JPH0150215B2 - - Google Patents
Info
- Publication number
- JPH0150215B2 JPH0150215B2 JP3325683A JP3325683A JPH0150215B2 JP H0150215 B2 JPH0150215 B2 JP H0150215B2 JP 3325683 A JP3325683 A JP 3325683A JP 3325683 A JP3325683 A JP 3325683A JP H0150215 B2 JPH0150215 B2 JP H0150215B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- solution
- tetradecinate
- ether
- hydroxy
- 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
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- INTCGJHAECYOBW-APWZRJJASA-N (2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-ol Chemical group C([C@](O)([C@@H](CN(C)C)C)C=1C=CC=CC=1)C1=CC=CC=C1 INTCGJHAECYOBW-APWZRJJASA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910010082 LiAlH Inorganic materials 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 3
- JYRIJBPELVXSTC-UHFFFAOYSA-N cycloprop-2-yn-1-one Chemical compound O=C1C#C1 JYRIJBPELVXSTC-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo(3.3.1)nonane Chemical compound C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Substances CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 1
- INTCGJHAECYOBW-UHFFFAOYSA-N 4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-ol Chemical compound C=1C=CC=CC=1C(O)(C(CN(C)C)C)CC1=CC=CC=C1 INTCGJHAECYOBW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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】
本発明は光学純度の高い４−ヒドロキシ−５−
テトラデシン酸メチルを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 4-hydroxy-5-
The present invention relates to a method for producing methyl tetradecanoate.
４−ヒドロキシ−５−テトラデシン酸メチル
は、マメコガネ性フエロモンを合成するための重
要な中間体である。マメコガネ性フエロモンの合
成方法は既に幾つかが知られているが、一つの代
表的な方法は、次のスキームに示すように、４−
オキソ−５−テトラデシン酸メチル(1)を不斉還元
して、光学活性な４−ヒドロキシ−５−テトラデ
シン酸メチル(2)とし、これをケン化して４−ヒド
ロキシ−５−テトラデシン酸(3)とする。次に、こ
れを例えばアミンにより光学分割して光学活性な
アミン塩(4)を得、再結晶した後、酸により処理
し、蒸留して、（Ｒ，Ｚ）−（−）−５−dec−１−
ynyloxacyclopentane−２−one(5)を得、これを
半還元することにより、目的とするマメコガネフ
エロモン、即ち、（Ｒ，Ｚ）−（−）−５−dec−１
−enyloxacyclopentane−２−one(6)を得ること
ができる。 Methyl 4-hydroxy-5-tetradecinate is an important intermediate for the synthesis of bean ferromone. Several methods are already known for synthesizing ferromone, but one typical method is as shown in the following scheme.
Methyl oxo-5-tetradecinate (1) is asymmetrically reduced to optically active methyl 4-hydroxy-5-tetradecinate (2), which is saponified to form 4-hydroxy-5-tetradecinate (3). shall be. Next, this is optically resolved using, for example, an amine to obtain an optically active amine salt (4), which is recrystallized, treated with an acid, and distilled to give (R,Z)-(-)-5-dec -1-
By obtaining ynyloxacyclopentane-2-one(5) and semi-reducing it, the desired bean ferromone, i.e., (R,Z)-(-)-5-dec-1
-enyloxacyclopentane-2-one(6) can be obtained.
しかしながら、マメコガネフエロモンは（Ｓ，
Ｚ）異性体の混入によりその活性が大幅に低下す
ることが知られており、例えば、0.5％の（Ｓ，
Ｚ）異性体が存在してもその活性は60％程度にま
で低下し、２％が存在すると活性は約1/3に低下
し、６％存在するときは最早活性を示さない。 However, Mamekoganepheromon (S,
It is known that the activity is significantly reduced by the contamination of Z) isomers, for example, 0.5% (S,
Z) Even if the isomer is present, its activity decreases to about 60%, when it is present at 2%, the activity is reduced to about 1/3, and when it is present at 6%, it no longer shows any activity.
