JPH0333696B2 - - Google Patents
Info
- Publication number
- JPH0333696B2 JPH0333696B2 JP7592087A JP7592087A JPH0333696B2 JP H0333696 B2 JPH0333696 B2 JP H0333696B2 JP 7592087 A JP7592087 A JP 7592087A JP 7592087 A JP7592087 A JP 7592087A JP H0333696 B2 JPH0333696 B2 JP H0333696B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- methyl
- methylalkylcarboxylic
- reaction
- added
- 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
- 239000002253 acid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004990 Smectic liquid crystal Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- YNBBQLUKHHSKPW-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 YNBBQLUKHHSKPW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- -1 amide ester Chemical class 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- YSEQNZOXHCKLOG-UHFFFAOYSA-N 2-methyl-octanoic acid Chemical compound CCCCCCC(C)C(O)=O YSEQNZOXHCKLOG-UHFFFAOYSA-N 0.000 description 3
- IGVGCQGTEINVOH-UHFFFAOYSA-N 2-methyloctan-1-ol Chemical compound CCCCCCC(C)CO IGVGCQGTEINVOH-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SAOSCTYRONNFTC-UHFFFAOYSA-N 2-methyl-decanoic acid Chemical compound CCCCCCCCC(C)C(O)=O SAOSCTYRONNFTC-UHFFFAOYSA-N 0.000 description 2
- PGVQYOFKBIIVSF-UHFFFAOYSA-N 2-methyldecanoyl chloride Chemical compound CCCCCCCCC(C)C(Cl)=O PGVQYOFKBIIVSF-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000877 Sex Attractant Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WHNBDXQTMPYBAT-ZCFIWIBFSA-N (2r)-2-butyloxirane Chemical compound CCCC[C@@H]1CO1 WHNBDXQTMPYBAT-ZCFIWIBFSA-N 0.000 description 1
- NJWSNNWLBMSXQR-MRVPVSSYSA-N (2r)-2-hexyloxirane Chemical compound CCCCCC[C@@H]1CO1 NJWSNNWLBMSXQR-MRVPVSSYSA-N 0.000 description 1
- AAMHBRRZYSORSH-SNVBAGLBSA-N (2r)-2-octyloxirane Chemical compound CCCCCCCC[C@@H]1CO1 AAMHBRRZYSORSH-SNVBAGLBSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JZEUFFFBEMAJHS-UHFFFAOYSA-N 2-methyldecan-1-ol Chemical compound CCCCCCCCC(C)CO JZEUFFFBEMAJHS-UHFFFAOYSA-N 0.000 description 1
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- GPGGNNIMKOVSAG-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzonitrile Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 GPGGNNIMKOVSAG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000187654 Nocardia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- BLWYXBNNBYXPPL-YFKPBYRVSA-N methyl (2s)-pyrrolidine-2-carboxylate Chemical compound COC(=O)[C@@H]1CCCN1 BLWYXBNNBYXPPL-YFKPBYRVSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、カイラルスメクチツク相を取り得る
強誘電性液晶物質、昆虫の性フエロモンなどの生
理活性物質等の合成中間体として有用な光学活性
を有するα−メチルアルキルカルボン酸を製造す
る方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an optical material useful as a synthetic intermediate for physiologically active substances such as ferroelectric liquid crystal substances capable of taking a chiral smectic phase and insect sex pheromones. The present invention relates to a method for producing an active α-methylalkylcarboxylic acid.
