JPS6330297B2 - - Google Patents
Info
- Publication number
- JPS6330297B2 JPS6330297B2 JP16369983A JP16369983A JPS6330297B2 JP S6330297 B2 JPS6330297 B2 JP S6330297B2 JP 16369983 A JP16369983 A JP 16369983A JP 16369983 A JP16369983 A JP 16369983A JP S6330297 B2 JPS6330297 B2 JP S6330297B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- methyl
- trans
- nonenoic acid
- nonenoic
- 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
- OCALSPDXYQHUHA-FNORWQNLSA-N 8-Methyl-6-nonenoic acid Chemical compound CC(C)\C=C\CCCCC(O)=O OCALSPDXYQHUHA-FNORWQNLSA-N 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- NVRVNSHHLPQGCU-UHFFFAOYSA-N 6-bromohexanoic acid Chemical compound OC(=O)CCCCCBr NVRVNSHHLPQGCU-UHFFFAOYSA-N 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- OCALSPDXYQHUHA-ALCCZGGFSA-N (z)-8-methylnon-6-enoic acid Chemical compound CC(C)\C=C/CCCCC(O)=O OCALSPDXYQHUHA-ALCCZGGFSA-N 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 description 12
- IASRMNRQZIRYHM-UHFFFAOYSA-N 6-carboxyhexyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCC(=O)O)C1=CC=CC=C1 IASRMNRQZIRYHM-UHFFFAOYSA-N 0.000 description 5
- 229960002504 capsaicin Drugs 0.000 description 5
- 235000017663 capsaicin Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ADLXTJMPCFOTOO-BQYQJAHWSA-N (E)-non-2-enoic acid Chemical compound CCCCCC\C=C\C(O)=O ADLXTJMPCFOTOO-BQYQJAHWSA-N 0.000 description 3
- ZPSOISAMGWYNQX-ONEGZZNKSA-N 6E-nonenoic acid Chemical compound CC\C=C\CCCCC(O)=O ZPSOISAMGWYNQX-ONEGZZNKSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WRPWWVNUCXQDQV-UHFFFAOYSA-N vanillylamine Chemical compound COC1=CC(CN)=CC=C1O WRPWWVNUCXQDQV-UHFFFAOYSA-N 0.000 description 3
- 229940053939 vanillylamine Drugs 0.000 description 3
- 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 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BBHJTCADCKZYSO-UHFFFAOYSA-N 4-(4-ethylcyclohexyl)benzonitrile Chemical compound C1CC(CC)CCC1C1=CC=C(C#N)C=C1 BBHJTCADCKZYSO-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 235000002568 Capsicum frutescens Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001247145 Sebastes goodei Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- -1 methyl-cis-6-nonenoic acid Chemical compound 0.000 description 1
- SOHCYNFHNYKSTM-UHFFFAOYSA-N methylsulfinylmethane;oxolane Chemical compound CS(C)=O.C1CCOC1 SOHCYNFHNYKSTM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 229960002860 zucapsaicin Drugs 0.000 description 1
- YKPUWZUDDOIDPM-VURMDHGXSA-N zucapsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C/C(C)C)=CC=C1O YKPUWZUDDOIDPM-VURMDHGXSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は８―メチル―トランス―６―ノネン酸
の新規な製造方法に関し、さらに詳しくは、トウ
ガラシの辛味成分カプサイシンの合成中間体であ
る８―メチル―トランス―６―ノネン酸を簡単な
工程で収率よく製造する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 8-methyl-trans-6-nonenoic acid. The present invention relates to a method for producing nonenoic acid with a high yield through simple steps.
カプサイシンは化学名Ｎ―（４―ヒドロキシ―
３―メトキシベンジル）―８―メチルノン―トラ
ンス―６―エンアミド（Ｎ―（４―Hydroxy―
３―methoxybenzyl）―８―methylnon―trans
―６―enamide）で示される化合物であつて、次
の式で示されるように、８―メチル―トランス―
６―ノネン酸とバニリルアミンを原料として合成
される。 Capsaicin has the chemical name N-(4-hydroxy-
3-methoxybenzyl)-8-methylnon-trans-6-enamide (N-(4-Hydroxy-
3-methoxybenzyl)-8-methylnon-trans
-6-enamide), as shown by the following formula, 8-methyl-trans-
It is synthesized using 6-nonenoic acid and vanillylamine as raw materials.
