JPS58185550A - Preparation of ethylene cyanohydrin - Google Patents
Preparation of ethylene cyanohydrinInfo
- Publication number
- JPS58185550A JPS58185550A JP57069410A JP6941082A JPS58185550A JP S58185550 A JPS58185550 A JP S58185550A JP 57069410 A JP57069410 A JP 57069410A JP 6941082 A JP6941082 A JP 6941082A JP S58185550 A JPS58185550 A JP S58185550A
- Authority
- JP
- Japan
- Prior art keywords
- oxabispropionitrile
- thermal decomposition
- basic catalyst
- weakly basic
- ethylene cyanohydrin
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
こノ発明はエチレンシアノヒドリンを得る新規な熱分解
反応に関するものである、
エチレンシアノヒドリンは抽出溶剤、ファインケミカル
ズ製品の原料等として有用であり、その製造法としては
エチレンクロルヒドリンとシアン化アルカリとの反応、
エチレンオキノドとシアノ化水素との反応が古（から知
られている。[Detailed Description of the Invention] This invention relates to a novel thermal decomposition reaction for obtaining ethylene cyanohydrin. Ethylene cyanohydrin is useful as an extraction solvent and a raw material for fine chemical products, and the method for producing it is based on ethylene chlorohydrin. reaction with alkali cyanide,
The reaction between ethylene oxide and hydrogen cyanide has been known since ancient times.
シアノ化合物を用いない製法としてはアクリロニトリル
の水和法（米国特許３０２４２６７）が知られているが
、この反応は３，３−オキサビスプロピ万ニトリルを生
じやす（、その生成なおさえ・二２仁めには大閂の水を
使用しなければならず、工ｆ−Ｖンシアノヒドリンの精
製コストが大きくなりや′セい。As a production method that does not use cyano compounds, the hydration method of acrylonitrile (US Pat. No. 3,024,267) is known, but this reaction tends to produce 3,3-oxabispropimannitrile (and it is difficult to suppress its production and to In this case, large-scale water must be used, which increases the cost of refining cyanohydrin.
Ｉ発明はこれら従来の合成法と異なり、熱分解反応によ
りエチレンシアノヒドリンな得るものでｔ・る。即ち、
出発物として３．３−オキサビスプロピオニトリルを用
い、弱塩基触媒の存在下にこれを′熱分解すれば、アク
リロニトリルと共にエチレン／アノヒドリンが得られる
。Unlike these conventional synthesis methods, the present invention produces ethylene cyanohydrin through a thermal decomposition reaction. That is,
By using 3,3-oxabispropionitrile as a starting material and thermally decomposing it in the presence of a weak basic catalyst, ethylene/anohydrin is obtained together with acrylonitrile.
０（ＣＨ２ＣＨ２ＣＮ）２−→ＨＯＣＨ２ＣＨ２ＣＮ十
ＣＨ２＝ＣＨＣＮ出発物の３．３〜オキサビスプロピオ
ニトリルはアクロニトリルの水利反応によって容易に得
られる（例えば、有機合成化学協会誌、昭和３８年３０
６自参照）。0(CH2CH2CN)2-→HOCH2CH2CN+CH2=CHCN The starting material 3.3-oxabispropionitrile can be easily obtained by a water-use reaction of acronitrile (for example, Journal of the Society of Organic Synthetic Chemistry, 1963, 30).
6).
３．３−オキサビスプロピオニトリルは、中性又は弱酸
性下では熱に安定で、分解せずに蒸溜精製−（′Ｉきる
。一方、強塩基の存在下に加熱すると分解してアクリロ
ニトリルと水とを生じ、また多量の中介物を生ずること
がわかった。3.3-Oxabispropionitrile is thermally stable under neutral or weakly acidic conditions and can be purified by distillation without decomposition.On the other hand, when heated in the presence of a strong base, it decomposes to form acrylonitrile. It was found that water and a large amount of intermediates were produced.