［従来の技術］
光学活性を有するα−メチルアルキルカルボン
酸の合成方法としては、従来、光学活性を有する
プロリンメチルエステルをアシル化してアミドエ
ステルとし、これをヨウ化メチルマグネシウムの
存在下にメチルエステル基を３級アルコールと
し、次いでアシル基をアルキル化し、得られるジ
アストレオマーを加水分解する方法〔Lin
Guoqiang，他、アクタ ケミカ スカンジナビ
カ（Acta Chemica Scandinavica）B38P795〜
801〕、及び光学活性を有する３−メトキシ−２−
フエニルオキサゾリンをアルキル化した後、加水
分解する方法〔Styrbjoern Bystroem，他、テト
ラヘドロン（Tetrahedron）37p2249〜2254〕等
不斉合成による方法が、提案されている。[Prior Art] Conventionally, as a method for synthesizing an optically active α-methylalkylcarboxylic acid, an optically active proline methyl ester is acylated to form an amide ester, and this is converted into a methyl ester in the presence of methylmagnesium iodide. A method in which the group is a tertiary alcohol, the acyl group is then alkylated, and the resulting diastereomer is hydrolyzed [Lin
Guoqiang, et al., Acta Chemica Scandinavica B38 P795~
801], and 3-methoxy-2- having optical activity
A method has been proposed in which phenyloxazoline is alkylated and then hydrolyzed [Styrbjoern Bystroem et al., Tetrahedron 37 p. 2249-2254] by iso-asymmetric synthesis.
［発明が解決しようとする問題点］
上記不斉合成による従来の方法は、得られる生
成物の光学純度が72％ee程で低く、また反応のス
テツプが長くて収率も低く、しかも、用いる試薬
が高価である等の欠点が有つた。[Problems to be solved by the invention] In the conventional method using the asymmetric synthesis described above, the optical purity of the obtained product is low at about 72% ee, and the reaction steps are long and the yield is low. It had drawbacks such as expensive reagents.
本発明者は、かかる現状に鑑み鋭意検討した結
果、光学活性を有する１，２−エポキシドを一定
の方法で反応させることによりラセミ化すること
なくα−メチルアルキルカルボン酸を合成できる
ことを見い出した。 As a result of intensive studies in view of the current situation, the present inventors have discovered that α-methylalkylcarboxylic acid can be synthesized without racemization by reacting optically active 1,2-epoxide in a certain manner.
本発明は、かかる知見に基づいて成されたもの
で、本発明の目的は、簡単な反応ステツプから成
り、生成物の収率が極めて高い、しかも高光学純
度で、製造コストの安価なα−メチルアルキルカ
ルボン酸の合成方法を提供することにある。 The present invention has been made based on this knowledge, and the object of the present invention is to produce an α-α-α-α-α-propyl alcohol that is composed of simple reaction steps, has an extremely high yield of a product, has high optical purity, and is inexpensive to produce. An object of the present invention is to provide a method for synthesizing methylalkylcarboxylic acid.
［問題点を解決するための手段］
本発明は、光学活性を有する１，２−エポキシ
アルカンを出発原料とし、これをトリメチルアル
ミニウムと反応させて２−メチル−１−アルカノ
ールとし、次いでこのアルコールを過マンガン酸
カリウムで酸化することから成る光学活性を有す
るα−メチルアルキルカルボン酸の製造方法であ
る。[Means for Solving the Problems] The present invention uses an optically active 1,2-epoxyalkane as a starting material, reacts this with trimethylaluminum to form 2-methyl-1-alkanol, and then converts this alcohol into 2-methyl-1-alkanol. This is a method for producing optically active α-methylalkylcarboxylic acid, which comprises oxidizing with potassium permanganate.
本発明の出発原料として用いる上記光学活性を
有する１，２−エポキシアルカンは、光学純度が
少なくとも70％ee以上のものが好ましい。また、
この場合のアルカンは、用途に応じて、適宜各種
の炭素数のものが選定されるが、炭素数として３
〜18のものが、その原料を安価に入手でき、特に
好ましい。このような１，２−エポキシアルカン
は、ノカルデイア属に属するエポキシ生産能を有
する菌株を、α−オレフインを含有する培地で好
気的条件下に反応させることによつて得ることが
できる（特公昭56−40号公報参照）。この微生物
を利用する方法により得られる１，２−エポキシ
アルカンが光学活性を有することは、その後に確
認されたものであるが、α−オレフインから極め
て簡便に、しかも安価に製造できるので、本発明
の出発物質として利用することは、特に有利であ
る。 The optically active 1,2-epoxyalkane used as a starting material in the present invention preferably has an optical purity of at least 70% ee. Also,
In this case, alkanes with various carbon numbers are selected depending on the purpose, but the carbon number is 3.
