JPS63130551A - Production of 4-pentenal compound - Google Patents
Production of 4-pentenal compoundInfo
- Publication number
- JPS63130551A JPS63130551A JP61274599A JP27459986A JPS63130551A JP S63130551 A JPS63130551 A JP S63130551A JP 61274599 A JP61274599 A JP 61274599A JP 27459986 A JP27459986 A JP 27459986A JP S63130551 A JPS63130551 A JP S63130551A
- Authority
- JP
- Japan
- Prior art keywords
- pentenal
- alumina
- compound
- solid acid
- formula
- 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.)
- Granted
Links
- -1 4-pentenal compound Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011973 solid acid Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229940085991 phosphate ion Drugs 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 9
- UADJTDURPOSPRM-UHFFFAOYSA-N 2-ethylpent-4-enal Chemical compound CCC(C=O)CC=C UADJTDURPOSPRM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 15
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 10
- QUMSUJWRUHPEEJ-UHFFFAOYSA-N 4-Pentenal Chemical compound C=CCCC=O QUMSUJWRUHPEEJ-UHFFFAOYSA-N 0.000 description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DTCCTIQRPGSLPT-ONEGZZNKSA-N (E)-2-pentenal Chemical compound CC\C=C\C=O DTCCTIQRPGSLPT-ONEGZZNKSA-N 0.000 description 2
- RCQKLWAPRHHRNN-UHFFFAOYSA-N 2-Methyl-4-pentenal Chemical compound O=CC(C)CC=C RCQKLWAPRHHRNN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- DTCCTIQRPGSLPT-UHFFFAOYSA-N beta-Aethyl-acrolein Natural products CCC=CC=O DTCCTIQRPGSLPT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- DXSDIWHOOOBQTJ-UHFFFAOYSA-N 2,2-dimethylpent-4-enal Chemical compound O=CC(C)(C)CC=C DXSDIWHOOOBQTJ-UHFFFAOYSA-N 0.000 description 1
- AXKYSFMQQVCVFG-UHFFFAOYSA-N 2-ethyl-2-prop-2-enylhexanal Chemical compound CCCCC(CC)(C=O)CC=C AXKYSFMQQVCVFG-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- XMLSXPIVAXONDL-PLNGDYQASA-N Jasmone Chemical class CC\C=C/CC1=C(C)CCC1=O XMLSXPIVAXONDL-PLNGDYQASA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Chemical class CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
の１
本発明は、４−ペンテナール化合物の新規な製造方法に
関するものである。本発明によって得られる４−ペンテ
ナール化合物は、香料、農薬、医薬品等の合成原料とし
て有用であり、例えばセスキテルペン類、ジャスモン等
の骨格形成に用いることができる。DETAILED DESCRIPTION OF THE INVENTION Part 1: The present invention relates to a novel method for producing a 4-pentenal compound. The 4-pentenal compound obtained by the present invention is useful as a synthetic raw material for fragrances, agricultural chemicals, pharmaceuticals, etc., and can be used, for example, to form the skeleton of sesquiterpenes, jasmone, etc.
差速！１支韮−
アルデヒドの一般的な製造方法としては、オレフィンの
オキソ化法、アルコールの脱水素法およびオルトリン酸
エステルのグリニヤール反応等が知られている。これら
の方法では、副反応が多いため製品の純度が悪くなりや
すく原料に制限があったり、高温下での反応のため異性
化が起こりやすくなったり、さらに工業的には高価な原
Ｌ（を必要とするなど多くの困難や不利益がある。Different speed! As general methods for producing monoaldehydes, olefin oxation methods, alcohol dehydrogenation methods, and Grignard reactions of orthophosphoric acid esters are known. In these methods, the purity of the product tends to deteriorate due to many side reactions, there are restrictions on raw materials, isomerization is likely to occur due to the reaction at high temperatures, and the raw material L (which is expensive for industrial purposes) is There are many difficulties and disadvantages, such as the need for
さらに４−ペンテナール（ヒ合物の製造方法としては、
従来アリール転位を利用する方法が知られており、例え
ばに、Ｃ，Ｂｒａｎｎｏｃｋ、 Ｊ、Ａ＋ｎ、Ｃｈｅｍ
、ＳＯＣ，。Furthermore, as a method for producing 4-pentenal (hypolysate),
Conventionally, methods using aryl rearrangement are known, for example, C, Brannock, J, A+n, Chem.
