヘキサノン誘導体は製造出来ない。ま
た、２−アミノシクロヘキサノンは遊離のアミン
の状態では不安定であり、ハロゲン化アルキルま
たはハロゲン化アラルキル誘導体と反応させて、
収率よくＮ−置換−２−アミノシクロヘキサノン
誘導体を製造することも簡単ではない。また、た
とえＮ−置換−２−アミノシクロヘキサノン誘導
体が得られたとしても、チオシアン酸カリウムと
反応させる前記公知例の方法では、本発明のごと
きＮ，N′−二置換−４，５，６，７−テトラヒ
ドロベンズイミダゾリン−２−チオン誘導体は製
造出来ない。
すなわち、前記の２つの公知例の組み合わせで
は原料および反応の両者の制約から、本発明のご
とき新規な４，５，６，７−テトラヒドロベンズ
イミダゾリン−２−チオン誘導体は製造が困難で
あつた。
本発明者らは、かかる新規なイミダゾリン−２
−チオン類の製造に関して鋭意努力した結果、本
発明に到達した。
本発明によつて提供される新規な４，５，６，
７−テトラヒドロベンズイミダゾリン−２−チオ
ン誘導体は、たとえば２−アミノシクロヘキサノ
ンオキシムまたはその誘導体とイソチオシアネー
ト類の反応物を酸性物質で処理することによつて
製造出来る。
（式中R1は水素、アルキル基、フエニル基、フ
エニルアルキル基、R2はアルキル基、フエニル
基、フエニルアルキル基を示す。）
本発明によつて提供される前記一般式によつて
表わされる新規な４，５，６，７−テトラヒドロ
ベンズイミダゾリン−２−チオン誘導体はゴム用
老化防止剤および防錆剤として有用である。
本発明を実施するにあたり使用される２−アミ
ノシクロヘキサノンオキシムは必須アミノ酸の１
つであるリジンの工業的製法の中間体であるα−
アミノ−ε−カプロラクタムの主要な原料の１つ
であり、例えば、次に示す方法により高収率で工
業的に製造される。
このα−アミノシクロヘキサノンオキシムの製
造方法において、アンモニアに代えて、Ｒ−
NH2（式中Ｒはアルキル基、フエニル基、フエニ
ルアルキル基）を使用した場合には
[Formula] Since this method involves a rearrangement reaction of an amino group via an intermediate, N-substituted-2-aminocyclohexanone derivatives cannot be produced. In addition, 2-aminocyclohexanone is unstable in the free amine state, so it can be reacted with an alkyl halide or an aralkyl halide derivative,
It is also not easy to produce N-substituted-2-aminocyclohexanone derivatives in good yield. Furthermore, even if an N-substituted-2-aminocyclohexanone derivative is obtained, in the above-mentioned known method of reacting with potassium thiocyanate, N,N'-disubstituted-4,5,6, 7-tetrahydrobenzimidazoline-2-thione derivatives cannot be produced. That is, it has been difficult to produce the novel 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivative of the present invention by combining the above two known examples due to limitations in both raw materials and reactions. The present inventors discovered such a novel imidazoline-2
- As a result of diligent efforts in the production of thiones, the present invention has been achieved. Novel 4,5,6, provided by the present invention
The 7-tetrahydrobenzimidazoline-2-thione derivative can be produced, for example, by treating a reaction product of 2-aminocyclohexanone oxime or its derivative with an isothiocyanate with an acidic substance. (In the formula, R 1 represents hydrogen, an alkyl group, a phenyl group, or a phenylalkyl group, and R 2 represents an alkyl group, a phenyl group, or a phenylalkyl group.) The novel 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivatives are useful as anti-aging agents and rust inhibitors for rubber. The 2-aminocyclohexanone oxime used in carrying out the present invention is one of the essential amino acids.