~18 are particularly preferred because their raw materials can be obtained at low cost. Such 1,2-epoxyalkanes can be obtained by reacting a strain of Nocardia that has epoxy-producing ability in a medium containing α-olefin under aerobic conditions (Tokuko Sho (See Publication No. 56-40). It was later confirmed that the 1,2-epoxyalkane obtained by the method using this microorganism has optical activity, but since it can be produced extremely easily and inexpensively from α-olefin, the present invention It is particularly advantageous to use them as starting materials.
本発明では、先ず、上記１，２−エポキシアル
カンをトリメチルアルミニウムと反応させて開環
して２−メチル−１−アルカノールに変換させる
が、これは、トリメチルアルミニウムのヘキサ
ン、デカン、テトラデカン、シクロヘキサン等の
有機溶媒溶液に、上記１，２−エポキシアルカン
を−80℃〜150℃、ただし低沸点の有機溶媒の場
合は還流温度まで、温度範囲で撹拌しながら滴下
し、１〜120時間反応させ、反応終了後の反応液
を希塩酸溶液に注入して加水分解することにより
行う。この反応では１，２−エポキシアルカン１
モルに対し、トリメチルアルミニウム0.5〜３モ
ル、特には、トリメチルアルミニウム１〜２モル
を使用することが好ましい。生成物である２−メ
チル−１−アルカノールは、抽出、相分離、蒸
留、カラムクロマトグラフイー等の公知の手段で
単離精製することができる。 In the present invention, first, the 1,2-epoxyalkane is reacted with trimethylaluminum to open the ring and convert it into 2-methyl-1-alkanol. The above-mentioned 1,2-epoxyalkane is added dropwise to the organic solvent solution in a temperature range of -80°C to 150°C, but up to reflux temperature in the case of a low boiling point organic solvent, and reacted for 1 to 120 hours. After the reaction is completed, the reaction solution is poured into a dilute hydrochloric acid solution and hydrolyzed. In this reaction, 1,2-epoxyalkane 1
Preferably, 0.5 to 3 mol, in particular 1 to 2 mol, of trimethylaluminum are used per mole. The product 2-methyl-1-alkanol can be isolated and purified by known means such as extraction, phase separation, distillation, and column chromatography.
次に、この操作により得られた２−メチル−１
−アルカノールを過マンガン酸カリウムで酸化す
るが、この酸化反応は、酸性下で行なうことが好
ましく、酸としては特に、硫酸を用いると良い。
反応操作は５〜40％の硫酸水溶液に２−メチル−
１−オクタノールを加え、１〜３倍モルの過マン
ガン酸カリウムを20〜30℃の温度を保ちながらゆ
つくり加え反応させる。 Next, 2-methyl-1 obtained by this operation
-Alkanol is oxidized with potassium permanganate, and this oxidation reaction is preferably carried out under acidic conditions, and sulfuric acid is particularly preferably used as the acid.
The reaction operation is to add 2-methyl-
Add 1-octanol and slowly add 1 to 3 times the mole of potassium permanganate while maintaining the temperature at 20 to 30°C to react.
以上の様にして得られた反応混合物を亜硫酸水
素ナトリウムの水溶液に加えると未反応過マンガ
ン酸カリウム及び、二酸化マンガンが水に溶け、
α−メチルアルキルカルボン酸を簡便にエーテル
等の有機溶媒で抽出することができる。その後、
抽出をくり返し、蒸留、カラムクロマトグラフイ
ー等の公知の手段でα−メチルアルキルカルボン
酸を単離精製することができる。 When the reaction mixture obtained as described above is added to an aqueous solution of sodium bisulfite, unreacted potassium permanganate and manganese dioxide are dissolved in water.
