JPH0463598A - Carboxylic acid having trifluoromethyl group and production thereof - Google Patents
Carboxylic acid having trifluoromethyl group and production thereofInfo
- Publication number
- JPH0463598A JPH0463598A JP17258190A JP17258190A JPH0463598A JP H0463598 A JPH0463598 A JP H0463598A JP 17258190 A JP17258190 A JP 17258190A JP 17258190 A JP17258190 A JP 17258190A JP H0463598 A JPH0463598 A JP H0463598A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- trifluoromethyl group
- lipase
- trifluoromethyl
- 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.)
- Pending
Links
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 102000004882 Lipase Human genes 0.000 claims abstract description 13
- 108090001060 Lipase Proteins 0.000 claims abstract description 13
- 239000004367 Lipase Substances 0.000 claims abstract description 13
- 235000019421 lipase Nutrition 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003905 agrochemical Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 101000968491 Pseudomonas sp. (strain 109) Triacylglycerol lipase Proteins 0.000 description 5
- -1 2-trifluoromethylnonanoic acid Chemical compound 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000013543 active substance Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- PZBFWLHXZOLQTQ-UHFFFAOYSA-N ethyl 2-(trifluoromethyl)butanoate Chemical compound CCOC(=O)C(CC)C(F)(F)F PZBFWLHXZOLQTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- JJBKSQGESJSIHC-UHFFFAOYSA-N 1,1,1-trifluoro-2-methylbutane Chemical compound CCC(C)C(F)(F)F JJBKSQGESJSIHC-UHFFFAOYSA-N 0.000 description 1
- XOXCOCDAUCEEMR-UHFFFAOYSA-N 2-(trifluoromethyl)butanoic acid Chemical compound CCC(C(O)=O)C(F)(F)F XOXCOCDAUCEEMR-UHFFFAOYSA-N 0.000 description 1
- BNPZSCCCDNKDPT-UHFFFAOYSA-N 2-(trifluoromethyl)hexanoic acid Chemical compound CCCCC(C(O)=O)C(F)(F)F BNPZSCCCDNKDPT-UHFFFAOYSA-N 0.000 description 1
- ULZXWRXUUYUBIV-UHFFFAOYSA-N 2-(trifluoromethyl)octanoic acid Chemical compound CCCCCCC(C(O)=O)C(F)(F)F ULZXWRXUUYUBIV-UHFFFAOYSA-N 0.000 description 1
- QAYZRUVLPNKTQU-UHFFFAOYSA-N 2-(trifluoromethyl)pent-4-enoic acid Chemical compound OC(=O)C(C(F)(F)F)CC=C QAYZRUVLPNKTQU-UHFFFAOYSA-N 0.000 description 1
- PANCHYASFLIUMK-UHFFFAOYSA-N 2-benzyl-3,3,3-trifluoropropanoic acid Chemical compound OC(=O)C(C(F)(F)F)CC1=CC=CC=C1 PANCHYASFLIUMK-UHFFFAOYSA-N 0.000 description 1
- DQOGDQIDOONUSK-UHFFFAOYSA-N 3,3,3-trifluoro-2-methylpropanoic acid Chemical compound OC(=O)C(C)C(F)(F)F DQOGDQIDOONUSK-UHFFFAOYSA-N 0.000 description 1
- NDZIGRYCYVFRGQ-UHFFFAOYSA-N 3-methyl-2-(trifluoromethyl)butanoic acid Chemical compound CC(C)C(C(O)=O)C(F)(F)F NDZIGRYCYVFRGQ-UHFFFAOYSA-N 0.000 description 1
- ZZNVBHMFMUVGHK-UHFFFAOYSA-N 5,5,5-trifluoro-4-methylpent-1-ene Chemical compound FC(F)(F)C(C)CC=C ZZNVBHMFMUVGHK-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- OHIFNJXUDQUIBY-UHFFFAOYSA-N ethyl 3,3,3-trifluoro-2-phenylpropanoate Chemical compound CCOC(=O)C(C(F)(F)F)C1=CC=CC=C1 OHIFNJXUDQUIBY-UHFFFAOYSA-N 0.000 description 1
- VQEALXBAXNTFPO-UHFFFAOYSA-N ethyl 3-methyl-2-(trifluoromethyl)butanoate Chemical compound CCOC(=O)C(C(C)C)C(F)(F)F VQEALXBAXNTFPO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、医薬、農薬、液晶化合物などの機能性材料な
どの原料として有用である新規なトリフルオロメチル基
を有するカルボン酸類およびその製造方法に関するもの
である。Detailed Description of the Invention (Industrial Application Field) The present invention relates to novel trifluoromethyl group-containing carboxylic acids that are useful as raw materials for functional materials such as medicines, agricultural chemicals, and liquid crystal compounds, and a method for producing the same. It is related to.
