JPH0597734A - Allyl rearrangement of allyl alcohols - Google Patents
Allyl rearrangement of allyl alcoholsInfo
- Publication number
- JPH0597734A JPH0597734A JP3257536A JP25753691A JPH0597734A JP H0597734 A JPH0597734 A JP H0597734A JP 3257536 A JP3257536 A JP 3257536A JP 25753691 A JP25753691 A JP 25753691A JP H0597734 A JPH0597734 A JP H0597734A
- Authority
- JP
- Japan
- Prior art keywords
- allyl
- rearrangement
- phenyl
- alcohols
- perrhenate
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
(57)【要約】
【目的】 アリルアルコール類をアリル転位させる新規
な触媒を提供することを目的とする。
【構成】 アリルアルコール類をアリル転位させる際
に、過レニウム酸塩およびアリールスルホン酸を触媒と
して用いることを特徴とする。(57) [Summary] [Objective] The object is to provide a novel catalyst for allyl rearrangement of allyl alcohols. [Structure] When allyl alcohols are subjected to allyl rearrangement, perrhenate and arylsulfonic acid are used as catalysts.
Description
【０００１】[0001]
【産業上の利用分野】本発明はアリルアルコール類のア
リル転位方法に関する。この方法は種々の農薬、医薬の
中間体等を合成するのに有効な方法である。FIELD OF THE INVENTION The present invention relates to a method for allyl rearrangement of allyl alcohols. This method is an effective method for synthesizing various agricultural chemicals, pharmaceutical intermediates and the like.
【０００２】[0002]
【従来の技術】アリルアルコール類をアリル転位させる
方法としては、強ブレンステッド酸を用いる方法（Bul
l. Chem. Soc. Jpn., 47, 226 (1974) ）、バナジウム
またはモリブデンの錯体を用いる方法（Bull. Chem. So
c. Jpn., 58, 844(1985) ）等が知られている。2. Description of the Related Art As a method for allyl rearrangement of allyl alcohols, a method using strong Bronsted acid (Bul
L. Chem. Soc. Jpn., 47, 226 (1974)), a method using a complex of vanadium or molybdenum (Bull. Chem. So.
c. Jpn., 58, 844 (1985)) and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来公
知の触媒系を用いる方法は、化合物によって転位活性が
異なり、必ずしも満足できるものではない。かかる事情
に鑑み、アリルアルコール類のアリル転位方法について
鋭意検討した結果、過レニウム酸塩およびアリールスル
ホン酸からなる新触媒を見出し、本発明を完成するに至
った。However, the method using a conventionally known catalyst system is not always satisfactory because the rearrangement activity differs depending on the compound. In view of such circumstances, as a result of extensive studies on a method for allylic rearrangement of allyl alcohols, a new catalyst composed of perrhenate and arylsulfonic acid was found, and the present invention was completed.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、過レ
ニウム酸塩およびアリールスルホン酸を触媒として用い
ることを特徴とする一級または二級アリルアルコール類
のアリル転位方法である。That is, the present invention is a method for ally rearrangement of primary or secondary allyl alcohols, which comprises using perrhenate and aryl sulfonic acid as catalysts.
【０００５】本発明に用いられるアリルアルコール類と
しては一級または二級アリルアルコールであって、三級
アリルアルコールは急速に脱水反応を起こし好ましくな
い。一級または二級アリルアルコールであれば特に限定
されるものではないが、例えばアリルアルコールとして
は、５−フェニル−２−ペンテン−１−オール等が、二
級アリルアルコールとしては５−フェニル−３−ヘキセ
ン−２−オール、５−ベンジル−２−シクロヘキセン−
１−オール等が挙げられる。The allyl alcohols used in the present invention are primary or secondary allyl alcohols, and tertiary allyl alcohol is not preferable because it rapidly undergoes dehydration reaction. It is not particularly limited as long as it is a primary or secondary allyl alcohol. For example, as allyl alcohol, 5-phenyl-2-penten-1-ol and the like, and as secondary allyl alcohol, 5-phenyl-3- Hexen-2-ol, 5-benzyl-2-cyclohexene-
1-all etc. are mentioned.