α-
It is one of the main raw materials for amino-ε-caprolactam, and is industrially produced in high yield by, for example, the following method. In this method for producing α-aminocyclohexanone oxime, R-
When using NH 2 (in the formula, R is an alkyl group, phenyl group, or phenyl alkyl group),
【式】（式中Ｒは前記と同じ）で表わ
されるα−アミノシクロヘキサノン誘導体が同様
に得られる。
また、イソチオシアネート類の製造方法に関し
ては数多くの提案がなされているが、本発明を実
施するにあたり、これらのいかなる方法で製造さ
れたチオイソシアネート類でも使用出来る。
以下、実施例により本発明をさらに詳細に説明
する。
実施例 １
２−アミノシクロヘキサノンオキシムまたはそ
の誘導体0.05モルと、これと等モルのイソチオシ
アネート類をベンゼン300ml中、60℃で３時間加
熱した。反応液を25℃まで冷却した後、使用した
２−アミノシクロヘキサノンオキシムまたはその
誘導体に対して２倍当量の塩化水素を含む１規定
塩酸を加え、激しく１時間撹拌した。溶媒を大部
分減圧、留去した後、残存物に対して10倍量（重
量）の水を加え、水と等量のクロロホルムで５回
抽出した。クロロホルム抽出液を合わせ、水洗し
た後クロロホルムを減圧留去して、粗４，５，
６，７−テトラヒドロベンズイミダゾリン−２−
チオン類を得た。これを溶媒で再結晶して得られ
た精製４，５，６，７−テトラヒドロベンズイミ
ダゾリン−２−チオン誘導体の同定は元素分析、
核磁気共鳴分光分析および紫外分光分析により行
なつた。
実施結果を表１〜３に示す。An α-aminocyclohexanone derivative represented by the formula (wherein R is the same as above) can be obtained in the same manner. Furthermore, although many proposals have been made regarding methods for producing isothiocyanates, thioisocyanates produced by any of these methods can be used in carrying out the present invention. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 0.05 mol of 2-aminocyclohexanone oxime or its derivative and an equimolar amount of isothiocyanate were heated at 60°C for 3 hours in 300 ml of benzene. After the reaction solution was cooled to 25° C., 1N hydrochloric acid containing twice the equivalent amount of hydrogen chloride relative to the 2-aminocyclohexanone oxime or its derivative used was added, and the mixture was vigorously stirred for 1 hour. After most of the solvent was distilled off under reduced pressure, 10 times the amount (weight) of water was added to the residue, and the mixture was extracted five times with chloroform in an equal amount to water. The chloroform extracts were combined, washed with water, and the chloroform was distilled off under reduced pressure to obtain crude 4, 5,
6,7-tetrahydrobenzimidazoline-2-
Thiones were obtained. The purified 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivative obtained by recrystallizing this from a solvent was identified by elemental analysis.
This was done by nuclear magnetic resonance spectroscopy and ultraviolet spectroscopy. The implementation results are shown in Tables 1-3.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
エニルアルキル基、R2はアルキル基、フエニル
基、フエニルアルキル基を示す。） で表わされる４，５，６，７−テトラヒドロベン
ズイミダゾリン−２−チオン誘導体。[Claims] 1. General formula (In the formula, R1 represents hydrogen, an alkyl group, a phenyl group, or a phenylalkyl group, and R2 represents an alkyl group, a phenyl group, or a phenylalkyl group.) 4,5,6,7-tetrahydrobenzimidazoline represented by -2-thione derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1080578A JPS54103870A (en) | 1978-02-02 | 1978-02-02 | Novel 4,5,6,7-tetrahydro-benzimidazoline-2-thione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1080578A JPS54103870A (en) | 1978-02-02 | 1978-02-02 | Novel 4,5,6,7-tetrahydro-benzimidazoline-2-thione derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54103870A JPS54103870A (en) | 1979-08-15 |
| JPS6411630B2 true JPS6411630B2 (en) | 1989-02-27 |
Family
ID=11760549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1080578A Granted JPS54103870A (en) | 1978-02-02 | 1978-02-02 | Novel 4,5,6,7-tetrahydro-benzimidazoline-2-thione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54103870A (en) |
-
1978
- 1978-02-02 JP JP1080578A patent/JPS54103870A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54103870A (en) | 1979-08-15 |
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