すなわち、８―メチル―トランス―６―ノネン
酸（）に塩化チオニルなどの酸クロリド化剤を
作用させて（）の酸クロリド化物を得たのち、
バニリルアミン（）を反応させればカプサイシ
ン（）が得られる。 That is, after reacting 8-methyl-trans-6-nonenoic acid () with an acid chloridizing agent such as thionyl chloride to obtain an acid chloride of (),
Capsaicin () is obtained by reacting vanillylamine ().
前記の８―メチル―トランス―６―ノネン酸
（）は、従来、次に示すような方法によつて合
成されている。 The above-mentioned 8-methyl-trans-6-nonenoic acid () has conventionally been synthesized by the following method.
しかしながら、この方法においては、５工程を
必要とするなど工程が煩雑であり、しかも８―メ
チル―トランス―６―ノネン酸の全収率が約５〜
14％と極めて低いという欠点がある。さらに中間
体の２―イソプロピル―３―クロルテトヤヒドロ
ピランは極めて不安定である。 However, this method is complicated, requiring 5 steps, and the total yield of 8-methyl-trans-6-nonenoic acid is approximately 5 to 50%.
The disadvantage is that it is extremely low at 14%. Furthermore, the intermediate 2-isopropyl-3-chlortetoyahydropyran is extremely unstable.
本発明者らは、このような欠点を克服し、簡単
な工程で収率よく８―メチル―トランス―６―ノ
ネン酸を製造する方法を提供すべく鋭意研究を重
ねた結果、６―ブロモカプロン酸を原料として用
い、これにトリフエニルホスフインを反応させた
のち、亜硝酸で処理することにより、その目的を
達成しうることを見出し、この知見に基づいて本
発明を完成するに至つた。 The present inventors have conducted intensive research to overcome these drawbacks and provide a method for producing 8-methyl-trans-6-nonenoic acid in a high yield through simple steps. As a result, 6-bromocaprone The inventors have discovered that the object can be achieved by using acid as a raw material, reacting it with triphenylphosphine, and then treating it with nitrous acid, and based on this knowledge, they have completed the present invention.
すなわち、本発明は、次式
に示すように、６―ブロモカプロン酸（）をト
リフエニルホスフインと反応させてホスホニウム
塩（）に変えたのち、これに塩基の存在下、イ
ソブチルアルデヒドと反応させて８―メチル―シ
ス―６―ノネン酸（）を生成させ、次いでこれ
を亜硝酸で処理することを特徴とする８―メチル
―トランス―６―ノネン酸（）の製造方法を提
供するものである。 That is, the present invention provides the following formula As shown in Figure 2, 6-bromocaproic acid () is reacted with triphenylphosphine to convert it into a phosphonium salt (), which is then reacted with isobutyraldehyde in the presence of a base to form 8-methyl-cis-6. - Provides a method for producing 8-methyl-trans-6-nonenoic acid (), which is characterized by producing nonenoic acid () and then treating it with nitrous acid.
本発明方法における原料として用いる６―ブロ
モカプロン酸（）は、例えばε―カプロラクト
ンを臭化水素酸で処理することにより容易に得ら
れる。この６―ブロモカプロン酸にそれと当モル
のトリフエニルホスフインを加え、120〜160℃の
温度で２〜６時間反応させることにより、６―カ
ルボキシヘキシルトリフエニルホスホニウムブロ
ミド（）が得られる。このものは、必要に応
じ、例えばクロロホルム―エーテル混合溶媒など
を用いて再結晶してもよい。 6-bromocaproic acid () used as a raw material in the method of the present invention can be easily obtained, for example, by treating ε-caprolactone with hydrobromic acid. 6-Carboxyhexyltriphenylphosphonium bromide (2) is obtained by adding an equimolar amount of triphenylphosphine to this 6-bromocaproic acid and reacting at a temperature of 120 to 160°C for 2 to 6 hours. This product may be recrystallized using, for example, a mixed solvent of chloroform and ether, if necessary.