α-methylalkylcarboxylic acid can be easily extracted with an organic solvent such as ether. after that,
After repeated extractions, α-methylalkylcarboxylic acid can be isolated and purified by known means such as distillation and column chromatography.
得られたα−メチルアルキルカルボン酸は、先
ず、酸ハロゲン化物とし、これにフエノールを反
応させて４−アルカノイルフエノールを得、次い
で、この４−アルカノイルフエノールと4′−アル
コキシビフエニル−４−カルボン酸とをエステル
化させることにより、カイラルスメクチツク相を
取る強誘電性液晶物質を得ることができる。 The obtained α-methylalkylcarboxylic acid is first converted into an acid halide, which is reacted with phenol to obtain 4-alkanoylphenol, and then this 4-alkanoylphenol and 4'-alkoxybiphenyl-4-carboxylic acid are converted into an acid halide. By esterifying the material with an acid, a ferroelectric liquid crystal material having a chiral smectic phase can be obtained.
一方、前述の文献〔Styrbjoern Bystroem，
他、テトラヘドロン（Tetrahedron）37p2249〜
2254〕に記載の方法に従うと昆虫の性フエロモン
を合成することができる。 On the other hand, the aforementioned literature [Styrbjoern Bystroem,
Others, Tetrahedron 37 p2249~
2254], insect sex pheromones can be synthesized.
［実施例］
（実施例 １）
トリメチルアルミニウムの１モル濃度のヘキサ
ン溶液１に、撹拌下に〔α〕25＋14.4゜（neat）の
（Ｒ）−１，２−エポキシオクタン85.8ｇ
（0.67mol）を30分で滴下後、２時間還流した。
冷却後、氷冷した12％塩酸水溶液にあけ、ヘキサ
ンで抽出し、ヘキサン層を水で洗浄した後、無水
硫酸ナトリウムで脱水し、溶媒を留去後、蒸留
（８mmHg、87〜92℃）し、純度90.4％の２−メチ
ル−１−オクタノール78.2ｇを得た。尚、純度は
シリコンSE−30を担持した２ｍのカラムを用い
てガスクロマトグラフイーにより測定した。ま
た、上記純度90.4％の２−メチル−１−オクタノ
ールを精留して得られる純度95.5％の２−メチル
−１−オクタノールの比旋光度は〔α〕25−9.6゜
（neat）だつた。[Example] (Example 1) 85.8 g of (R)-1,2-epoxyoctane of [α] 25 +14.4° (neat) was added to 1 molar solution of trimethylaluminum in hexane under stirring.
(0.67 mol) was added dropwise over 30 minutes, and the mixture was refluxed for 2 hours.
After cooling, pour into ice-cooled 12% aqueous hydrochloric acid solution, extract with hexane, wash the hexane layer with water, dehydrate with anhydrous sodium sulfate, remove the solvent, and then distill (8 mmHg, 87-92°C). , 78.2 g of 2-methyl-1-octanol with a purity of 90.4% was obtained. The purity was measured by gas chromatography using a 2 m column supporting silicon SE-30. Further, the specific optical rotation of 2-methyl-1-octanol with a purity of 95.5% obtained by rectifying the 2-methyl-1-octanol with a purity of 90.4% was [α] 25 −9.6° (neat).
