JPS629578B2 - - Google Patents
Info
- Publication number
- JPS629578B2 JPS629578B2 JP55099599A JP9959980A JPS629578B2 JP S629578 B2 JPS629578 B2 JP S629578B2 JP 55099599 A JP55099599 A JP 55099599A JP 9959980 A JP9959980 A JP 9959980A JP S629578 B2 JPS629578 B2 JP S629578B2
- Authority
- JP
- Japan
- Prior art keywords
- cis
- trans
- isomer
- acetate
- alkenyl ester
- 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
- 238000000034 method Methods 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 4
- 229940098795 (3z)- 3-hexenyl acetate Drugs 0.000 description 3
- 239000000877 Sex Attractant Substances 0.000 description 3
- NPFVOOAXDOBMCE-PLNGDYQASA-N cis-3-Hexenyl acetate Natural products CC\C=C/CCOC(C)=O NPFVOOAXDOBMCE-PLNGDYQASA-N 0.000 description 3
- RRGOKSYVAZDNKR-ARJAWSKDSA-M cis-3-hexenylacetate Chemical compound CC\C=C/CCCC([O-])=O RRGOKSYVAZDNKR-ARJAWSKDSA-M 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- NPFVOOAXDOBMCE-UHFFFAOYSA-N trans-3-hexenyl acetate Natural products CCC=CCCOC(C)=O NPFVOOAXDOBMCE-UHFFFAOYSA-N 0.000 description 3
- YJINQJFQLQIYHX-PLNGDYQASA-N 11Z-Tetradecenyl acetate Chemical compound CC\C=C/CCCCCCCCCCOC(C)=O YJINQJFQLQIYHX-PLNGDYQASA-N 0.000 description 2
- 241000255777 Lepidoptera Species 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YJINQJFQLQIYHX-UHFFFAOYSA-N trans-11-tetradecenyl acetate Natural products CCC=CCCCCCCCCCCOC(C)=O YJINQJFQLQIYHX-UHFFFAOYSA-N 0.000 description 2
- XFXOLBNQYFRSLQ-UHFFFAOYSA-N 3-amino-2-naphthoic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(N)=CC2=C1 XFXOLBNQYFRSLQ-UHFFFAOYSA-N 0.000 description 1
- MFFQOUCMBNXSBK-SNAWJCMRSA-N 9E-Dodecenyl acetate Chemical compound CC\C=C\CCCCCCCCOC(C)=O MFFQOUCMBNXSBK-SNAWJCMRSA-N 0.000 description 1
- MFFQOUCMBNXSBK-PLNGDYQASA-N 9Z-Dodecenyl acetate Chemical compound CC\C=C/CCCCCCCCOC(C)=O MFFQOUCMBNXSBK-PLNGDYQASA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IOUUIFSIQMVYKP-UHFFFAOYSA-N Tetradecanoyl acetate Natural products CCCCCCCCCCCCCCOC(C)=O IOUUIFSIQMVYKP-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- UECPLNNAVLEZGO-CCEZHUSRSA-N [(e)-tetradec-1-enyl] acetate Chemical compound CCCCCCCCCCCC\C=C\OC(C)=O UECPLNNAVLEZGO-CCEZHUSRSA-N 0.000 description 1
- DFRXMRZQBMFKMI-PLNGDYQASA-N [(z)-non-6-enyl] acetate Chemical compound CC\C=C/CCCCCOC(C)=O DFRXMRZQBMFKMI-PLNGDYQASA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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)
Description
【発明の詳細な説明】
本発明はシス―アルケニルエステル化合物をト
ランス―アルケニルエステル化合物に異性化させ
る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for isomerizing a cis-alkenyl ester compound to a trans-alkenyl ester compound.
チヨウやガ類などのリンシモク
（Lepidoptera）系害虫の性フエロモン物質は、
主に直鎖状で脂肪族二重結合を１つまたは２つも
つ化学構造のものであり、その二重結合はシス体
のものが多いが、シス体とトランス体との混合組
成になつているものも少なくない。 The sex pheromone substances of Lepidoptera pests such as lepidoptera and moths are
It has a chemical structure that is mainly linear and has one or two aliphatic double bonds, and the double bonds are often in the cis form, but they can have a mixed composition of the cis form and the trans form. There are quite a few.