【０００６】本発明に用いられる過レニウム酸塩として
は、過レニウム酸テトラアンモニウム、過レニウム酸テ
トラメチルアンモニウム、過レニウム酸テトラエチルア
ンモニウム、過レニウム酸テトラプロピルアンモニウ
ム、過レニウム酸テトラブチルアンモニウム、過レニウ
ム酸テトラペンチルアンモニウム等が挙げられる。The perrhenate used in the present invention includes tetraammonium perrhenate, tetramethylammonium perrhenate, tetraethylammonium perrhenate, tetrapropylammonium perrhenate, tetrabutylammonium perrhenate and perrhenium. Acid tetrapentylammonium etc. are mentioned.
【０００７】本発明に用いられるアリールスルホン酸と
しては、ベンゼンスルホン酸、パラトルエンスルホン酸
およびメタニトロベンゼンスルホン酸等が挙げられる。Examples of the aryl sulfonic acid used in the present invention include benzene sulfonic acid, paratoluene sulfonic acid and metanitrobenzene sulfonic acid.
【０００８】本発明は通常、溶媒の存在下に行われる。
溶媒は特に限定されるものではないが、ジクロルメタン
が好ましく用いられる。The present invention is usually carried out in the presence of a solvent.
The solvent is not particularly limited, but dichloromethane is preferably used.
【０００９】反応は通常、アリルアルコール類を溶解し
たジクロルメタン溶液と過レニウム酸塩とアリールスル
ホン酸のジクロルメタン溶液とを混合し、常温または必
要により加熱して溶媒の還流下に攪拌して行われる。The reaction is usually carried out by mixing a solution of dichloromethane in which allyl alcohol is dissolved, a solution of perrhenate and a solution of arylsulfonic acid in dichloromethane, and heating the mixture at room temperature or if necessary while stirring under reflux of the solvent.
【００１０】二級アリルアルコールの場合は反応時間が
長いと脱水生成物が多くなるので、化合物によって反応
時間を適宜制限することが好ましい。In the case of secondary allyl alcohol, a long reaction time results in a large amount of dehydrated products, so it is preferable to appropriately limit the reaction time depending on the compound.
【００１１】[0011]
【発明の効果】本発明の過レニウム酸およびアリールス
ルホン酸からなる触媒は一級または二級アリルアルコー
ル類のアリル転位反応に優れた活性を有し、その利用価
値は大きい。INDUSTRIAL APPLICABILITY The catalyst of the present invention comprising perrhenic acid and arylsulfonic acid has excellent activity for the allyl rearrangement reaction of primary or secondary allyl alcohols, and its utility value is great.
【００１２】[0012]
【実施例】以下、本発明を実施例でさらに詳細に説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１３】実施例１ ５−フェニル−２−ペンテン−１−オール（５３．５ｍ
ｇ，０．３３ｍｍｏｌ）のジクロルメタン（２ｍｌ）溶
液と、過レニウム酸テトラブチルアンモニウム（Inorga
nic Synthesis 26, 391 (1989)に記載の方法により合成
した。）（１６．６ｍｇ，０．０３３ｍｍｏｌ）とパラ
トルエンスルホン酸一水和物（３．３ｍｇ，０．０１７
ｍｍｏｌ）のジクロルメタン（１．５ｍｌ）溶液を混合
し、室温で２時間攪拌して転位反応を行った。Example 1 5-Phenyl-2-penten-1-ol (53.5 m
g, 0.33 mmol) in dichloromethane (2 ml) and tetrabutylammonium perrhenate (Inorga
It was synthesized by the method described in nic Synthesis 26, 391 (1989). ) (16.6 mg, 0.033 mmol) and paratoluenesulfonic acid monohydrate (3.3 mg, 0.017)
Dichloromethane (1.5 ml) solution of (mmol) was mixed and stirred at room temperature for 2 hours to carry out rearrangement reaction.