（従来の技術）
一般に、フッ素化合物には特異的な物性や生理活性を有
するものが多く、その合成研究も多い〔例えば、化学総
説、「新しいフッ素化学」、日本化学金線、学会出版セ
ンター（Ｉ９８０） ）。(Prior art) In general, many fluorine compounds have specific physical properties and physiological activities, and there are many synthetic studies on them [for example, Chemistry Review, "New Fluorine Chemistry", Nippon Kagaku Gold Wire, Gakkai Publishing Center ( I980) ).
トリフルオロメチル基を有する化合物は、次の一般式（
ＩＩ［）、
ＲＣＨＣ００ＣｚＨｓ 、 （ＩＩ）０Ｆ。A compound having a trifluoromethyl group has the following general formula (
II[), RCHC00CzHs, (II)0F.
（式中、Ｒは２重結合を含んでいても良い直鎖または技
分かれしたアルキル基または芳香族基を表す）で示され
る化合物として知られており、これはマロン酸を出発原
料にした方法やグリニヤール試薬を用いた方法で製造す
ることができる（Ｅｖｅｒｅｔｔｅｔ ａｌ、、 Ｊ、
Ｏｒｇ、Ｃｈｅｍ、 Ｑ、 ３７０２ （Ｉ９８４）ま
たはＫｉｔａｚｕｍｅ ｅｔ ａｌ、、 Ｊ、５ｙｎ
ｔｈ、Ｏｒｇ、Ｃｈｅｍ、 ８，６１４（Ｉ９８８）
）。(In the formula, R represents a linear or branched alkyl group or an aromatic group that may contain a double bond.) This is a method using malonic acid as a starting material. It can be produced by a method using a Grignard reagent or a Grignard reagent (Everett et al., J.
Org, Chem, Q, 3702 (I984) or Kitazume et al, J, 5yn.
th, Org, Chem, 8,614 (I988)
).
（発明が解決しようとする課題）
そこで、本発明の目的は、上述のように医薬、農薬、液
晶化合物などの原料として有用なトリフルオロメチル基
を有する化合物の新規なもの、特にはその光学活性体を
提供することにある。(Problems to be Solved by the Invention) Therefore, an object of the present invention is to create a novel compound having a trifluoromethyl group that is useful as a raw material for medicines, agricultural chemicals, liquid crystal compounds, etc., particularly its optical activity. It's about offering your body.
（課題を解決するための手段）
本発明は、上記目的を達成するためになされたもので、
本発明のトリフルオロメチル基を有する化合物は、次の
一般式（Ｉ）、
Ｒ，−ＣＨ−Ｃ０ＯＨ（Ｉ）
ＣＦ。(Means for Solving the Problems) The present invention has been made to achieve the above objects, and
The compound having a trifluoromethyl group of the present invention has the following general formula (I): R, -CH-C0OH (I) CF.
（式中、Ｒ，は末端に不飽和結合を含んでいても良い直
鎖もしくは枝分れしたアルキル基または芳香族基を表す
）で示される新規なトリフルオロメチル基を有するカル
ボン酸類、特にはその光学活性体である。(In the formula, R represents a linear or branched alkyl group or an aromatic group which may contain an unsaturated bond at the terminal.) Carboxylic acids having a novel trifluoromethyl group, especially It is its optically active form.
また、本発明は、次の一般式（Ｉ［）、Ｒｚ Ｃ）Ｉ
ＣＯＯＲｘ （ＩＩ）ＣＦ３
（式中、Ｒ２は不飽和結合を含んでいても良い直鎖もし
くは枝分れしたアルキル基または芳香族基を、またＲ１
は低級アルキル基を表す）で示されるトリフルオロメチ
ル基を有するカルボン酸エステル類をリパーゼを用いて
加水分解することを特徴とする上記式（Ｉ）で示される
新規なトリフルオロメチル基を有するカルボン酸類の製
造方法に関するものである。Further, the present invention provides the following general formula (I[), Rz C)I
COORx (II) CF3 (wherein, R2 is a linear or branched alkyl group or an aromatic group which may contain an unsaturated bond, and R1
represents a lower alkyl group) A novel carboxylic acid ester having a trifluoromethyl group represented by the above formula (I) is hydrolyzed using lipase. This invention relates to a method for producing acids.