,SOC,.
８１、３３７９−８３．（Ｉ９５９＞および Ｐ、Ｃ，
ＳＩａｇｎｕｓ ｓｔ、ａｌ、。81, 3379-83. (I959> and P, C,
SIagnus st, al.
５ｙｎｔｈ、 Ｃｏｍｍｕｎ、、 Ｉｔ）（４）、 ２
７３−８．（Ｉ９８１））の報告がある。しかしこれら
の方法は、いずれら均一系の酸触媒を用いるため、工業
的には耐酸性の反応装置が必要となるうえ後処理ら複雑
となっている。5ynth, Commun,, It) (4), 2
73-8. (I981)) has been reported. However, since these methods use a homogeneous acid catalyst, they require an acid-resistant reactor and are complicated in post-treatment.
また２−エチル−４−ペンテナールなどの２位に水素原
子の残っているアルデヒドを合成する場合は著しく収率
が低下する。Furthermore, when an aldehyde having a hydrogen atom remaining at the 2-position, such as 2-ethyl-4-pentenal, is synthesized, the yield decreases significantly.
その池の４−ペンテナール（ヒ合拘の製造方法としては
、アリルブロマイドとイソブチルアルデヒド３アルカリ
の存在下反応させる方法（Ｖ、Ｇ、Ｐ！Ｊ−ｒｏｈ已
ｉＬ、 ａｌ、、 Ｃｈｌ！ｍ、 Ｉｎｄ、、
（Ｉ８）、 ７３１−２．（Ｉ９７！り）が知られ
ているが、この方法は収率が低く４−ペンテナール化合
物の工業的製造方法としては好ましくない。The method for producing 4-pentenal (Higatsu) is a method of reacting allyl bromide with isobutyraldehyde in the presence of 3-alkali (V, G, P! J-roh
iL, al,, Chl! m, Ind,,
(I8), 731-2. (I97!ri) is known, but this method has a low yield and is not preferred as an industrial method for producing 4-pentenal compounds.
日が しようとする口題占
本発明は、通常の反応装置を用い、持に２位に水素原子
のある４−ペンテナール化合物を比較的高収率で工業的
に製造する方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention aims to provide a method for industrially producing a 4-pentenal compound having a hydrogen atom at the 2-position in a relatively high yield using a conventional reaction apparatus. purpose.
本発明は、一般式（■ン
０＼／バ〉
〔式中Ｒ１、Ｒ２は水素原子または炭素数１ないし７の
アルモル基を表し、Ｒ１とＲ２は互いに同一でも相異な
っていてもよい〕
で示さ２’Ｌるジアリルアセタール化合物を固体酸触媒
の存在下に加熱することを特徴とする一般式（〔式中Ｒ
１、Ｒ２は前記定義に同じ〕
で示される４−ペンテナール化合物の製造方法に関する
ものである。The present invention has the following general formula: The general formula ([in the formula, R
1 and R2 are the same as defined above] The present invention relates to a method for producing a 4-pentenal compound represented by the following.
本発明の出発物質となるジアリルアセタール化合物は、
前記一般式（Ｉ）で示される化合物であり、例えばプロ
ピオンアルデヒド、ブチルアルデヒド、イソブチルアル
デヒド、ｎ−バレルアルデヒド、２−エチル−ヘキサナ
ール、２−メチルオクナタールなどのアルデヒドのジア
リルアセタール化合物が挙げられる。The diallyl acetal compound serving as the starting material of the present invention is
Examples of the compound represented by the general formula (I) include diallylacetal compounds of aldehydes such as propionaldehyde, butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethyl-hexanal, and 2-methylocnatal.