このようにして得られた（−）２−メチル−１
−オクタノール24.7ｇ（0.17mol）に水330ml、濃
硫酸46.6ｇを加えた後、撹拌しながら、過マンガ
ン酸カリウム63.4ｇを反応温度30℃以下に保ちな
がらゆつくり加えた。その後、氷水340mlに反応
混合物を移し、亜硫酸水素ナトリウム51.5ｇを加
え、塩酸を用いてPH１以下にした後、エーテルで
抽出した。このエーテル層からα−メチルオクタ
ン酸を10％水酸化ナトリウム水溶液で抽出した。 (-)2-methyl-1 thus obtained
- After adding 330 ml of water and 46.6 g of concentrated sulfuric acid to 24.7 g (0.17 mol) of octanol, 63.4 g of potassium permanganate was slowly added while stirring while keeping the reaction temperature below 30°C. Thereafter, the reaction mixture was transferred to 340 ml of ice water, 51.5 g of sodium bisulfite was added, the pH was adjusted to below 1 using hydrochloric acid, and the mixture was extracted with ether. α-Methyloctanoic acid was extracted from this ether layer with a 10% aqueous sodium hydroxide solution.
次に、この水層に氷水100ml、濃塩酸110mlを加
えPH１以下とし、α−メチルオクタン酸をクロロ
ホルムで抽出、有機層を水で洗浄した後、硫酸マ
グネシウムで乾燥した。別後、減圧蒸留（0.28
mmHg、91〜94℃）で（＋）α−メチルオクタン
酸を15.28ｇ（0.097mol、収率64％）得た。 Next, 100 ml of ice water and 110 ml of concentrated hydrochloric acid were added to this aqueous layer to bring the pH to below 1, and α-methyloctanoic acid was extracted with chloroform. The organic layer was washed with water and then dried over magnesium sulfate. After separation, vacuum distillation (0.28
mmHg, 91-94°C), 15.28 g (0.097 mol, yield 64%) of (+)α-methyloctanoic acid was obtained.
1H−NMR（CDCl3中，TMS基準，ppm）：
11.8（ｂ，1H）、2.5（ｍ，1H）、1.7〜1.2（ｍ，
13H）、0.9（ｔ，3H）
IR（cm-1）：2910、1700
〔α〕25：＋14.0゜
（実施例 ２）
（Ｒ）−１，２−エポキシデカンを原料とし、
実施例１と同様の方法でトリメチルアルミニウム
とヘキサン中で反応させることにより２−メチル
−１−デカノール（83％ee）を得、更に硫酸酸性
下、過マンガン酸カリウムで酸化することによ
り、ラセミ化することなくα−メチルデカン酸を
得た。 1H -NMR (in CDCl 3 , TMS standard, ppm):
11.8 (b, 1H), 2.5 (m, 1H), 1.7~1.2 (m,
13H), 0.9 (t, 3H) IR (cm -1 ): 2910, 1700 [α] 25 : +14.0° (Example 2) Using (R)-1,2-epoxydecane as a raw material,
2-Methyl-1-decanol (83% ee) was obtained by reacting trimethylaluminum in hexane in the same manner as in Example 1, and racemized by further oxidation with potassium permanganate under acidic sulfuric acid. α-Methyldecanoic acid was obtained without any addition.
1H−NMR（CDCl3中，TMS基準，ppm）：
11.8（ｂ，1H）、2.5（ｍ，1H）、1.7〜1.2（ｍ，
17H）、0.9（ｔ，3H）
IR（cm-1）：2910、1700、1460
〔α〕25：＋12.3゜
（実施例 ３）
（Ｒ）−１，２−エポキシヘキサンを原料とし、
実施例１と同様の方法でトリメチルアルミニウム
とヘキサン中で反応させることにより２−メチル
−１−ヘキサノール（67％ee）を得、更に硫酸酸
性下、過マンガン酸カリウムで酸化することによ
り、ラセミ化することなくα−メチルヘキサン酸
を得た。 1H -NMR (in CDCl 3 , TMS standard, ppm):
11.8 (b, 1H), 2.5 (m, 1H), 1.7~1.2 (m,
17H), 0.9 (t, 3H) IR (cm -1 ): 2910, 1700, 1460 [α] 25 : +12.3° (Example 3) Using (R)-1,2-epoxyhexane as a raw material,
2-Methyl-1-hexanol (67% ee) was obtained by reacting with trimethylaluminum in hexane in the same manner as in Example 1, and racemized by further oxidation with potassium permanganate under acidic sulfuric acid. α-Methylhexanoic acid was obtained without addition.