本発明の上記式（Ｉ）で示される具体的化合物としては
、２−トリフルオロメチルプロパン酸、２−トリフルオ
ロメチルブタン酸、２−トリフルオロメチルペンクン酸
、２−トリフルオロメチルヘキサン酸、２−トリフルオ
ロメチルへブタン酸、２−トリフルオロメチルオクタン
酸、２−トリフルオロメチルノナン酸、２−トリフルオ
ロメチルデカン酸、２−トリフルオロメチルウンデカン
酸、２−トリフルオロメチルドデカン酸、２−トリフル
オロメチル−３−メチルブタン酸、２−トリフルオロメ
チル−４−ペンテン酸、２−トリフルオロメチル−２−
フェニルエタン酸、２−トリフルオロメチル−３−フェ
ニルプロパン酸等を例示することができる。Specific compounds represented by the above formula (I) of the present invention include 2-trifluoromethylpropanoic acid, 2-trifluoromethylbutanoic acid, 2-trifluoromethylpencunic acid, 2-trifluoromethylhexanoic acid, 2-trifluoromethylhebutanoic acid, 2-trifluoromethyloctanoic acid, 2-trifluoromethylnonanoic acid, 2-trifluoromethyldecanoic acid, 2-trifluoromethylundecanoic acid, 2-trifluoromethyldodecanoic acid, 2 -trifluoromethyl-3-methylbutanoic acid, 2-trifluoromethyl-4-pentenoic acid, 2-trifluoromethyl-2-
Examples include phenylethanoic acid and 2-trifluoromethyl-3-phenylpropanoic acid.
なお、上記一般式（Ｉ）中、Ｒ１で表した末端に不飽和
結合を有することもあるアルキル基は、特には制限がな
いが、実用上の見地から炭素数１〜１０とすることが望
ましい。Ｒ３のうち、末端に不飽和結合を有するアルキ
ル基のものは、内部に不飽和結合を有するものに比べて
、液晶化合物とした時に優れたものができる。In addition, in the above general formula (I), the alkyl group that may have an unsaturated bond at the terminal represented by R1 is not particularly limited, but from a practical standpoint, it is desirable to have 1 to 10 carbon atoms. . Among R3, those having an alkyl group having an unsaturated bond at the terminal can produce a liquid crystal compound superior to those having an internal unsaturated bond.
上記化合物は、２−位の炭素が不斉炭素であり、この炭
素を中心として光学活性が付与された光学活性体も本発
明に包含されるものである。この光学活性体は、特に、
生理活性に優れた医薬、農薬さらには強誘電性液晶化合
物などの中間原料として有用である。In the above compound, the carbon at the 2-position is an asymmetric carbon, and the present invention also includes an optically active substance that is endowed with optical activity centered on this carbon. This optically active substance is particularly
It is useful as an intermediate raw material for pharmaceuticals with excellent physiological activity, agricultural chemicals, and ferroelectric liquid crystal compounds.
上記一般式（■）の化合物の代表的なものについて、次
に理化学的性質を述べる。Next, the physical and chemical properties of typical compounds of the above general formula (■) will be described.