しかるに、弱塩基の存在下に加熱すると、この弱塩基の
触媒作用の下にエチレン／アノしトリ／とアクリロニト
リルな生ずる熱分ｌｉｄ反応が起ることが新たに見出さ
れた。弱塩基としては強塩基と弱酸とに由来する弱塩基
性の塩、ｔｌＪえば、酢酸ナトリウム、酢酸カリウム、
酢酸テトラエチルアンモニウムなどが好Ｍ４である。弱
酸として匪醒以外のカルボン酸１．炭酸など任意の弱酸
を用（・ることかでき、強塩基もアルカリ又はアルカリ
土類金属、第四級アンモニウム・、その他の’ｉｆｉ塩
基（１） ＨＵなど）などを月４いることができ、弱【
疲とジ虫塩基を罰１合わせた結果、例えば炭酸水素ナト
リウムの如く弱ＩＭ革性になるものであればよ（・。ま
た、塩の他にも水酸化力ルンウムの如き熱分解温ｒ隻で
女ボな弱塩基は）咄媒として用（・ることができる１弱
塩基触媒の有効な１史用ｉ′は実願にもとづいてきめれ
ばよいが、連結３．３−オキサビスプロピオニトリルに
対して０．１％〜ｌＯ％、特に０５〜５％である。However, it has been newly discovered that when heated in the presence of a weak base, a thermal lid reaction occurs under the catalytic action of the weak base to produce ethylene/anothitri/acrylonitrile. Weak bases include weak base salts derived from strong bases and weak acids, such as sodium acetate, potassium acetate,
Tetraethylammonium acetate and the like are preferred M4. 1. Carboxylic acids other than diluting as weak acids. Any weak acid such as carbonic acid can be used, and strong bases such as alkali or alkaline earth metals, quaternary ammonium, and other 'ifi bases (1) HU, etc. can be used. weak【
As long as the combination of fatigue and oxidizing base results in weak IM properties, such as sodium bicarbonate (...Also, in addition to salt, pyrolysis temperatures such as hydroxide, etc. The effective i' of the weak base catalyst can be determined based on the actual application, but the linked 3,3-oxabispro 0.1% to 10%, in particular 05 to 5%, based on pionitrile.
熱分解温度は１２０〜２００″Ｃの温度範囲で実施する
ことができるが、１４０〜１６０℃程度が好ましく、）
蝦（媒の（Φ知、藺用祉とあわせて実馴にもとづき選べ
ばよ見・。The thermal decomposition temperature can be carried out in the temperature range of 120 to 200"C, but it is preferably about 140 to 160"C.)
Please choose based on your actual experience, along with your knowledge and knowledge.
本発明は３．３−オキサビスプロピオニトリルの゛中凸
に弱塩基触媒を加え、加熱して実施することもできるが
、アクリロニトリルの水和による：（，３−オキサビス
プロピオニトリルの合成反応液を用いてもよい。例えば
、水酸化ナトリウム触媒を用いてアクリロニトリルを水
和して得た反応液に酢酸を加えれば弱塩基性の酢酸ナト
リウム触媒が系内で形成され、低沸分を除去した後、あ
るいは除去しながら加熱して熱分解をおこなう。The present invention can also be carried out by adding a weak base catalyst to the convex center of 3.3-oxabispropionitrile and heating, but the synthesis of 3-oxabispropionitrile by hydration of acrylonitrile A reaction solution may also be used.For example, if acetic acid is added to the reaction solution obtained by hydrating acrylonitrile using a sodium hydroxide catalyst, a weakly basic sodium acetate catalyst will be formed in the system, and the low boiling point will be removed. Thermal decomposition is performed by heating after or while removing.
熱分解のやり方は、実施例では減圧の分解蒸留方式を示
した。このように減圧で加熱し、生成するアクリロニト
リルとエチレンシアノヒドリンを留出させながら熱分解
をおこなうと高沸分の生成が少（有利である。必要に応
じ連続的熱分解など公知の反応技術を適用できることは
もちろんである。As for the method of thermal decomposition, a reduced pressure decomposition distillation method is shown in the examples. In this way, heating under reduced pressure and performing thermal decomposition while distilling out the acrylonitrile and ethylene cyanohydrin produced produces fewer high-boiling components (it is advantageous).If necessary, known reaction techniques such as continuous thermal decomposition can be applied. Of course it is possible.