このため、従来より光学的に純粋なマメコガネ
フエロモンの合成が多くの研究者によつて研究さ
れているが、尚種々の問題を有している。例え
ば、上記のスキームにおいて(1)から(2)への不斉還
元にα−ピネンを用いる方法が提案されている
が、一般にこの方法によれば、(1)に対してα−ピ
ネンを大量に用いる必要があり、しかも、これを
回収することができず、更に、例えば、α−ピネ
ンと９−ボラビシクロ〔3.3.1〕ノナンを不斉還
元剤とする場合には、反応に数日間を要する。こ
のように従来の方法によれば、効率や費用の点に
おいて多くの問題がある。 For this reason, many researchers have been researching the synthesis of optically pure bean pheromone, but there are still various problems. For example, in the above scheme, a method using α-pinene for the asymmetric reduction from (1) to (2) has been proposed, but generally speaking, according to this method, a large amount of α-pinene is added to (1). Furthermore, when α-pinene and 9-borabicyclo[3.3.1]nonane are used as asymmetric reducing agents, the reaction takes several days. It takes. As described above, the conventional methods have many problems in terms of efficiency and cost.
本発明者は上記した問題を解決するために鋭意
研究した結果、４−オキソ−５−テトラデシン酸
メチルを不斉還元するに際して、（2S，3R）−
（＋）−４−ジメチルアミノ−１，２−ジフエニル
−３−メチル−２−ブタノールを還元剤成分とす
る不斉還元剤を用いることにより、短時間の反応
によつてほぼ定量的に光学純度の高い４−ヒドロ
キシ−５−テトラデシン酸メチルを得ることがで
きることを見出して、本発明に至つたものであ
る。 As a result of intensive research to solve the above-mentioned problems, the present inventor found that (2S,3R)-
By using an asymmetric reducing agent containing (+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-butanol as a reducing agent component, optical purity can be achieved almost quantitatively through a short reaction time. The inventors have discovered that it is possible to obtain methyl 4-hydroxy-5-tetradecinate having a high carbon content, leading to the present invention.
即ち、本発明による４−ヒドロキシ−５−テト
ラデシン酸メチルの製造方法は、４−オキソ−５
−テトラデシン酸メチルを（2S，3R）−（＋）−４
−ジメチルアミノ−１，２−ジフエニル−３−メ
チル−２−ブタノールと一般式
MXH4
（但し、ＭはLi又はNaを示し、ＸはAl又はＢを
示す。）
とからなる還元剤により不斉還元することを特徴
とする。 That is, the method for producing methyl 4-hydroxy-5-tetradecinate according to the present invention
-Methyl tetradecinate (2S,3R)-(+)-4
-dimethylamino-1,2-diphenyl-3-methyl-2-butanol and a reducing agent with the general formula MXH 4 (where M represents Li or Na, and X represents Al or B). It is characterized by giving back.
本発明において不斉還元剤成分として用いる
（2S，3R）−（＋）−４−ジメチルアミノ−１，２
−ジフエニル−３−メチル−２−ブタノール(7)は
次式で表わされ、市販されているため、容易に入
手することができる。 (2S,3R)-(+)-4-dimethylamino-1,2 used as an asymmetric reducing agent component in the present invention
-Diphenyl-3-methyl-2-butanol (7) is represented by the following formula and is commercially available, so it can be easily obtained.
不斉還元剤の他の成分は一般式
MXH4
で表わされる金属ハイドライドであつて、ここ
に、ＭはLi又はNaを示し、ＸはAl又はＢを示
す。従つて好ましい具体例として、LiAlH4、
NaAlH4、LiBH4、NaBH4等を挙げることがで
きるが、特にLiAlHが好ましく用いられる。 The other component of the asymmetric reducing agent is a metal hydride represented by the general formula MXH 4 , where M represents Li or Na and X represents Al or B. Therefore, as preferred specific examples, LiAlH 4 ,
Examples include NaAlH 4 , LiBH 4 , NaBH 4 and the like, and LiAlH is particularly preferably used.