1H−NMR（CDCl3中，TMS基準，ppm）：
11.8（ｂ，1H）、2.5（ｍ，1H）、1.7〜1.2（ｍ，
9H）、0.9（ｔ，3H）
IR（cm-1）：2910、1700、1460
〔α〕25：＋12.4゜
（参考例）
上記実施例２で得られた（＋）α−メチルデカ
ン酸を用いて次ぎの方法で強誘電性液晶物質であ
る（＋）４−（２−メチル）デカノイルフエニル，
4′−オクチルオキシビフエニル−４−カルボン酸
エステルを合成した。 1H -NMR (in CDCl 3 , TMS standard, ppm):
11.8 (b, 1H), 2.5 (m, 1H), 1.7~1.2 (m,
9H), 0.9 (t, 3H) IR (cm -1 ): 2910, 1700, 1460 [α] 25 : +12.4° (Reference example) The (+)α-methyldecanoic acid obtained in Example 2 above was The ferroelectric liquid crystal material (+)4-(2-methyl)decanoyl phenyl,
4'-octyloxybiphenyl-4-carboxylic acid ester was synthesized.
フラスコに、実施例２で合成したα−メチルカ
ルボン酸4.9ｇをとり、室温で撹拌しながら滴下
ロートから塩化チオニル4.8ｇを６分間滴下した。
40分間室温で反応させた後、80℃で30分間更に撹
拌反応させる。塩化チオニルを減圧で留去し、
（＋）α−メチルデカン酸クロリド、5.4ｇを得
た。 4.9 g of the α-methylcarboxylic acid synthesized in Example 2 was placed in a flask, and 4.8 g of thionyl chloride was added dropwise from the dropping funnel over 6 minutes while stirring at room temperature.
After reacting at room temperature for 40 minutes, the reaction was further stirred at 80°C for 30 minutes. Thionyl chloride was distilled off under reduced pressure.
5.4 g of (+)α-methyldecanoic acid chloride was obtained.
次に、無水塩化メチレン2.5mlにフエノール
2.32ｇ（25mmol）を入れ、窒素下−12℃で塩化
アルミニウム7.76ｇ（97mmol）を加えたものに、
−15℃の温度で、上記で得られた（＋）α−メチ
ルデカン酸クロリド、5.39ｇ（26mmol）を滴下
して加え、塩氷水で冷却しながら２時間撹拌し
た。この反応混合物を氷水300mlに入れ、塩化メ
チレンで抽出、水洗いした後、硫酸マグネシウム
で乾燥、別、濃縮後、フエニル−２−メチルデ
カン酸エステル4.3ｇを得た。このフエニル−２
−メチルデカン酸エステルを塩化メチレン25ml中
に入れ窒素下で−10℃の温度で、塩化アルミニウ
ム4.48ｇ（58mmol）を加え、ゆつくり室温に戻
した後、４時間加熱還流した。得られた反応混合
物を氷水200mlに移し、クロロホルムで抽出、有
機層を水で洗浄した後、硫酸マグネシウムで乾
燥、別、濃縮後、シリカゲルによるカラムクロ
ストグラフイーで単離精製し、赤褐色液体の
（＋）４−（２−メチル）デカノイルフエノール
1.77ｇ（9.6mmol収率40％）を得た。 Next, add phenol to 2.5 ml of anhydrous methylene chloride.
2.32g (25mmol) and 7.76g (97mmol) of aluminum chloride were added at -12℃ under nitrogen.