一般式（Ｉ）のジアリルアセタール１ヒ合物は、アルデ
ヒドをアリルアルコールでアセタール化することにより
容易に得られる。なお、原料のジアリルアセタール中に
はアセタール化反応の未反応物であるアリルアルコール
やアルデヒドが残留していてもよい。The diallyl acetal compound of general formula (I) can be easily obtained by acetalizing an aldehyde with allyl alcohol. Note that allyl alcohol and aldehyde, which are unreacted products of the acetalization reaction, may remain in the diallyl acetal as a raw material.
本発明の目的１ヒ合物の４−ペンテナール（ヒ金物は一
般式（ｎ）で示される化合物であり、例えば２−メチル
−４−ペンテナール、２−エチル−４＝ペンテナール、
２，２−ジメチル−４−ペンテナール、２−プロピル−
４−ペンテナール、２−エチル−２−ブチル−４−ペン
テナール、２−メチル−２−ヘキシル−４−ペンテナー
ルなどがある。Objects of the present invention 1. 4-pentenal compounds (Arsenal compounds are compounds represented by the general formula (n), such as 2-methyl-4-pentenal, 2-ethyl-4=pentenal,
2,2-dimethyl-4-pentenal, 2-propyl-
Examples include 4-pentenal, 2-ethyl-2-butyl-4-pentenal, and 2-methyl-2-hexyl-4-pentenal.
本発明方法において触媒として用いられる固体酸は、［
酸イオンおよびアルミナまたは硫酸イオン、リン酸イオ
ンおよびアルミナを焼成して得られるものである。固体
酸を構成する各原子の比率は、硫酸イオンおよびアルミ
ナの場合、Ｓ ／’ Ａ ｔ；が０．０１ないし０．０
６で、硫酸イオン、リン酸イオンおよびアルミナの場合
、（Ｐ＋Ｓ）、／ＡＱが０．０２ないし０．２、Ｓ 、
／ Ｐが０．０２ないし０．８である。The solid acid used as a catalyst in the method of the present invention is [
It is obtained by firing acid ions and alumina or sulfate ions, phosphate ions and alumina. In the case of sulfate ions and alumina, the ratio of each atom constituting the solid acid is S/'A t; 0.01 to 0.0.
6, in the case of sulfate ion, phosphate ion and alumina, (P+S), /AQ is 0.02 to 0.2, S,
/P is 0.02 to 0.8.
本発明方法において用いる固体酸の使用量は、−ｉ式（
Ｉ）のジアリルアセクール化合物に対して０．１ないし
２０重量％、好ましくは０．５ないし１０重量％である
。固体酸の使用量が２０重量％を超えると分解、重合が
生じやすくなり、また選択率も低下する、０．５重量％
未満では反応が遅くなる。The amount of solid acid used in the method of the present invention is determined by the formula -i (
The amount is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the diallylacecure compound I). If the amount of solid acid used exceeds 20% by weight, decomposition and polymerization will easily occur, and the selectivity will also decrease, 0.5% by weight
If it is less than that, the reaction will be slow.