【００１４】反応液に飽和炭酸水素ナトリウム溶液とジ
エチルエーテルを加えて攪拌した。有機層を塩水で洗
い、無水硫酸ナトリウムで乾燥した。次いで溶媒のジク
ロルメタンを真空に引いて除き、得られた粗生成物を薄
層クロマトグラフ（シリカゲル、展開液はヘキサンと酢
酸エチルが５：１の溶液）で転位生成物を分離した。転
位生成物である５−フェニル−１−ペンテン−３−オー
ルが収率５３％で得られた。原料の５−フェニル−２−
ペンテン−１−オールが３３％残っていた。A saturated sodium hydrogen carbonate solution and diethyl ether were added to the reaction solution and the mixture was stirred. The organic layer was washed with brine and dried over anhydrous sodium sulfate. Then, the solvent dichloromethane was removed by drawing a vacuum, and the obtained crude product was separated into rearrangement products by thin layer chromatography (silica gel, the developing solution was a solution of hexane and ethyl acetate of 5: 1). The rearranged product, 5-phenyl-1-penten-3-ol, was obtained with a yield of 53%. Raw material 5-phenyl-2-
33% of the penten-1-ol remained.
【００１５】反応を更に長く行っても転位生成物である
５−フェニル−１−ペンテン−３−オールと残存する原
料である５−フェニル−２−ペンテン−１−オールの割
合が変わらないことから平衡関係が存在するものと考え
られる。なお、過レニウム酸テトラブチルアンモニウム
またはパラトルエンスルホン酸一水和物単独では転位反
応は起こらなかった。Since the rearrangement product 5-phenyl-1-penten-3-ol and the remaining raw material 5-phenyl-2-penten-1-ol do not change in proportion even if the reaction is carried out for a longer period of time. It is considered that there is an equilibrium relationship. The rearrangement reaction did not occur with tetrabutylammonium perrhenate or paratoluenesulfonic acid monohydrate alone.
【００１６】実施例２ ５−フェニル−２−ペンテン−１−オールの代わりに６
−フェニル−３−ヘキセン−２−オールを用い、５分間
攪拌反応した以外は実施例１と同様に行った。結果は６
−フェニル−２−ヘキセン−４−オールが４０％の収率
で得られ、原料が５６％残った。なお、反応を１８時間
行ったところ、６−フェニル−２，４−ヘキサジエンが
６６％、６−フェニル−１，３−ヘキサジエンが１７％
の収率で得られた。Example 2 6 in place of 5-phenyl-2-penten-1-ol
The same procedure as in Example 1 was performed except that -phenyl-3-hexen-2-ol was used and the reaction was carried out with stirring for 5 minutes. The result is 6
-Phenyl-2-hexen-4-ol was obtained in a yield of 40%, leaving 56% starting material. When the reaction was carried out for 18 hours, 6-phenyl-2,4-hexadiene was 66% and 6-phenyl-1,3-hexadiene was 17%.
It was obtained with a yield of.
【００１７】実施例３ ５−フェニル−２−ペンテン−１−オールの代わりに６
−ベンジル−２−シクロヘキセン−１−オールを用い、
５分間攪拌反応した以外は実施例１と同様に行った。結
果は４−ベンジル−２−シクロヘキセン−１−オールが
４９％、５−ベンジル−１，３−シクロヘキサジエンお
よび３−ベンジリデン−１−シクロヘキセンの脱水生成
物が１０％の収率で得られ、原料が３３％残った。な
お、反応を２３時間行ったところ、脱水生成物が７５％
の収率で得られた。Example 3 6 in place of 5-phenyl-2-penten-1-ol
-Benzyl-2-cyclohexen-1-ol,
The same procedure as in Example 1 was carried out except that the reaction was carried out with stirring for 5 minutes. As a result, 49% of 4-benzyl-2-cyclohexen-1-ol and a dehydration product of 5-benzyl-1,3-cyclohexadiene and 3-benzylidene-1-cyclohexene were obtained in a yield of 10%. Remained 33%. When the reaction was performed for 23 hours, the dehydration product was 75%.
