JPH0571572B2 - - Google Patents
Info
- Publication number
- JPH0571572B2 JPH0571572B2 JP1225085A JP22508589A JPH0571572B2 JP H0571572 B2 JPH0571572 B2 JP H0571572B2 JP 1225085 A JP1225085 A JP 1225085A JP 22508589 A JP22508589 A JP 22508589A JP H0571572 B2 JPH0571572 B2 JP H0571572B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- niobic acid
- arylacetaldehyde
- catalyst
- ethylene oxide
- 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
- 239000002253 acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 aryl ethylene oxide Chemical compound 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明はニオブ酸を触媒として利用する異性化
反応により、アリールエチレンオキサイドを出発
原料としてアリールアセトアルデヒドを製造する
ためのアリールエチレンオキサイドの処理方法に
関するものである。
本発明によつて製造されるアリールアセトアル
デヒドはフエニルアラニン等のアミノ酸や香料等
を製造するための中間体として有用である。
〔従来の技術〕
アリールエチレンオキサイドを相当するアリー
ルアセトアルデヒドに異性化するための異性化反
応については、従来、チタン含有ゼオライト（特
開昭59−46238号）、イオン交換樹脂（特開昭57−
18643号）、酸性白土（特公昭49−25932号）等の
触媒を利用する方法が知られている。
しかしながら、これら従来の触媒を利用する方
法は一般的に副反応を充分抑制することが困難で
あり、それらの中で比較的反応成績が良好とされ
ているイオン交換樹脂の場合は耐熱性及び耐溶媒
性の点で触媒自体の安定性に問題があつた。
〔発明が解決しようとする課題〕
本発明に於いて、出発原料及び取得目的物はい
ずれも反応性に富む物質であるため、従来の触媒
を利用する方法では副反応を抑制することが困難
であるか又はある程度抑制し得る場合でも使用す
る触媒自体の安定性が劣る等種々の問題があつ
た。
本発明者等は、これら従来の問題を解決し、緩
和な条件で副生物が少なく且つ収率良く目的物を
取得することが出来るような新規な触媒反応を見
出すことを目的として種々研究を重ねた結果、ニ
オブ酸がアリールエチレンオキサイドのエポキシ
環に対して非常に選択特異的な作用を示し、異性
化反応に対して優れた触媒作用を発揮すると共
に、長時間使用しても活性低下が少なく、取扱の
容易な触媒であることを見出し、本発明を完成し
た。
〔課題を解決するための手段〕
本発明は、
(1) アリールエチレンオキサイドを有機溶媒中で
ニオブ酸を処理してアリールアセトアルデヒド
を製造することを特徴とするアリールアセトア
ルデヒドの製造方法。
(2) ニオブ酸が100〜500℃で焼成処理されたもの
であることを特徴とする上記(1)記載の方法。
に関するものである。
本発明の方法は次の化学式で示すことが出来
る。
[Industrial Application Field] The present invention relates to a method for treating aryl ethylene oxide to produce arylacetaldehyde using aryl ethylene oxide as a starting material through an isomerization reaction using niobic acid as a catalyst. The arylacetaldehyde produced by the present invention is useful as an intermediate for producing amino acids such as phenylalanine, fragrances, and the like. [Prior Art] Regarding the isomerization reaction for isomerizing aryl ethylene oxide to the corresponding arylacetaldehyde, titanium-containing zeolite (Japanese Unexamined Patent Publication No. 59-46238) and ion exchange resin (Unexamined Japanese Patent Application No. 57-1989) have been conventionally used.
18643) and acid clay (Japanese Patent Publication No. 49-25932). However, in general, it is difficult to sufficiently suppress side reactions in methods using these conventional catalysts, and in the case of ion exchange resins, which are said to have relatively good reaction results, they have poor heat resistance and There were problems with the stability of the catalyst itself in terms of solvent properties. [Problem to be solved by the invention] In the present invention, since both the starting raw material and the object to be obtained are highly reactive substances, it is difficult to suppress side reactions using conventional methods using catalysts. Even in cases where it can be suppressed to some extent or to some extent, there have been various problems such as poor stability of the catalyst itself. The present inventors have conducted various studies with the aim of solving these conventional problems and discovering a new catalytic reaction that can obtain the target product under mild conditions with few by-products and high yield. As a result, niobic acid showed a very selective and specific effect on the epoxy ring of aryl ethylene oxide, and exhibited an excellent catalytic effect on the isomerization reaction, with little loss of activity even after long-term use. discovered that the catalyst was easy to handle, and completed the present invention. [Means for Solving the Problems] The present invention provides a method for producing arylacetaldehyde, which comprises: (1) producing arylacetaldehyde by treating arylethylene oxide with niobic acid in an organic solvent. (2) The method described in (1) above, wherein the niobic acid is calcined at 100 to 500°C. It is related to. The method of the present invention can be represented by the following chemical formula.