このようにして得られた６―カルボキシヘキシ
ルトリフエニルホスニウムブロミドに、これと当
モルのイソブチルアルデヒドを、水素化ナトリウ
ムなどの塩基の存在下、室温で６〜10時間反応さ
せると、８―メチル―シス―６―ノネン酸（）
が得られる。この場合、ジメチルスルホキシド―
テトラヒドロフラン混合溶媒などを用いることが
好ましい。 When the thus obtained 6-carboxyhexyltriphenylphosnium bromide is reacted with the equimolar amount of isobutyraldehyde at room temperature in the presence of a base such as sodium hydride for 6 to 10 hours, 8-methyl -cis-6-nonenoic acid ()
is obtained. In this case, dimethyl sulfoxide
It is preferable to use a tetrahydrofuran mixed solvent or the like.
次に、この反応生成物から８―メチル―シス―
６―ノネン酸（）を取り出し、これを亜硝酸で
60〜80℃の温度において10分間〜２時間処理する
と、８―メチル―トランス―６―ノネン酸（）
主体の混合物が得られる。この混合物は平衡にあ
りトランス体（）とシス体（）の比率は約
75：１である。なお８―メチル―６―ノネン酸混
合物を酸塩化物とし、バニリルアミンと処理する
と、カプサイシンとシス―カプサイシンの混合物
となるが、エーテルなどで再結晶することにより
純粋なカプサイシンを得ることができる。本発明
の製造方法によれば８―メチル―トランス―６―
ノネン酸（）の全収率は50〜60％である。 Next, from this reaction product, 8-methyl-cis-
Take out 6-nonenoic acid () and add it with nitrous acid.
When treated for 10 minutes to 2 hours at a temperature of 60 to 80°C, 8-methyl-trans-6-nonenoic acid ()
A mixture of main substances is obtained. This mixture is in equilibrium and the ratio of trans isomer () and cis isomer () is approximately
The ratio is 75:1. Note that when the 8-methyl-6-nonenoic acid mixture is converted into an acid chloride and treated with vanillylamine, a mixture of capsaicin and cis-capsaicin is obtained, but pure capsaicin can be obtained by recrystallizing with ether or the like. According to the production method of the present invention, 8-methyl-trans-6-
The overall yield of nonenoic acid () is 50-60%.
本発明方法によると、トウガラシの辛味成分カ
プサイシンの合成中間体である８―メチル―トラ
ンス―６―ノネン酸が、従来の方法に比べて極め
て簡単な工程で収率よく得られる。 According to the method of the present invention, 8-methyl-trans-6-nonenoic acid, which is an intermediate for the synthesis of capsaicin, the pungent component of chili peppers, can be obtained in high yield through extremely simple steps compared to conventional methods.
次に実施例によつて本発明をさらに詳細に説明
する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
６―カルボキシヘキシルトリフエニルホスホニ
ウムブロミドの合成
６―ブロモカプロン酸25.8ｇ（0.132モル）と
トリフエニルホスフイン34.7ｇ（0.132モル）と
を、145℃で４時間かきまぜながら加熱し、次い
で冷却したのち、クロロホルム―エーテル混合溶
媒より再結晶して６―カルボキシヘキシルトリフ
エニルホスホニウムブロミド58.3ｇを得る。この
ものの融点は202〜203℃であり、収率は96％であ
つた。Example 1 Synthesis of 6-carboxyhexyl triphenylphosphonium bromide 25.8 g (0.132 mol) of 6-bromocaproic acid and 34.7 g (0.132 mol) of triphenylphosphine were heated at 145°C with stirring for 4 hours, and then cooled. Thereafter, it was recrystallized from a chloroform-ether mixed solvent to obtain 58.3 g of 6-carboxyhexyl triphenylphosphonium bromide. The melting point of this product was 202-203°C, and the yield was 96%.