本発明による不斉還元剤は、好ましくは、上記
した金属ハイドライドのジエチルエーテル、テト
ラヒドロフラン等のエーテル系有機溶液に撹拌下
に温度−30℃乃至50℃、好ましくは−10℃乃至常
温で金属ハイドライドに対して２〜５倍モル、好
ましくは２〜2.5倍モルの（2S，3R）−（＋）−４
−ジメチルアミノ−１，２−ジフエニル−３−メ
チル−２−ブタノール(7)の上記同様のエーテル溶
液を添加し、撹拌することにより得られる。 The asymmetric reducing agent according to the present invention is preferably added to an ether-based organic solution of the above-mentioned metal hydride such as diethyl ether or tetrahydrofuran at a temperature of -30°C to 50°C, preferably -10°C to room temperature, with stirring. 2 to 5 times the mole, preferably 2 to 2.5 times the mole of (2S,3R)-(+)-4
-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (7) by adding the same ether solution as above and stirring.
前記アセチレンケトン(1)をこの不斉還元剤にて
還元するには、このケトン(1)に対して１〜10倍モ
ル、好ましくは１〜５倍モルの金属ハイドライド
を用いて得た不斉還元剤の溶液を−120℃〜50℃、
好ましくは−100℃〜常温とし、これに上記ケト
ンを加え、撹拌下に１〜５時間程度反応させれば
よい。反応を終了させるには、例えば水飽和エー
テルを加える。このようにして反応を終了させた
後、塩酸水溶液、次に飽和食塩水で反応溶液を洗
浄し、乾燥した後、濃縮すれば、ほぼ定量に４−
ヒドロキシ−５−テトラデシン酸メチルの粗生成
物を得ることができる。 In order to reduce the acetylene ketone (1) with this asymmetric reducing agent, an asymmetric reducing agent obtained using a metal hydride in an amount of 1 to 10 times, preferably 1 to 5 times in mole, relative to the ketone (1) is used. Reducer solution at -120℃~50℃,
Preferably, the temperature is -100°C to room temperature, the above ketone is added thereto, and the reaction is allowed to proceed for about 1 to 5 hours while stirring. To terminate the reaction, for example, water-saturated ether is added. After the reaction is completed in this way, the reaction solution is washed with an aqueous hydrochloric acid solution and then with a saturated saline solution, dried, and concentrated.
A crude product of methyl hydroxy-5-tetradecinate can be obtained.
このようにして得られるヒドロキシ酸(3)の光学
純度は、反応条件により若干異なるが、通常、75
〜90％e.e.（enatiomeric excess）である。 The optical purity of the hydroxy acid (3) obtained in this way varies slightly depending on the reaction conditions, but is usually 75
~90% ee (enatiomeric excess).
また、反応終了後に反応溶液を洗浄した上記塩
酸水溶液に食塩を飽和させ、カ性アルカリ水溶液
でアルカリ性とした後、エーテル抽出し、このエ
ーテル層を乾燥、濃縮することにより、不斉還元
に用いたアミノアルコール(7)をほぼ定量的に回収
することができる。 In addition, after the reaction was completed, the reaction solution was washed with the above hydrochloric acid aqueous solution, saturated with salt, made alkaline with a caustic alkali aqueous solution, extracted with ether, and this ether layer was dried and concentrated to be used for asymmetric reduction. Amino alcohol (7) can be recovered almost quantitatively.
以下に本発明の実施例を挙げる。 Examples of the present invention are listed below.
実施例
LiAlH4 228mgに乾燥エーテル100mlを加えて０
℃に冷却した。（2S，3R）−（＋）−４−ジメチル
アミノ−１，２−ジフエニル−３−メチル−２−
ブタノール(7)3.83ｇを乾燥エーテル20mlに溶解し
た溶液を上記金属ハイドライドエーテル溶液に２
分間を要して滴下し、更に０℃にて２分間撹拌し
た後、−100℃まで冷却した。Example Add 100ml of dry ether to 228mg of LiAlH 4
Cooled to ℃. (2S,3R)-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-
A solution of 3.83 g of butanol (7) dissolved in 20 ml of dry ether was added to the above metal hydride ether solution.
The mixture was added dropwise over a period of 1 minute, stirred for 2 minutes at 0°C, and then cooled to -100°C.