以下、実施例により本発明を具体的に説明す
る。
実施例 １
100cm3のベンゼンを内容積300cm3の反応容器にい
れ、200℃で空気焼成したニオブ酸触媒250mgとと
もに加熱還流し、その後スチレンオキサイド
8mmolを加え、さらに３時間還流を続けた。生
成物をガスクロマトグラフにより分析したとこ
ろ、6.09mmolのフエニルアセトアルデヒドが生
成していた。（収率76％）。
実施例 ２
100cm3のベンゼンを内容積300cm3反応容器にい
れ、300℃で空気焼成したニオブ酸触媒250mgとと
もに加熱還流し、その後スチレンオキサイド
8mmolを加え、さらに３時間還流を続けた。生
成物をガスクロマトグラフにより分析したとこ
ろ、7.12mmolのフエニルアセトアルデヒドが生
成していた。（収率89％）。
上記実施例に於いて、出発原料のアリールエチ
レンオキサイドと、スチレンオキサイドを利用す
る例を示したが、本発明はスチレンオキサイドの
ベンゼン環に反応に不活性な置換基が結合してい
る化合物の場合も同様に実施し得るものである。
〔発明の効果〕
本発明のニオブ酸を触媒として利用する方法に
よれば、アリールエチレンオキサイドのエポキシ
環部位を非常に効率良く、加水分解又は異性化す
ることが出来る。
Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 100 cm 3 of benzene was placed in a reaction vessel with an internal volume of 300 cm 3 and heated to reflux with 250 mg of niobic acid catalyst calcined in air at 200°C, and then styrene oxide was added.
8 mmol was added and reflux was continued for an additional 3 hours. Analysis of the product by gas chromatography revealed that 6.09 mmol of phenylacetaldehyde had been produced. (yield 76%). Example 2 100 cm 3 of benzene was placed in a 300 cm 3 reaction vessel, heated to reflux with 250 mg of niobic acid catalyst calcined in air at 300°C, and then styrene oxide was added.
8 mmol was added and reflux was continued for an additional 3 hours. Analysis of the product by gas chromatography revealed that 7.12 mmol of phenylacetaldehyde had been produced. (yield 89%). In the above example, an example was shown in which the starting materials aryl ethylene oxide and styrene oxide were used, but the present invention deals with compounds in which a substituent inert to the reaction is bonded to the benzene ring of styrene oxide. can also be implemented in the same way. [Effects of the Invention] According to the method of the present invention using niobic acid as a catalyst, the epoxy ring moiety of aryl ethylene oxide can be hydrolyzed or isomerized very efficiently.
Claims (1)
ニオブ酸で処理してアリールアセトアルデヒドを
製造することを特徴とするアリールアセトアルデ
ヒドの製造方法。 ２ ニオブ酸が100〜500℃で焼成処理されたもの
であることを特徴とする請求項１記載の製造方
法。[Scope of Claims] 1. A method for producing arylacetaldehyde, which comprises producing arylacetaldehyde by treating arylethylene oxide with niobic acid in an organic solvent. 2. The manufacturing method according to claim 1, wherein the niobic acid is calcined at 100 to 500°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1225085A JPH0390042A (en) | 1989-08-31 | 1989-08-31 | Method for treating arylethylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1225085A JPH0390042A (en) | 1989-08-31 | 1989-08-31 | Method for treating arylethylene oxide |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5112073A Division JPH07119182B2 (en) | 1993-04-15 | 1993-04-15 | Method for producing aryl ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0390042A JPH0390042A (en) | 1991-04-16 |
| JPH0571572B2 true JPH0571572B2 (en) | 1993-10-07 |
Family
ID=16823776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1225085A Granted JPH0390042A (en) | 1989-08-31 | 1989-08-31 | Method for treating arylethylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0390042A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4592258B2 (en) * | 2003-05-07 | 2010-12-01 | 出光興産株式会社 | Process for producing 2-alkylalkane-1,2-diols |
| JP4734056B2 (en) * | 2005-07-25 | 2011-07-27 | 出光興産株式会社 | Method for producing 2-position branched long chain alkyl aldehyde |
-
1989
- 1989-08-31 JP JP1225085A patent/JPH0390042A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0390042A (en) | 1991-04-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |