JPS636543B2 - - Google Patents
Info
- Publication number
- JPS636543B2 JPS636543B2 JP11065879A JP11065879A JPS636543B2 JP S636543 B2 JPS636543 B2 JP S636543B2 JP 11065879 A JP11065879 A JP 11065879A JP 11065879 A JP11065879 A JP 11065879A JP S636543 B2 JPS636543 B2 JP S636543B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- cyclohexane
- malonitrile
- dicyanomethylene
- bis
- 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
- JXPDNDHCMMOJPC-UHFFFAOYSA-N 2-hydroxybutanedinitrile Chemical compound N#CC(O)CC#N JXPDNDHCMMOJPC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- POXIZPBFFUKMEQ-UHFFFAOYSA-N 2-cyanoethenylideneazanide Chemical group [N-]=C=[C+]C#N POXIZPBFFUKMEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- NXQNMVFWIRBUHX-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)cyclohexylidene]propanedinitrile Chemical compound N#CC(C#N)=C1CCC(=C(C#N)C#N)CC1 NXQNMVFWIRBUHX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940000635 beta-alanine Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- NMGSDTSOSIPXTN-UHFFFAOYSA-N cyclohexa-1,2-diene Chemical compound C1CC=C=CC1 NMGSDTSOSIPXTN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は１・４−ビス（ジシアノメチレン）シ
クロヘキサン（）の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,4-bis(dicyanomethylene)cyclohexane ().
この化合物は従来シクロヘキサン−１・４−ジ
オンとマロンニトリルの縮合反応によつて製造し
うることが知られている。 It has been known that this compound can be produced by a condensation reaction of cyclohexane-1,4-dione and malonitrile.
しかしながら、シクロヘキサン１・４−ジオン
の製造は必ずしも容易ではない。 However, production of cyclohexane 1,4-dione is not always easy.
本発明者は、たとえばベンゾキノンから誘導で
きる１・４−ジ低級アルコキシ−１・４−シクロ
ヘキサジエンが意外にもマロンニトリルと縮合反
応して化合物（）を生成することを発見して本
発明を完成するに至つた。 The present inventor completed the present invention by unexpectedly discovering that 1,4-dilower alkoxy-1,4-cyclohexadiene, which can be derived from benzoquinone, undergoes a condensation reaction with malonitrile to produce the compound (). I came to the conclusion.
本発明は、１・４−ジ低級アルコキシ−１・４
−シクロヘキサジエン（）をマロンニトリルと
縮合させることを特徴とする１・４−ビス（ジシ
アノメチレン）シクロヘキサン（）の製造法で
ある。 The present invention provides 1,4-di-lower alkoxy-1,4
- A method for producing 1,4-bis(dicyanomethylene)cyclohexane (), which is characterized by condensing cyclohexadiene () with malonitrile.
本発明の反応は次のように式示される。 The reaction of the present invention is illustrated as follows.
原料化合物（）のジ低級アルコキシ基は反応
の進行と共に離脱するものであるから反応を妨げ
ない限りいずれでもよいが、メトキシ基が一般に
入手し易い。 Since the di-lower alkoxy group of the starting compound () will be removed as the reaction progresses, any type of di-lower alkoxy group may be used as long as it does not interfere with the reaction, but a methoxy group is generally easily available.
化合物（）とマロンニトリルとの反応は両者
を無溶媒もしくは溶媒中で混合、接触させること
によつて行われる。 The reaction between the compound () and malonitrile is carried out by mixing the two without a solvent or in a solvent and bringing them into contact.
反応は触媒によつて促進される。触媒として
は、たとえばβ−アラニン、グリシンなどのアミ
ノ酸や酢酸アンモンなどが挙げられる。 The reaction is accelerated by a catalyst. Examples of the catalyst include amino acids such as β-alanine and glycine, and ammonium acetate.
反応は加熱下に進行しやすく、反応温度は約50
−100℃の範囲で選択するのが望ましい。 The reaction tends to proceed under heating, and the reaction temperature is approximately 50℃.
It is desirable to select within the range of -100℃.
反応の進行と共に化合物の（）の低級アルコ
キシ基は相当するアルコールとなつて離脱するか
ら、所望により蒸溜してアルコールを除きつゝ反
応させてもよい。 As the reaction progresses, the lower alkoxy group in parentheses of the compound separates into the corresponding alcohol, so if desired, the reaction may be carried out while removing the alcohol by distillation.