実輛例 １
３．３−オキサビスプロピオニトリル（純度Ｃ子８３％
）３ｏ、ｏ、９、酢酸テトラエチルアンモニウム０．５
９の混合物をクライゼン型蒸溜装置を用い、減圧下１／
ＩＱ〜１５０°（油浴）１コて加熱し、分解蒸留を行っ
たところ、１５．９７．９油秋物をイ（）だ（留出温度
１００〜１０５０／ｌＯｍＩＩＩＩＩ９）。Actual example 1 3.3-oxabispropionitrile (purity C 83%
) 3o, o, 9, tetraethylammonium acetate 0.5
Using a Claisen type distillation apparatus, the mixture of 9 was distilled to 1/2 under reduced pressure.
When heated at IQ~150° (oil bath) and subjected to decomposition distillation, 15.97.9 oil fall was obtained (distillation temperature 100~1050/lOmIII9).
ガスクロマトグラフィー分析結果はエチレンシアノヒド
リン’ｌ ２．．１ ％、３．３−オキサビスプロピオ
ニトリル：つ（）％で、エチレン７アノヒドリン１（ｖ
率は８５・１チであった。Gas chromatography analysis results show ethylene cyanohydrin'l 2. ．． 1%, 3.3-oxabispropionitrile: 2()%, ethylene 7 anohydrin 1(v
The rate was 85.1ch.
なお、アセトン−ドライアイス冷媒系を用いｔニドラッ
プ（′こ１す１１．７ｇのアクリロニトリルを回収した
。残留分は１．５９であった。Incidentally, using an acetone-dry ice refrigerant system, 11.7 g of acrylonitrile was recovered by t-nidrapping. The residual amount was 1.59.
実施例 ２
：３，３−オキザビスプロビオニトリル３０ｇ及び酢酸
ナトリウム０３ｇを混合物を減圧下１．１０〜１５０に
て分解蒸留した。Example 2: A mixture of 30 g of 3,3-oxabisprobionitrile and 03 g of sodium acetate was subjected to decomposition distillation under reduced pressure at 1.10 to 150 ml.
＋ ｆ） ｔ）〜１１０°１５朋Ｈ夕留出分１７．１５
９（ａ ｃ 結’４４、エチレンシアノヒドリン７４６
チ、１（３−オキサビスプロピオニ） ＩＪル２１５％
）を（ｉｆだ。エチレンンアノヒドリン収率７５１チ、
回収アクリロニトリル１０．５９、残留分１．１．Ｓ＋
、。+ f) t) ~ 110° 15 Tomo H evening distillate 17.15
9 (a c ’44, ethylene cyanohydrin 746
1 (3-oxabispropioni) IJ 215%
) is (if. Ethylene anohydrin yield is 751 cm,
Recovered acrylonitrile 10.59, residual 1.1. S+
,.
ｊ′怖例 ３
アクリロニトリル２６５ｇ、水１８．０９、アセトニト
リル１００ｇ、４０％テトラエチルアンモニウムヒドロ
キシド０．４ｇの混合物を５５〜６０°にて６時間反応
させた。酢酸な（１，］ 、５＋ １（１え、減圧下で
低沸分（未反応アクリロニトリル、アセトニトリル、水
）を留去し、粗３，３−オキサビスプロピオニトリル２
５．４４ｇを得た。j' Example 3 A mixture of 265 g of acrylonitrile, 18.09 g of water, 100 g of acetonitrile, and 0.4 g of 40% tetraethylammonium hydroxide was reacted at 55 to 60° for 6 hours. Acetic acid (1,), 5 + 1 (1), low-boiling components (unreacted acrylonitrile, acetonitrile, water) were distilled off under reduced pressure to obtain crude 3,3-oxabispropionitrile 2
5.44g was obtained.