本発明の固体酸を調製するには、硫酸、リン酸あるいは
それらのアルミニウム塩またはアンモニウム塩などを水
に溶解して得な硫酸イオンまたはリン酸イオンを含む水
溶液にアルミナを加えてよく混合し、乾燥後焼成すれば
よい。焼成温度は３００゛Ｃ以上、好ましくは５００な
いし９００℃であり、焼成時間は工ないし１０時間、好
ましくは２ないし４時間が適当である。得られた固体酸
はそのまま、もしくは２ないし１０倍量の水で煮沸！、
ｆＳｌ’Ａ ：’、＠過水、先して反応に用いる。なお
、固体酸に用いるアルミナは特に限定されないが、英用
上扮木またはビーズ状の２・−アルミナが好ましい６本
発明の反応温度は、１００ないし２００ ’Ｃが好まし
く、１００°Ｃ未満では反応が進行せず、また２ ００
Ｃを超足ると副反応が生じやすくなる。To prepare the solid acid of the present invention, alumina is added to an aqueous solution containing sulfate ions or phosphate ions obtained by dissolving sulfuric acid, phosphoric acid, or their aluminum or ammonium salts in water, and the mixture is thoroughly mixed. It can be fired after drying. The firing temperature is 300°C or higher, preferably 500 to 900°C, and the firing time is approximately 1 to 10 hours, preferably 2 to 4 hours. The obtained solid acid can be used as is or boiled with 2 to 10 times the amount of water! ,
fSl'A:', @perfused water, used in the reaction first. The alumina used for the solid acid is not particularly limited, but 2-alumina in the form of English-grade wood or beads is preferred.6 The reaction temperature in the present invention is preferably 100 to 200'C, and the reaction temperature is less than 100°C. did not progress and 200
If too much C is added, side reactions are likely to occur.
不発明の反応は、以下に示すように脱アリルアルコール
と熱転位反応により目的の４−ペンテナール（ヒ合物が
得られるものである。The uninvented reaction is one in which the desired 4-pentenal (hypolysate) is obtained by a thermal rearrangement reaction with deallylated alcohol, as shown below.
八〇
上記反応器つ）ら明ら７１）なように本発明の方法では
、目的の４−ペンテナール化合物の他にアリルアルコー
ルが副成するので、反応生成物からアリルアルコールを
除く操作が必要となる。本発明における好ましい実施態
様を以下に示すが、この方法に限定されるものではない
。80 As shown in the above-mentioned reactor71), in the method of the present invention, allyl alcohol is produced as a by-product in addition to the target 4-pentenal compound, so an operation to remove allyl alcohol from the reaction product is required. Become. Preferred embodiments of the present invention are shown below, but the present invention is not limited to this method.
原料となるジアリルアセタールと固体酸を充填塔を取り
付けた反応器に仕込み、加熱、攪拌を行い、充填塔より
反応生成物を留出させる。目的の４−ペンテナール化合
物がアリルアルコールと共沸する場合は、反応時に反応
器へ連続的にジアリルアセタールを供給する連続法によ
っても反応させることができる。４−ペンテナール化合
物とアリルアルコールが共沸して留出した場合は、留出
物を精留することにより目的の４−ペンテナール化合物
が得られ、また４−ペンテナール化合物が反応装置中に
残っている場合には、固体酸を濾別した後に蒸留するこ
と仲より目的の４−ペンテナール化合物が得られる。反
応装置に取り付ける充填塔は、原料のジアリルアセター
ルと副成するアリルアルコールとを分離できるものであ
ればよい。The raw materials, diallyl acetal and solid acid, are charged into a reactor equipped with a packed column, heated and stirred, and the reaction product is distilled out from the packed column. When the target 4-pentenal compound is azeotropic with allyl alcohol, the reaction can also be carried out by a continuous method in which diallyl acetal is continuously supplied to the reactor during the reaction. When a 4-pentenal compound and allyl alcohol are azeotropically distilled, the desired 4-pentenal compound can be obtained by rectifying the distillate, and the 4-pentenal compound remains in the reaction apparatus. In some cases, the desired 4-pentenal compound can be obtained by filtering off the solid acid and then distilling it. The packed column attached to the reaction apparatus may be any type as long as it can separate diallyl acetal as a raw material and allyl alcohol as a by-product.
すなわち、反応時に生成するアリルアルコールもしくは
アリルアルコールと４−ペンテナール化合物を留出させ
、原料ジアリルアセタールを反応器内に留まるようにさ
せればよい。That is, allyl alcohol or the allyl alcohol and 4-pentenal compound produced during the reaction may be distilled off, and the raw material diallyl acetal may remain in the reactor.
制御
本発明の方法によって効率よく４−ペンテナール化合物
が得られる詳細な作用機構は不明であるが、以下のよう
な理由によるものと思われる。Control Although the detailed mechanism of action by which a 4-pentenal compound is efficiently obtained by the method of the present invention is unknown, it is believed to be due to the following reasons.