It was obtained with a yield of.
【００１８】比較例１ ５−フェニル−２−ペンテン−１−オールの代わりに６
−フェニル−２−メチル−３−ヘキセン−２−オールを
用いて３０分間反応行ったところ、脱水生成物である６
−フェニル−２−メチル−１、３−ヘキサジエンが９５
％の収率で得られた。Comparative Example 1 6 instead of 5-phenyl-2-penten-1-ol
When a reaction was carried out for 30 minutes using -phenyl-2-methyl-3-hexen-2-ol, it was a dehydration product 6
-Phenyl-2-methyl-1,3-hexadiene 95
Obtained in a yield of%.
Claims (1)
酸を触媒として用いることを特徴とする一級または二級
アリルアルコール類のアリル転位方法。1. A method for allyl rearrangement of primary or secondary allyl alcohols, which comprises using perrhenate and arylsulfonic acid as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3257536A JPH0597734A (en) | 1991-10-04 | 1991-10-04 | Allyl rearrangement of allyl alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3257536A JPH0597734A (en) | 1991-10-04 | 1991-10-04 | Allyl rearrangement of allyl alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597734A true JPH0597734A (en) | 1993-04-20 |
Family
ID=17307650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3257536A Pending JPH0597734A (en) | 1991-10-04 | 1991-10-04 | Allyl rearrangement of allyl alcohols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597734A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112729A (en) * | 2003-10-02 | 2005-04-28 | Japan Science & Technology Agency | Method for producing rearranged unsaturated compound |
-
1991
- 1991-10-04 JP JP3257536A patent/JPH0597734A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112729A (en) * | 2003-10-02 | 2005-04-28 | Japan Science & Technology Agency | Method for producing rearranged unsaturated compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5110987A (en) | Method of preparing sphingosine derivatives | |
| JPS6127384B2 (en) | ||
| JPH0597734A (en) | Allyl rearrangement of allyl alcohols | |
| US4970345A (en) | Process for preparing oxocyclopentene derivatives | |
| SU638597A1 (en) | 4-methyl-2-propenyltetrahydropyranol-4 as fragrant substance for perfumery compositions | |
| JP3055248B2 (en) | Method for producing α, β-unsaturated carbonyl compound | |
| SU643503A1 (en) | Carbamates of 4-b-oxy-2,9-dioxatricyclo-(4,3,1,03,7)-decanes showing sedative-hypnotic activity | |
| Greaves et al. | Synthesis and reactions of allenic amides: Allenes-XXXI | |
| US2917544A (en) | Method of transforming 4-(alpha-hydroxybenzal) oxazoline-5-one compounds into n-acylated aminodiols | |
| IL46789A (en) | 3,5-bis-ethylenedioxy-13beta-alkyl-4,5-seco-delta9,11gonadien-17-ones | |
| SU1705271A1 (en) | Method of primary @@@-acetylene alcohols synthesis | |
| JPS61118348A (en) | Manufacture of hydroxymethylenealkoxyacetic acid ester | |
| US3706780A (en) | Phenyldialkylbicyclo-(2,2,2)-oct-2-ene nitriles | |
| US4725689A (en) | Preparation of 2-amino-3-cyano-5-dialkoxymethylpyrazines and intermediates for this method | |
| JPS6054361A (en) | Production of indole derivative | |
| SU767100A1 (en) | Method of purifying papaverine base | |
| SU570592A1 (en) | Method of preparing alkyl esters of propargyl alcohol | |
| SU438249A1 (en) | The method of obtaining adamantyl-1-aldehyde | |
| SU598864A1 (en) | Method of obtaining citral and methylcitral | |
| SU655306A3 (en) | Method of obtaining esters of carbanilic acid | |
| JPS61197573A (en) | 5,6-epoxidized trans-vitamin d3 | |
| JPH01308249A (en) | Production of 7-hydroxyindole-2-carboxylic acid compound | |
| JPH0528693B2 (en) | ||
| JP2001114754A (en) | Method for producing S-alkylisothiourea | |
| JPS6143336B2 (en) |