このようにして、本発明の方法により１・４−
ジ低級アルコキシ−１・４−シクロヘキサジエン
から直接１・４−ビス（ジシアノメチレン）シク
ロヘキサンをほぼ定量的収率で得ることができ
る。 In this way, by the method of the present invention, 1.4-
1,4-bis(dicyanomethylene)cyclohexane can be obtained directly from di-lower alkoxy-1,4-cyclohexadiene in a nearly quantitative yield.
次に実施例を示す。 Next, examples will be shown.
実施例 １
還流冷却器、温度計、滴下漏斗を付けた50ml容
量の四つ口フラスコに１・４−ジメトキシ−１・
４−シクロヘキサジエン2.0ｇとマロンニトリル
1.9ｇを入れ、73−75℃に保ちながら、0.8％β−
アラニン水溶液４mlを約１時間かけて滴下し、そ
の後１時間15分、75℃に保ちながら撹拌を続け
る。Example 1 1,4-dimethoxy-1.
2.0g of 4-cyclohexadiene and malonitrile
Add 1.9g of 0.8% β- while keeping at 73-75℃.
Add 4 ml of aqueous alanine solution dropwise over about 1 hour, then continue stirring while maintaining the temperature at 75°C for 1 hour and 15 minutes.
反応終了後水を注加し、結晶をろ別し、水洗、
次いでエチルエーテルで洗滌したのち、減圧で乾
燥し2.76ｇの結晶を得た。収率93％、m.p.195−
203℃、IR：2207cm-1（Ｃ≡Ｎ伸縮）。本品を１・
４−ビス（ジシアノメチレン）シクロヘキサンの
標品と同定した。 After the reaction is complete, add water, filter out the crystals, wash with water,
After washing with ethyl ether, the crystals were dried under reduced pressure to obtain 2.76 g of crystals. Yield 93%, mp195−
203℃, IR: 2207cm -1 (C≡N expansion and contraction). This product 1・
It was identified as a standard specimen of 4-bis(dicyanomethylene)cyclohexane.
実施例 ２
例１における0.8％β−アラニン水溶液の代り
に0.7％グリシン水溶液４mlを用いるほかは例１
と同様にして１・４−ビス（ジシアノメチレン）
シクロヘキサンの結晶2.73ｇ（収率92.0％）を得
た。Example 2 Example 1 except that 4 ml of 0.7% glycine aqueous solution was used instead of the 0.8% β-alanine aqueous solution in Example 1.
Similarly, 1,4-bis(dicyanomethylene)
2.73 g (yield 92.0%) of cyclohexane crystals were obtained.
Claims (1)
ヘキサジエンをマロンニトリルと縮合させること
を特徴とする１・４−ビス（ジシアノメチレン）
シクロヘキサンの製造法。1 1,4-bis(dicyanomethylene) characterized by condensing 1,4-dilower alkoxy-1,4-cyclohexadiene with malonitrile
Method for producing cyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11065879A JPS5634661A (en) | 1979-08-29 | 1979-08-29 | Preparation of 1,4-bis dicyanomethylene cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11065879A JPS5634661A (en) | 1979-08-29 | 1979-08-29 | Preparation of 1,4-bis dicyanomethylene cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5634661A JPS5634661A (en) | 1981-04-06 |
| JPS636543B2 true JPS636543B2 (en) | 1988-02-10 |
Family
ID=14541210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11065879A Granted JPS5634661A (en) | 1979-08-29 | 1979-08-29 | Preparation of 1,4-bis dicyanomethylene cyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5634661A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230040762A (en) * | 2021-09-16 | 2023-03-23 | 현대제철 주식회사 | Vehicle Structure and Method of Manufacturing the same |
| KR20230040763A (en) * | 2021-09-16 | 2023-03-23 | 현대제철 주식회사 | Vehicle Structure and Method of Manufacturing the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59100740A (en) * | 1982-11-24 | 1984-06-11 | 河本製機株式会社 | Control of warp yarn winding tension force |
| JPS6170038A (en) * | 1984-09-10 | 1986-04-10 | 三菱レイヨン株式会社 | Automatic winding method and device for warping machine |
| JPS61296138A (en) * | 1985-06-25 | 1986-12-26 | 株式会社 エンジニアリングト−ヨ− | Wefting machine |
-
1979
- 1979-08-29 JP JP11065879A patent/JPS5634661A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230040762A (en) * | 2021-09-16 | 2023-03-23 | 현대제철 주식회사 | Vehicle Structure and Method of Manufacturing the same |
| KR20230040763A (en) * | 2021-09-16 | 2023-03-23 | 현대제철 주식회사 | Vehicle Structure and Method of Manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5634661A (en) | 1981-04-06 |
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