すなわち、本発明方法の固体酸がルイス酸として働き、
適度な温度つまり熱転位の進行しやすい温度で脱アリル
アルコールが起こることから、重合しゃすいα−不飽和
エーテル１の濃度を常に低く保ち、重合を防ぐと同時に
速やかに目的の４＝ペンテナ一ル化合物へ転位させるた
めと思われる。That is, the solid acid of the method of the present invention acts as a Lewis acid,
Since deallylated alcohol occurs at a moderate temperature, that is, a temperature at which thermal rearrangement tends to proceed, the concentration of the polymerizable α-unsaturated ether 1 is always kept low to prevent polymerization and at the same time quickly convert the desired 4=pentenal ether. This seems to be due to rearrangement into compounds.
以下に本発明を実施例により詳細に説明する。The present invention will be explained in detail below using examples.
実」［例」−
留出部にガラスピーズを約ｉｏａｍ充填した塔を装着し
たＩＱのフラスコに、アリルアルコールを含む純度８２
．６％のブチルアルデヒドジアリルアセタール５００ｇ
と、固体酸く５重量％の硫酸イオンと１０重量％のリン
酸イオンを担持したγ−アルミナ）１０ｇを仕込み加熱
攪拌を行い、塔頂の温度が１００〜１１０°Ｃの範囲で
留出させると同時に留出量と等量の原料を反応フラスコ
内に滴下した。反応時間５５時間で原料を３５７９．９
５ｇ使用し、留出液量は３１３３９４ｇとなり留出液中
には２−エチル−４−ペンテナール、アリルアルコール
の他に少量のヘキサンおよびブチルアルデヒドジアリル
アセタール、２−ブテニルアリルエーテル等が含まれて
いた。この留出液を精留して２−エチル−４−ペンテナ
ール１５３３．１１ｇ〈理論収率８９．７％）を得た。[Example] - An IQ flask equipped with a column filled with about ioam of glass beads in the distillation section contains allyl alcohol with a purity of 82.
．． 6% butyraldehyde diallyl acetal 500g
and 10 g of solid acid (gamma-alumina carrying 5% by weight of sulfate ions and 10% by weight of phosphate ions) are charged, heated and stirred, and distilled while the temperature at the top of the column is in the range of 100 to 110°C. At the same time, an amount of raw material equivalent to the distilled amount was dropped into the reaction flask. 3579.9% raw material in 55 hours reaction time
5 g was used, and the amount of distillate was 313,394 g. The distillate contained 2-ethyl-4-pentenal, allyl alcohol, and small amounts of hexane, butyraldehyde diallyl acetal, 2-butenyl allyl ether, etc. Ta. This distillate was rectified to obtain 1533.11 g of 2-ethyl-4-pentenal (theoretical yield: 89.7%).
実施例２
約３０ｃｍの充填塔（ガラス製のスパイラル状充填物を
詰めたもの）を取り付けたＩＣの四ツロフラスコに、ブ
チルアルデヒドジアリルアセタール４２５ｇと、固体酸
く５重量％の硫酸イオンと１０％のリン酸イオンを担持
したγ−アルミナ）３０ｇを仕込み、加熱攪拌を行い、
充填塔の塔頂の温度が９５〜１１５°Ｃになるように保
ち、生成物を留出させた。このときの反応液の温度は、
１５Ｏ〜１８５°Ｃであった。Example 2 425 g of butyraldehyde diallyl acetal, 5% by weight of solid acid sulfate ions, and 10% of 30 g of γ-alumina (supporting phosphate ions) was charged, heated and stirred,
The temperature at the top of the packed column was maintained at 95 to 115°C, and the product was distilled out. The temperature of the reaction solution at this time is
The temperature was 150 to 185°C.