２−トリフルオロメチルブタン
■沸点＝８０〜８３°Ｃ／１５０ ｍｍＨｇ■’Ｈ−Ｎ
ＭＲ（ＣＤＣｈ） ：
１１．１ （ｓ、ＩＨ）、 ２．８〜３．４ （ｍ、Ｉ
Ｈ）、 ０．６〜２．４（ｍ ５Ｈ）
■”Ｆ−ＮＭＲ：
９．７ （３Ｆ、ｄ、Ｊ、４ｒ ＝７．５Ｈｚ）■〔α
） ２ｔ４０．９２（ｃ １．００５． ＣＨ：１ＯＨ
）−２−トリフルオロメチルヘキサン
■’Ｈ−ＮＩ’１Ｒ（ＣＤＣｌ２）
１０．４ （ｓ、ＩＨ）、 ２．９〜３．５ （ｍ、Ｉ
Ｈ）、 ０．８〜２．４（ｍ、９８）
■”Ｆ−ＮＭＲニ
ー９．２ （３ｐ、ｄ、 Ｊ ＨＦ ＝７．５Ｈ２）■
〔α） ” ニー１４．９ （ｃ １．０． Ｃ）＋３
０Ｈ）２−トリフルオロメチル−４−ペンテン■’Ｈ−
ＮＭＲ（ＣＤＣｈ）
８．８ （ｓ、ＬＨ）、 ５．８〜６．０ （＋
ｎ、ＬＨ）、 ５．０〜５．４０（ｍ、２Ｈ）
■”Ｆ−ＮＭＲ：
１０．１１（３Ｆ、ｄ、 Ｊ ＨＦ ＝７．３１（Ｚ
）■〔α） ”： −７，６（ｃ １．１． ＣＨ３０
Ｈ）■’ Ｈ−ＮＭＲ（ＣＤＣＩ ２） ：９．０（ｓ
、ＩＨ）、 ７．２〜８．１ （ｍ、ＩＨ）、
４．０〜４．４（ｍ、ＩＨ）、３．２（ｍ、２Ｈ）、２
．４〜２．６（ｍ、ＩＨ）■１９Ｆ−ＮＭＲ：
１０．０ （３Ｆ、 ｄ、 ＪＨＦ ＝８．５Ｈ
ｚ）■〔α） ”： −４，８（ｃ Ｏ，４Ｂ、 ＣＨ
３０Ｈ）■’Ｈ−ＮＭＲ（ＣＤＣ１３） ：
８．６０（ｓ、ＩＨ）、７．２〜７．４ （ｍ、５Ｈ
）、３．４ （ｍ、ＩＨ）。2-Trifluoromethylbutane Boiling point = 80-83°C/150 mmHg ■'H-N
MR (CDCh): 11.1 (s, IH), 2.8-3.4 (m, I
H), 0.6 to 2.4 (m 5H) ■"F-NMR: 9.7 (3F, d, J, 4r = 7.5Hz) ■ [α
) 2t40.92(c 1.005.CH:1OH
)-2-Trifluoromethylhexane ■'H-NI'1R (CDCl2) 10.4 (s, IH), 2.9-3.5 (m, I
H), 0.8-2.4 (m, 98) ■"F-NMR knee 9.2 (3p, d, JHF = 7.5H2)■
[α) ” Knee 14.9 (c 1.0. C) +3
0H) 2-trifluoromethyl-4-pentene■'H-
NMR (CDCh) 8.8 (s, LH), 5.8-6.0 (+
n, LH), 5.0 to 5.40 (m, 2H) ■”F-NMR: 10.11 (3F, d, J HF = 7.31 (Z
) ■ [α) ”: -7,6 (c 1.1. CH30
H) ■' H-NMR (CDCI 2): 9.0 (s
, IH), 7.2-8.1 (m, IH),
4.0-4.4 (m, IH), 3.2 (m, 2H), 2
．． 4-2.6 (m, IH) ■19F-NMR: 10.0 (3F, d, JHF = 8.5H
z) ■ [α) ”: -4,8(c O,4B, CH
30H) ■'H-NMR (CDC13): 8.60 (s, IH), 7.2-7.4 (m, 5H
), 3.4 (m, IH).
３．４（ｍ、ＩＨ）、３．２（ｍ、２Ｈ）■ＩｑＦ−Ｎ
ＭＲ：
１０．０ （３Ｆ、ｄ、 ＪＨＦ □７．２Ｈｚ）
■〔α） ２２： ４３．０ （ｃ Ｏ，４８，Ｃ
Ｈ：１ＯＨ）■１９Ｆ−ＮＭＲ：
１３．０ （３Ｆ、ｄ、 ＪＨＦ ＝９．４Ｈｚ）
上記一般式（Ｉ）で示される化合物は、上記一般式（ｎ
）で示されるトリフルオロメチル基を有するカルボン酸
エステル類を出発原料として合成することができる。上
記一般式（Ｕ）中のＲ２で表した不飽和結合を有するこ
ともあるアルキル基は、特には制限がないが、実用上の
見地から炭素数１〜１０とすることが望ましく、またＲ
１はメチル、エチル、プロピル、ブチル等の低級アルキ
ル基であれば、容易に加水分解できる。3.4 (m, IH), 3.2 (m, 2H) ■IqF-N
MR: 10.0 (3F, d, JHF □7.2Hz)
■ [α) 22: 43.0 (c O, 48, C
H: 1OH) ■ 19F-NMR: 13.0 (3F, d, JHF = 9.4Hz)
The compound represented by the above general formula (I) is a compound represented by the above general formula (n
) can be synthesized using carboxylic acid esters having a trifluoromethyl group as starting materials. The alkyl group, which may have an unsaturated bond, represented by R2 in the above general formula (U) is not particularly limited, but from a practical standpoint, it is desirable to have 1 to 10 carbon atoms, and R
If 1 is a lower alkyl group such as methyl, ethyl, propyl, butyl, it can be easily hydrolyzed.