At a temperature of -15°C, 5.39 g (26 mmol) of (+)α-methyldecanoic acid chloride obtained above was added dropwise, and the mixture was stirred for 2 hours while cooling with salt ice water. The reaction mixture was poured into 300 ml of ice water, extracted with methylene chloride, washed with water, dried over magnesium sulfate, separated, and concentrated to obtain 4.3 g of phenyl-2-methyldecanoic acid ester. This phenyl-2
-Methyl decanoic acid ester was placed in 25 ml of methylene chloride under nitrogen at a temperature of -10°C, and 4.48 g (58 mmol) of aluminum chloride was added thereto, the mixture was slowly returned to room temperature, and then heated under reflux for 4 hours. The resulting reaction mixture was transferred to 200 ml of ice water, extracted with chloroform, the organic layer was washed with water, dried over magnesium sulfate, separated, concentrated, isolated and purified by column clostography using silica gel, and a reddish brown liquid ( +) 4-(2-methyl)decanoylphenol
1.77g (9.6mmol yield 40%) was obtained.
次に、水−エタノールの混合溶媒240mlに水酸
化ナトリウム50ｇを溶解させた溶液に、市販の
4′−オクチルオキシ−４−シアノビフエニル10ｇ
（32mmol）を加え、加熱還流下、３時間反応さ
せた。反応混合物を塩酸で酸性にした後、別
し、エタノール−酢酸溶媒で再結晶し固体物を得
た。この生成物についてKBr法による赤外スペ
クトル分析を行なつた結果、3400cm-1、3200cm
-1、2950〜2850cm-1、1650cm-1、1600cm-1にそれ
ぞれ吸収が認められ、4′−オクチルオキシビフエ
ニル−４−カルボン酸であることが確認できた。
塩化メチレン５mlに4′−オクチルオキシビフエニ
ル−４−カルボン酸450mg（1.4mmol）、（＋）４
−（２−メチル）デカノイルフエノール350mg
（1.4mmol）、４−ジメチルアミノピリジン10mgを
入れた混合物に、Ｎ，N′−ジシクロヘキシルカ
ルボジイミド275mg（1.4mmol）を加えた。これ
を４時間加熱還流した後、過し、液を塩化メ
チレンで抽出、水洗し、硫酸マグネシウムで乾
燥、別、濃縮後、得られた固体をエタノールで
再結晶することにより白色固体の４−（２−メチ
ル）デカノイルフエニル，4′−オクチルオキシビ
フエニル−４−カルボン酸エステルを得た。この
化合物の理化学的性状を次に示す。 Next, add commercially available
4'-octyloxy-4-cyanobiphenyl 10g
(32 mmol) was added, and the mixture was reacted for 3 hours under heating under reflux. The reaction mixture was made acidic with hydrochloric acid, separated, and recrystallized from an ethanol-acetic acid solvent to obtain a solid. Infrared spectrum analysis of this product using the KBr method revealed 3400 cm -1 and 3200 cm
Absorption was observed at -1 , 2950 to 2850 cm -1 , 1650 cm -1 and 1600 cm -1 , and it was confirmed that it was 4'-octyloxybiphenyl-4-carboxylic acid.
450 mg (1.4 mmol) of 4'-octyloxybiphenyl-4-carboxylic acid in 5 ml of methylene chloride, (+)4
-(2-methyl)decanoylphenol 350mg
(1.4 mmol) and 10 mg of 4-dimethylaminopyridine, 275 mg (1.4 mmol) of N,N'-dicyclohexylcarbodiimide was added. After heating under reflux for 4 hours, it was filtered, and the liquid was extracted with methylene chloride, washed with water, dried over magnesium sulfate, separated, concentrated, and the resulting solid was recrystallized with ethanol to form a white solid, 4-( 2-Methyl)decanoyl phenyl, 4'-octyloxybiphenyl-4-carboxylic acid ester was obtained. The physicochemical properties of this compound are shown below.