たとえばナシヒメシンクイガの性フエロモン物
質は、シス―９―ドデセニルアセテートとトラン
ス―９―ドデセニルアセテートの比率が93：７と
なつており、またツヅリモンハマキのそれはシス
―11―テトラデセニルアセテートとトランス―11
―テトラデセニルアセテートの比率が１：１とな
つている。 For example, the sex pheromone substance of the Nashihime Shinki moth has a ratio of cis-9-dodecenyl acetate to trans-9-dodecenyl acetate of 93:7, and that of the Tsuzurimon moth has a cis-11-tetradecenyl acetate ratio. Nyl acetate and trans-11
-The ratio of tetradecenyl acetate is 1:1.
工業的に上記のようなシス体とトランス体の混
合組成をもつ性フエロモン物質を合成する場合、
シス体は三重結合を接触部分水添すれば得られる
という工業的合成法はあるが、その場合副生する
トランス体の組成を多くする条件で行つてもトラ
ンス体の比率はせいぜい２〜５％になるにすぎな
い。したがつて、トランス体の混合組成比をさら
に増す必要がある場合にはトランス体を単独に合
成し、シス体に混合しなければならないが、トラ
ンス体を得る工業的合成法はいまだ見出されてい
ない。 When industrially synthesizing a sex pheromone substance having a mixed composition of cis and trans forms as described above,
There is an industrial synthesis method in which the cis isomer can be obtained by catalytic partial hydrogenation of the triple bond, but in that case, even if the process is carried out under conditions that increase the composition of the by-product trans isomer, the ratio of the trans isomer is at most 2 to 5%. It just becomes. Therefore, if it is necessary to further increase the mixed composition ratio of the trans isomer, it is necessary to synthesize the trans isomer alone and mix it with the cis isomer, but an industrial synthesis method for obtaining the trans isomer has yet to be found. Not yet.
そこで、比較的容易に得られるシス体をトラン
ス体に異性化する簡単な方法が存在すれば、その
利用メリツトは非常に大である。 Therefore, if there were a simple method for isomerizing the relatively easily obtained cis isomer into the trans isomer, it would be of great benefit.
本発明はかかる課題を解決すべく鋭意研究を重
ねた結果完成されたもので、これは一般式
CH3（CH2）n CH＝CH（CH2）oOR ……（）
（式中のＲはホルミル基、アセチル基などのア
シル基を示し、またｍは１〜10、ｎは２〜10の整
数である）で表されるシス―アルケニルエステル
化合物を、セレン金属の存在下に加熱し、トラン
ス―アルケニルエステル化合物に異性化させるこ
とを特徴とする不飽和脂肪族エステルの異性化方
法を要旨とするものである。 The present invention was completed as a result of intensive research to solve such problems, and is based on the general formula CH 3 (CH 2 ) n CH=CH (CH 2 ) o OR ... () (R in the formula represents an acyl group such as a formyl group or an acetyl group, and m is an integer of 1 to 10 and n is an integer of 2 to 10) is heated in the presence of selenium metal, The gist of this invention is a method for isomerizing unsaturated aliphatic esters, which is characterized by isomerizing them into trans-alkenyl ester compounds.
これを説明すると、本発明で対象とされる一般
式（）で表わされるシス―アルケニルエステル
化合物としては、シス―３―ヘキセニルアセテー
ト、シス―３―ヘキセニルホルメート、シス―３
―オクテニルアセテート、シス―６―ノネニルア
セテートなどが例示される。 To explain this, the cis-alkenyl ester compounds represented by the general formula () targeted by the present invention include cis-3-hexenyl acetate, cis-3-hexenyl formate, cis-3
-octenyl acetate, cis-6-nonenyl acetate, and the like.
本発明の方法は、シス―アルケニルエステル化
合物をセレン金属の存在下に加熱することにより
行われるが、この際セレン金属は粉末状であるこ
とがよく、またその使用量はシス―アルケニルエ
ステル化合物に対しおおむね0.1〜５重量％の範
囲とすればよい。 The method of the present invention is carried out by heating the cis-alkenyl ester compound in the presence of selenium metal, but at this time, the selenium metal is often in powder form, and the amount used is determined depending on the cis-alkenyl ester compound. The amount may be approximately 0.1 to 5% by weight.