この場合、上記一般式（Ｕ）で示される出発原料を、リ
パーゼを用いて加水分解するが、このリパーゼとしては
リパーゼＰ、またはリパーゼＰＳが望ましい。具体的に
は、上記式（ＩＴ）で示されるエステル類およびリパー
ゼを含む水溶液をｐＨ５〜７に調整しながら攪拌する。In this case, the starting material represented by the above general formula (U) is hydrolyzed using a lipase, and the lipase is preferably lipase P or lipase PS. Specifically, an aqueous solution containing the ester represented by the above formula (IT) and lipase is stirred while adjusting the pH to 5 to 7.
これにより、容易に反応が進行し、−Ｃ式（Ｉ）で示さ
れる新規なトリフルオロメチル基を有するカルボン酸類
を得ることができる。なお、この場合の反応温度は、室
温から４０°Ｃぐらいを適宜選択すれば良い。Thereby, the reaction proceeds easily and a novel trifluoromethyl group-containing carboxylic acid represented by the -C formula (I) can be obtained. Note that the reaction temperature in this case may be appropriately selected from room temperature to about 40°C.
さらに、このリパーゼのうち、リパーゼＰまたはリパー
ゼＰＳを用いることによって、ラセミ体の一般式（ＩＩ
）を用いて不斉加水分解を進行させることができ、光学
活性なトリフルオロメチル基を有するカルボン酸類を得
ることができる。Furthermore, by using lipase P or lipase PS among these lipases, the racemic general formula (II
) can be used to advance asymmetric hydrolysis, and carboxylic acids having an optically active trifluoromethyl group can be obtained.
（実施例） 次に、本発明を実施例により具体的に説明する。(Example) Next, the present invention will be specifically explained using examples.
２−トリフルオロメチルブタン酸エチルエステル５．３
ｇ （０，０３ｍｍｏｌ） 、リパーゼＰ ４．８ｇ
および水１０ｍ１の混合物を反応温度４０″Ｃに保ちな
がら２４時間攪拌した。このとき、反応溶液内のｐＨを
５〜７に保つようにした（反応溶液内のｐＨが５以下に
なったときには、０．ＩＮ水酸化ナトリウム水溶液を用
いてｐＨが５〜７になるように調整した）。反応が４５
％進行したところ（すなわち０．Ｉ Ｎ水酸化ナトリウ
ム水溶液を１１４ ｍｆｆ１加えたところ）で、０．Ｉ
Ｎ水酸化ナトリウム水溶液を少量加えてｐＨを９とし、
反応温度を６０°Ｃに上げて反応を停止した。2-trifluoromethylbutanoic acid ethyl ester 5.3
g (0.03 mmol), lipase P 4.8 g
and 10 ml of water was stirred for 24 hours while maintaining the reaction temperature at 40"C. At this time, the pH in the reaction solution was maintained at 5 to 7 (when the pH in the reaction solution became 5 or less, (The pH was adjusted to 5 to 7 using a 0.IN aqueous solution of sodium hydroxide).
% (i.e., 114 mff1 of 0.IN aqueous sodium hydroxide solution was added), 0. I
Add a small amount of N sodium hydroxide aqueous solution to adjust the pH to 9,
The reaction temperature was raised to 60°C to stop the reaction.
反応終了後、室温で一晩放置して、凝固したリパーゼＰ
を濾別して、濾液からイソプロピルエーテルを用いて抽
出し、未反応のエステルを回収した。濾液は、水冷下、
塩酸を用いてｐ）ＩＩとした後に、イソプロピルエーテ
ルを用いて抽出し、抽出液を飽和食塩水、水で洗浄し、
無水硫酸ナトリウムで乾燥した。硫酸ナトリウムを濾別
した後に、イソプロピルエーテルを留去し、残渣を減圧
蒸留して、目的物５００ ｎａｇを得た。After the reaction is complete, leave it at room temperature overnight to solidify the lipase P.
was filtered, and the filtrate was extracted with isopropyl ether to recover unreacted ester. The filtrate is cooled with water,
After converting to p)II using hydrochloric acid, extracting using isopropyl ether, washing the extract with saturated saline and water,
It was dried with anhydrous sodium sulfate. After filtering off the sodium sulfate, isopropyl ether was distilled off and the residue was distilled under reduced pressure to obtain 500 nag of the target product.