シアノエチル化粗収率は８５．１％。The cyanoethylation crude yield was 85.1%.
この粗液を減圧下１４０〜１５ｏ０に加熱し、分解蒸留
した。１００〜１０５°／１ｏｎｉ町留出部＋ ４．１
ｇ（ＧＣ：エチレンシアノヒドリン９２３チ、３．３
〜才キサビスプロピオニトリル２７％）、エチレンシア
ノヒドリンの熱分解時の収率は８９３チ。This crude liquid was heated under reduced pressure to 140-15o0 and subjected to decomposition distillation. 100~105°/1oni town distillation department + 4.1
g (GC: ethylene cyanohydrin 923 g, 3.3
~ xabispropionitrile (27%), the yield during thermal decomposition of ethylene cyanohydrin was 893.
比較例 １
３．３−オキサビスプロピオニトリル３０．９及び水酸
化す） ＩＪウム０１５９の混合物を減圧ド（１０１１
ｒＭＨｇ ） １４０〜１５０’に加熱ｔ、 タト、
Ｚろ、アクリｏ二）リルと水の混合物１８４ｙ回収シタ
のみで、エチレンシアノヒドリンは得られなかった。ま
た、残留した高沸分がｔ ｏ、 ｏ ｇあった。Comparative Example 1 A mixture of 3.3-oxabispropionitrile 30.9 and hydroxide) IJium 0159 was heated under reduced pressure (1011
rMHg) Heat to 140-150't, Tato,
Only a mixture of acrylic acid and water was recovered, and no ethylene cyanohydrin was obtained. In addition, there were t o, o g of high-boiling components remaining.
特許出願人 ダイセル化学工業株式会社patent applicant Daicel Chemical Industries, Ltd.
Claims (1)
在下熱分解することを特徴とするエチレンシアノヒドリ
ンの製造法。3. A method for producing ethylene cyanohydrin, which comprises thermally decomposing 3-oxabispropionitrile in the presence of a weak base catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069410A JPS58185550A (en) | 1982-04-23 | 1982-04-23 | Preparation of ethylene cyanohydrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069410A JPS58185550A (en) | 1982-04-23 | 1982-04-23 | Preparation of ethylene cyanohydrin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58185550A true JPS58185550A (en) | 1983-10-29 |
Family
ID=13401804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57069410A Pending JPS58185550A (en) | 1982-04-23 | 1982-04-23 | Preparation of ethylene cyanohydrin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58185550A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4709072A (en) * | 1985-06-27 | 1987-11-24 | Basf Aktiengesellschaft | Joint preparation of ethylene cyanohydrin and its ethers |
| JP2001233844A (en) * | 2000-01-25 | 2001-08-28 | F Hoffmann La Roche Ag | Method for producing 3-hydroxypropionitrile |
| WO2003087041A1 (en) * | 2002-04-18 | 2003-10-23 | Dsm Ip Assets B.V. | Continuous process for the manufacture of 3-hydroxy propionitrile |
-
1982
- 1982-04-23 JP JP57069410A patent/JPS58185550A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4709072A (en) * | 1985-06-27 | 1987-11-24 | Basf Aktiengesellschaft | Joint preparation of ethylene cyanohydrin and its ethers |
| JP2001233844A (en) * | 2000-01-25 | 2001-08-28 | F Hoffmann La Roche Ag | Method for producing 3-hydroxypropionitrile |
| US6462219B2 (en) | 2000-01-25 | 2002-10-08 | Roche Vitamins, Inc. | Process for producing 3-hydroxypropionitrile |
| EP1120404A3 (en) * | 2000-01-25 | 2003-05-14 | F. Hoffmann-La Roche Ag | Preparation of hydroxypropionitrile |
| WO2003087041A1 (en) * | 2002-04-18 | 2003-10-23 | Dsm Ip Assets B.V. | Continuous process for the manufacture of 3-hydroxy propionitrile |
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