留出液中には、アリルアルコール、２−ブテニルアリル
エーテルおよび２−エチル−４−ペンテナールが含まれ
ており、これを精留して、２−エチル−４−ペンテナー
ルを無色透明な液（＊（沸点１３７〜１４０°Ｃ）とし
て１７５ｇ（理論収率６２．５％）得た。The distillate contains allyl alcohol, 2-butenyl allyl ether and 2-ethyl-4-pentenal, which is rectified to produce 2-ethyl-4-pentenal as a colorless and transparent liquid ( *(boiling point 137-140°C) 175g (theoretical yield 62.5%) was obtained.
１哩纏肱１
本発明方法の固体酸を用いることにより、耐酸性でない
通常の反応装置を使用して４−ペンテナール化合物（特
に２位に水素原子の残っている４−ペンテナール（ヒ合
拘）を選択的に高収率かつ工業的に有利に製造すること
ができる。1 By using the solid acid of the method of the present invention, 4-pentenal compounds (especially 4-pentenal with a hydrogen atom remaining at the 2-position) can be prepared using a conventional reaction apparatus that is not acid-resistant. can be selectively produced in high yield and industrially advantageously.
Claims (1)
７のアルキル基を表し、Ｒ＿１とＲ＿２は互いに同一で
も相異なっていてもよい〕 で示されるジアリルアセタール化合物を、硫酸イオンお
よびアルミナ、または硫酸イオン、リン酸イオンおよび
アルミナを焼成して得られる固体酸の存在下に加熱する
ことを特徴とする一般式（II） ▲数式、化学式、表等があります▼（II） 〔式中Ｒ＿１、Ｒ＿２は前記定義に同じ〕 で示される４−ペンテナール化合物の製造方法。 ２、固体酸を構成する原子比が、硫酸イオンおよびアル
ミナの場合、Ｓ／Ａｌが０．０１ないし０．０６で、硫
酸イオン、リン酸イオンおよびアルミナの場合、（Ｐ＋
Ｓ）／Ａｌが０．０２ないし０．２、Ｓ／Ｐが０．０２
ないし０．８の固体酸である特許請求の範囲第１項記載
の方法。[Claims] 1. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_2 represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, and R_1 and R_2 may be the same or different from each other] is heated in the presence of sulfate ions and alumina, or a solid acid obtained by firing sulfate ions, phosphate ions, and alumina. A method for producing a 4-pentenal compound represented by the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R_1 and R_2 are the same as defined above]. 2. When the atomic ratio constituting the solid acid is sulfate ion and alumina, S/Al is 0.01 to 0.06, and when sulfate ion, phosphate ion and alumina are used, (P+
S)/Al is 0.02 to 0.2, S/P is 0.02
The method according to claim 1, wherein the solid acid has a concentration of 0.8 to 0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61274599A JPH0749380B2 (en) | 1986-11-18 | 1986-11-18 | Process for producing 4-pentenal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61274599A JPH0749380B2 (en) | 1986-11-18 | 1986-11-18 | Process for producing 4-pentenal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63130551A true JPS63130551A (en) | 1988-06-02 |
| JPH0749380B2 JPH0749380B2 (en) | 1995-05-31 |
Family
ID=17543982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61274599A Expired - Lifetime JPH0749380B2 (en) | 1986-11-18 | 1986-11-18 | Process for producing 4-pentenal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749380B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4984957A (en) * | 1988-08-08 | 1991-01-15 | Kubota, Ltd. | Work-implement adapter for front loader |
| FR2661408A1 (en) * | 1990-04-27 | 1991-10-31 | Rhone Poulenc Nutrition Animal | PROCESS FOR THE PREPARATION OF CITRAL. |
-
1986
- 1986-11-18 JP JP61274599A patent/JPH0749380B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4984957A (en) * | 1988-08-08 | 1991-01-15 | Kubota, Ltd. | Work-implement adapter for front loader |
| FR2661408A1 (en) * | 1990-04-27 | 1991-10-31 | Rhone Poulenc Nutrition Animal | PROCESS FOR THE PREPARATION OF CITRAL. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0749380B2 (en) | 1995-05-31 |
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