またnmr（CDCl3、δin ppm）は、1.8―2.0（ｍ、
6H、CH2CH2CH2CH2CO）、2.4―2.65（ｍ、2H、
CH2CO）、3.7―4.2（ｍ、2H、PCH2）、8.2―8.8
（Ａ、15H、Arom atic H's）、10.75（ｂ、1H、
CO2H）であり、jr（nujol）は、1705、1435、
1115cm-1であつた。 In addition, nmr (CDCl 3 , δin ppm) is 1.8-2.0 (m,
6H, CH 2 CH 2 CH 2 CH 2 CO), 2.4-2.65 (m, 2H,
CH2CO ), 3.7-4.2 (m, 2H, PCH2 ), 8.2-8.8
(A, 15H, Aromatic H's), 10.75 (b, 1H,
CO 2 H), jr (nujol) is 1705, 1435,
It was 1115 cm -1 .
実施例 ２
８―メチル―シス―６―ノネン酸の合成
６―カルボキシヘキシルトリフエニルホスホニ
ウムブロミド22.85ｇ（50ミリモル）をジメチル
スルホキシド―テトラヒドロフラン（１：１）混
合溶媒150mlに溶解し、これにさらにイソブチル
アルデヒド3.61ｇ（50ミリモル）を加える。この
溶液を水素化ナトリウム2.4ｇ（100ミリモル）
に、窒素雰囲気下０℃で30分間で滴下する。次い
で室温で８時間かきまぜたのち、反応混合物を氷
水400mlに注ぐ。次にベンゼンを用いてトリフエ
ニルホスフインオキシドを抽出したのち、水溶液
を２規定の塩酸で酸性にする。この水溶液をエー
テルで抽出し、抽出液を飽和食塩水で洗浄したの
ち、無水硫酸ナトリウムで乾燥する。次いでエー
テルをエバポレーターで留去後、減圧蒸留して８
―メチル―シス―６―ノネン酸6.25ｇを得る。こ
のものの沸点は107〜109℃／3.5torrであり、収
率は74％であつた。（シス体：トランス体11：
１）
またnmr（CDCl3、δin ppm）は、0.95（ｄ、
6H、（CH3）2C）、1.3―1.82（ｍ、4H、
CH2CH2CH2CO）、1.98―2.2（ｍ、2H、CH＝CH
−CH2）、2.4（ｔ、2H、CH2CO）、2.2―2.9（ｍ、
1H、（CH3）2CH）、5.1―5.5（ｍ、2H、CH＝
CH）、11.5（ｂ、1H、CO2H）であり、ir（液膜）
は3000―2500、1715、1370、735cm-1であつた。Example 2 Synthesis of 8-methyl-cis-6-nonenoic acid 22.85 g (50 mmol) of 6-carboxyhexyl triphenylphosphonium bromide was dissolved in 150 ml of dimethyl sulfoxide-tetrahydrofuran (1:1) mixed solvent, and to this was added isobutyl Add 3.61 g (50 mmol) of aldehyde. Add this solution to 2.4 g (100 mmol) of sodium hydride.
The solution was added dropwise for 30 minutes at 0°C under a nitrogen atmosphere. Then, after stirring at room temperature for 8 hours, the reaction mixture was poured into 400 ml of ice water. Next, triphenylphosphine oxide is extracted using benzene, and the aqueous solution is made acidic with 2N hydrochloric acid. This aqueous solution is extracted with ether, and the extract is washed with saturated brine and then dried over anhydrous sodium sulfate. Next, the ether was distilled off using an evaporator, and then distilled under reduced pressure to give 8
-6.25 g of methyl-cis-6-nonenoic acid is obtained. The boiling point of this product was 107-109°C/3.5 torr, and the yield was 74%. (cis form: trans form 11:
1) Also, nmr (CDCl 3 , δin ppm) is 0.95 (d,
6H, (CH 3 ) 2 C), 1.3-1.82 (m, 4H,
CH 2 CH 2 CH 2 CO), 1.98-2.2 (m, 2H, CH=CH
−CH 2 ), 2.4 (t, 2H, CH 2 CO), 2.2−2.9 (m,
1H, (CH 3 ) 2 CH), 5.1-5.5 (m, 2H, CH=
CH), 11.5 (b, 1H, CO 2 H), ir (liquid film)
were 3000-2500, 1715, 1370, and 735 cm -1 .