1H NMR（CDCl3中，TMS基準，ppm）：8.3
〜7.0（12H）、4.0（ｔ，2H）、3.4（ｍ，1H）、1.9
〜0.9（ｍ，35H）
IR（KBr cm-1）：2950〜2850、1735、1680、
1600
Mass：570（M+）
上記化合物を偏光顕微鏡を用いて組織の変化を
観察した結果、昇温過程において59.0℃で強誘電
性相の液晶状態となり124.0℃でスメクテイツク
Ａ相の液晶に変化し、152.0℃で等方性液体とな
つた。また降温過程では、150.7℃でスメクテイ
ツクＡ相の液晶状態と成り、125℃でスメクテイ
ツクＣ相の液晶に変化し、58.0℃で固体結晶とな
つた。 1H NMR (in CDCl 3 , TMS standard, ppm): 8.3
~7.0 (12H), 4.0 (t, 2H), 3.4 (m, 1H), 1.9
~0.9 (m, 35H) IR (KBr cm -1 ): 2950 ~ 2850, 1735, 1680,
1600 Mass: 570 (M + ) As a result of observing changes in the structure of the above compound using a polarizing microscope, it was found that during the heating process, it became a ferroelectric phase liquid crystal at 59.0℃ and changed to a smectic A phase liquid crystal at 124.0℃. , it became an isotropic liquid at 152.0℃. During the cooling process, it became a smectic A phase liquid crystal at 150.7°C, changed to a smectic C phase liquid crystal at 125°C, and became a solid crystal at 58.0°C.
また厚さ3μｍのポリエチレンテレフタレート
フイルムをスペンサーとし、ネサガラスで構成し
たセルに上記化合物を封入し、100Hzの交流をか
け三角波法により、自発分極を測定した結果60℃
で、210nc／cm2と非常に大きい自発分極を示し
た。 In addition, the above compound was sealed in a cell made of Nesa glass using a polyethylene terephthalate film with a thickness of 3 μm as a spacer, and the spontaneous polarization was measured using the triangular wave method by applying an alternating current of 100 Hz at 60°C.
It showed a very large spontaneous polarization of 210 nc/cm 2 .
［発明の効果］
本発明は、α−メチルアルキルカルボン酸を簡
単な反応ステツプで、収率良く、しかも高光学純
度で、安価に合成できるという極めて優れた効果
を奏するものである。[Effects of the Invention] The present invention has an extremely excellent effect in that α-methylalkylcarboxylic acid can be synthesized with simple reaction steps, in good yield, with high optical purity, and at low cost.
Claims (1)
を出発原料とし、これをトリメチルアルミニウム
と反応させて２−メチル−１−アルカノールと
し、次いでこのアルコールを過マンガン酸カリウ
ムで酸化することを特徴とする光学活性を有する
α−メチルアルキルカルボン酸の製造方法。1 An optical method characterized by using an optically active 1,2-epoxyalkane as a starting material, reacting it with trimethylaluminum to produce 2-methyl-1-alkanol, and then oxidizing this alcohol with potassium permanganate. A method for producing active α-methylalkylcarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7592087A JPS63243058A (en) | 1987-03-31 | 1987-03-31 | Production of optically active alpha-methylalkylcarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7592087A JPS63243058A (en) | 1987-03-31 | 1987-03-31 | Production of optically active alpha-methylalkylcarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63243058A JPS63243058A (en) | 1988-10-07 |
| JPH0333696B2 true JPH0333696B2 (en) | 1991-05-20 |
Family
ID=13590229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7592087A Granted JPS63243058A (en) | 1987-03-31 | 1987-03-31 | Production of optically active alpha-methylalkylcarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63243058A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0643362B2 (en) * | 1988-10-21 | 1994-06-08 | 日本鉱業株式会社 | Process for producing optically active 2-fluoroalkanoic acid |
| JPH0643363B2 (en) * | 1989-10-27 | 1994-06-08 | 日本鉱業株式会社 | Process for producing optically active 2-fluoro-2-methylalkanoic acid |
-
1987
- 1987-03-31 JP JP7592087A patent/JPS63243058A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63243058A (en) | 1988-10-07 |
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