反応温度は高い方が異性化反応の速度が大きく
なるが、通常は150〜200℃の温度に加熱して行う
ことがよい。異性化は反応時間に応じて進行し、
反応時間を長くすればそれに応じトランス体への
異性化率が高くなる。したがつて、本発明の方法
はシス体100％のものに対して実施する場合のほ
かシス体とトランス体との混合組成のものに対し
ても実施することができ、この後者の場合にはト
ランス体の混合比のより増加したものが得られ
る。また、反応温度、反応時間の調節により、シ
ス体とトランス体との混合比率を目的の値に調整
することも容易にできる。 The higher the reaction temperature, the faster the rate of isomerization reaction, but it is usually best to heat the reaction to a temperature of 150 to 200°C. Isomerization progresses depending on the reaction time,
The longer the reaction time, the higher the isomerization rate to the trans isomer. Therefore, the method of the present invention can be carried out not only on 100% cis isomers but also on those with a mixed composition of cis and trans isomers; in this latter case, An increased mixing ratio of trans isomers is obtained. Further, by adjusting the reaction temperature and reaction time, the mixing ratio of the cis isomer and the trans isomer can be easily adjusted to a desired value.
つぎに、具体的実施例をあげる。 Next, specific examples will be given.
実施例 １
シス―３―ヘキセニルアセテート200ｇ、セレ
ン粉末１ｇを500ml反応フラスコに入れ、反応温
度150℃にてかくはんし、60分間加熱反応させた
ところ、トランス体／シス体＝1.48の混合物が得
られた。Example 1 200 g of cis-3-hexenyl acetate and 1 g of selenium powder were placed in a 500 ml reaction flask, stirred at a reaction temperature of 150°C, and heated for 60 minutes. A mixture of trans isomer/cis isomer = 1.48 was obtained. Ta.
なお、反応開始時のトランス体／シス体比は
0.02であつた。 In addition, the trans isomer/cis isomer ratio at the start of the reaction is
It was 0.02.
実施例 ２
シス―３―ヘキセニルアセテートの代りに、シ
ス―11―テトラデセニルアセテート（トランス
体／シス体＝0.03）を使用し、反応温度を170℃
としたほかは前例と同様にして60分間加熱反応さ
せたところ、トランス体／シス体＝2.04の混合物
が得られた。Example 2 Cis-11-tetradecenyl acetate (trans form/cis form = 0.03) was used instead of cis-3-hexenyl acetate, and the reaction temperature was 170°C.
When the heating reaction was carried out for 60 minutes in the same manner as in the previous example, a mixture of trans isomer/cis isomer = 2.04 was obtained.
Claims (1)
10の整数をそれぞれ示す）で表されるシス―アル
ケニルエステル化合物を、セレン金属の存在下に
加熱し、トランス―アルケニルエステル化合物に
異性化させることを特徴とする不飽和脂肪族エス
テルの異性化方法。[Claims] 1 General formula CH 3 (CH 2 ) n CH=CH (CH 2 ) o OR (R in the formula is an acyl group, m is 1 to 10, n is 2 to
A method for isomerizing unsaturated aliphatic esters, which comprises heating a cis-alkenyl ester compound represented by (each representing an integer of 10) in the presence of selenium metal to isomerize it into a trans-alkenyl ester compound. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9959980A JPS5724326A (en) | 1980-07-21 | 1980-07-21 | Isomerization of unsaturated aliphatic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9959980A JPS5724326A (en) | 1980-07-21 | 1980-07-21 | Isomerization of unsaturated aliphatic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5724326A JPS5724326A (en) | 1982-02-08 |
| JPS629578B2 true JPS629578B2 (en) | 1987-02-28 |
Family
ID=14251553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9959980A Granted JPS5724326A (en) | 1980-07-21 | 1980-07-21 | Isomerization of unsaturated aliphatic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5724326A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0263722U (en) * | 1988-10-28 | 1990-05-14 | ||
| JPH0339583U (en) * | 1989-08-29 | 1991-04-16 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5665833A (en) * | 1979-11-02 | 1981-06-03 | Nissan Chem Ind Ltd | Isomerization of beta-gamma unsaturated alcohol and its derivative |
-
1980
- 1980-07-21 JP JP9959980A patent/JPS5724326A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5665833A (en) * | 1979-11-02 | 1981-06-03 | Nissan Chem Ind Ltd | Isomerization of beta-gamma unsaturated alcohol and its derivative |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0263722U (en) * | 1988-10-28 | 1990-05-14 | ||
| JPH0339583U (en) * | 1989-08-29 | 1991-04-16 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5724326A (en) | 1982-02-08 |
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