実施例 ３
８―メチル―トランス―６―ノネン酸の合成
８―メチル―シス―６―ノネン酸7.7ｇ（45.3
ミリモル）を窒素雰囲気中70℃に温めておき、こ
れに２規定の亜硝酸ナトリウム水溶液3.2mlと６
規定硝酸2.2mlを加え、70℃で0.5時間激しくかき
まぜる。次いで反応混合物を室温まで冷却後、氷
水を加えエーテルで抽出する。この抽出液を飽和
食塩水で洗浄後、無水硫酸ナトリウムで乾燥し、
エバポレーターにてエーテルを留去する。残渣を
減圧蒸留してトランス体を主とする８―メチル―
６―ノネン酸を得る。（トランス体：スシ体
7.5：１）
このものの収率は77％、沸点は117〜120℃／
2.8torrで、nmr（CDCl3、δin ppm）は、0.98（ｄ、
6H、（CH3）2C）、1.16―1.86（ｍ、4H、
CH2CH2CH2CO）1.9―2.3（ｍ、2H、CH＝CH−
CH2）、2.4（ｔ、2H、CH2CO）、1.96−2.9（ｍ、
1H、（CH3）2CH）、5.38−5.6（ｍ、2H、CH＝
CH）、11.5（ｂ、1H、CO2H）であり、ir（液膜）
は3000−2500、1710、1370、967、735cm-1であつ
た。Example 3 Synthesis of 8-methyl-trans-6-nonenoic acid 7.7 g (45.3
mmol) at 70°C in a nitrogen atmosphere, and add 3.2 ml of 2N sodium nitrite aqueous solution and 6
Add 2.2 ml of normal nitric acid and stir vigorously at 70°C for 0.5 hour. Then, after cooling the reaction mixture to room temperature, ice water was added and extracted with ether. This extract was washed with saturated saline, dried over anhydrous sodium sulfate,
Ether is distilled off using an evaporator. The residue is distilled under reduced pressure to obtain 8-methyl, which is mainly trans-isomer.
6-nonenoic acid is obtained. (Trans body: Sushi body
7.5:1) The yield of this product is 77%, and the boiling point is 117-120℃/
At 2.8 torr, nmr (CDCl 3 , δin ppm) is 0.98 (d,
6H, (CH 3 ) 2 C), 1.16-1.86 (m, 4H,
CH 2 CH 2 CH 2 CO) 1.9-2.3 (m, 2H, CH=CH-
CH 2 ), 2.4 (t, 2H, CH 2 CO), 1.96−2.9 (m,
1H, (CH 3 ) 2 CH), 5.38−5.6 (m, 2H, CH=
CH), 11.5 (b, 1H, CO 2 H), ir (liquid film)
were 3000−2500, 1710, 1370, 967, and 735 cm -1 .
Claims (1)
インと反応させてホスホニウム塩に変えた後、こ
れに塩基の存在下、イソブチルアルデヒドと反応
させて８―メチル―シス―６―ノネン酸を生成さ
せ、次いでこれを亜硝酸で処理することを特徴と
する８―メチル―トランス―６―ノネン酸の製造
方法。1 6-bromocaproic acid is reacted with triphenylphosphine to convert it into a phosphonium salt, which is then reacted with isobutyraldehyde in the presence of a base to form 8-methyl-cis-6-nonenoic acid, and then A method for producing 8-methyl-trans-6-nonenoic acid, which comprises treating it with nitrous acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16369983A JPS6054336A (en) | 1983-09-05 | 1983-09-05 | Preparation of 8-methyl-trans-6-nonenoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16369983A JPS6054336A (en) | 1983-09-05 | 1983-09-05 | Preparation of 8-methyl-trans-6-nonenoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6054336A JPS6054336A (en) | 1985-03-28 |
| JPS6330297B2 true JPS6330297B2 (en) | 1988-06-17 |
Family
ID=15778929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16369983A Granted JPS6054336A (en) | 1983-09-05 | 1983-09-05 | Preparation of 8-methyl-trans-6-nonenoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6054336A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092122A2 (en) * | 2003-04-08 | 2004-10-28 | Algorx Pharmaceuticals, Inc. | Preparation and purification of synthetic capsaicin |
-
1983
- 1983-09-05 JP JP16369983A patent/JPS6054336A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6054336A (en) | 1985-03-28 |
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