次に、４−オキソ−５−テトラデシン酸メチル
(1)1.26ｇを乾燥エーテル20mlに溶解した溶液を上
記還元剤溶液に30分間を要して滴下し、この後、
−100℃で２時間、更に−70〜−65℃の温度で２
時間撹拌した後、水飽和エーテルを加えて反応を
終了させた。反応溶液を1N塩酸水溶液で３回洗
浄し、飽和食塩水で洗浄した後、無水硫酸マグネ
シウム上で乾燥した。この後、濾過し、濃縮して
粗４−ヒドロキシ−５−テトラデシン酸メチル
1.23ｇを得た。（収率97％）。光学純度は、Eu
（tfmc）3の存在下の核磁気共鳴スペクトルから79
％e.e.であつた。 Next, methyl 4-oxo-5-tetradecinate
(1) A solution of 1.26 g dissolved in 20 ml of dry ether was added dropwise to the above reducing agent solution over a period of 30 minutes, and then
2 hours at -100℃, then 2 hours at a temperature of -70 to -65℃
After stirring for an hour, water-saturated ether was added to terminate the reaction. The reaction solution was washed three times with 1N aqueous hydrochloric acid solution, washed with saturated brine, and then dried over anhydrous magnesium sulfate. This was followed by filtration and concentration to give crude methyl 4-hydroxy-5-tetradecinate.
1.23g was obtained. (Yield 97%). Optical purity is Eu
(tfmc) from the nuclear magnetic resonance spectrum in the presence of 79
It was %ee.
また、反応溶液を洗浄した上記塩酸水溶液に食
塩を飽和させ、1Nカ性ソーダ水溶液を加えてア
ルカリ性とした後、エーテル抽出し、このエーテ
ル層を乾燥し、濃縮することにより、（2S，3R）
−（＋）−４−ジメチルアミノ−１，２−ジフエニ
ル−３−メチル−２−ブタノール(7)を回収率98.5
％で回収することができた。 In addition, the reaction solution was washed with the hydrochloric acid aqueous solution, saturated with common salt, made alkaline by adding 1N caustic soda aqueous solution, extracted with ether, and the ether layer was dried and concentrated to obtain (2S, 3R).
-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-butanol (7) recovery rate 98.5
% could be recovered.
Claims (1)
（2S，3R）−（＋）−４−ジメチルアミノ−１，２
−ジフエニル−３−メチル−２−ブタノールと一
般式 MXH4 （但し、ＭはLi又はNaを示し、ＸはAl又はＢを
示す。） とからなる還元剤により不斉還元することを特徴
とする４−ヒドロキシ−５−テトラデシン酸メチ
ルの製造方法。[Claims] 1. Methyl 4-oxo-5-tetradecinate is (2S,3R)-(+)-4-dimethylamino-1,2
-diphenyl-3-methyl-2-butanol and a reducing agent having the general formula MXH 4 (where M represents Li or Na, and X represents Al or B). A method for producing methyl 4-hydroxy-5-tetradecinate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3325683A JPS59157055A (en) | 1983-02-28 | 1983-02-28 | Preparation of 4-hydroxy-5-tetradecynoic acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3325683A JPS59157055A (en) | 1983-02-28 | 1983-02-28 | Preparation of 4-hydroxy-5-tetradecynoic acid methyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59157055A JPS59157055A (en) | 1984-09-06 |
| JPH0150215B2 true JPH0150215B2 (en) | 1989-10-27 |
Family
ID=12381420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3325683A Granted JPS59157055A (en) | 1983-02-28 | 1983-02-28 | Preparation of 4-hydroxy-5-tetradecynoic acid methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59157055A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2598950B2 (en) * | 1988-03-07 | 1997-04-09 | 日東電工株式会社 | Process for producing optically active (R) methyl 4-hydroxy-5-tetradecanoate |
| JP2898747B2 (en) * | 1989-12-27 | 1999-06-02 | 日東電工株式会社 | Method for producing optically active hydroxyester and method for producing and purifying optically active 5-membered lactone |
| US7237757B2 (en) | 2001-09-14 | 2007-07-03 | Wayo Co., Ltd | Article support |
-
1983
- 1983-02-28 JP JP3325683A patent/JPS59157055A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59157055A (en) | 1984-09-06 |
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