２−トリフルオロメチルヘキサン酸エチルエステル８．
０ ｇ （０，０４ｍｍｏｌ） 、リパーゼｐｓ １０
．Ｏｇおよび水２０ｍ１を用いて実施例１と同様の反応
を行った。反応終了後、実施例Ｉと同様の後処理を行っ
た後に、ヘキサン：ジクロロメタン−９：１（Ｖ／Ｖ）
を展開溶媒に用いたシリカゲルクロマトグラフィーによ
って精製し目的物９００ ｍｇを得た。2-trifluoromethylhexanoic acid ethyl ester8.
0 g (0.04 mmol), lipase ps 10
．． A reaction similar to Example 1 was carried out using Og and 20 ml of water. After completion of the reaction, after performing the same post-treatment as in Example I, hexane:dichloromethane-9:1 (V/V)
The product was purified by silica gel chromatography using a developing solvent to obtain 900 mg of the desired product.
Ｐ ２．Ｏｇおよび水１０＋ｎｊ！を用いて実施例２と
同様の反応および後処理を行って、目的物３００ ｍｇ
を得た。P2. Og and water 10+nj! The same reaction and post-treatment as in Example 2 were carried out using
I got it.
２−トリフルオロメチル−４−ペンタン酸エチルエステ
ル８．８ ｇ （０，０４闘Ｏ１）、リパーゼＰＳ ３
．４ｇおよび水２０ｍ１を用いて実施例２と同様の反応
および後処理を行って、目的物１６２ｇを得た。2-trifluoromethyl-4-pentanoic acid ethyl ester 8.8 g (0.04 to O1), Lipase PS 3
．． The same reaction and post-treatment as in Example 2 were carried out using 4 g and 20 ml of water to obtain 162 g of the target product.
２−トリフルオロメチル−３−メチルブタン酸エチルエ
ステル１．８ ｇ （０，０１ａｎｏｌ） 、リパーゼ
Ｐ３、Ｏｇおよび水１０ｎ＋１！、を用いて実施例２と
同様の反応および後処理を行って、目的物３０ ｍｇを
得た。2-trifluoromethyl-3-methylbutanoic acid ethyl ester 1.8 g (0.01 anol), lipase P3, Og and water 10n+1! The same reaction and post-treatment as in Example 2 were carried out using , to obtain 30 mg of the target product.
２−トリフルオロメチル−２−フェニルエタン酸エチル
エステル２．３ ｇ （０，０１ｍｍｏｌ） 、リパー
ゼ２−トリフルオロメチル−３−メチルプロパン酸エチ
ルエステル５．９ ｇ （０，０２ｍｍｏｌ） 、リパ
ーゼＰ ４．Ｏｇおよび水３０ｍ！を用いて実施例２と
同様の反応および後処理を行って、目的物１．２ｇを得
た。2-trifluoromethyl-2-phenylethanoic acid ethyl ester 2.3 g (0.01 mmol), lipase 2-trifluoromethyl-3-methylpropanoic acid ethyl ester 5.9 g (0.02 mmol), lipase P 4 ．． Og and water 30m! The same reaction and post-treatment as in Example 2 were carried out using 1.2 g of the target product.
（発明の効果）
以上説明してきたように、本発明の新規な化合物は、医
薬、農薬、液晶化合物などの機能性有機材料などの原料
として有用なものであり、またこの化合物を製造する本
発明の方法は、温和な条件で、しかも簡便に行い得るも
のであり、また、特には、本発明の化合物の光学活性体
を極めて容易に得ることができるという格別の効果を奏
するものである。(Effects of the Invention) As explained above, the novel compound of the present invention is useful as a raw material for functional organic materials such as medicines, agricultural chemicals, and liquid crystal compounds, and the present invention for producing this compound The method described above can be easily carried out under mild conditions, and particularly has the special effect that the optically active form of the compound of the present invention can be obtained extremely easily.
Claims (1)
直鎖もしくは枝分れしたアルキル基または芳香族基を表
す）で示される新規なトリフルオロメチル基を有するカ
ルボン酸類。 ２、一般式（ I ）で示される化合物が光学活性である
請求項１記載の新規なトリフルオロメチル基を有するカ
ルボン酸類。 ３、次の一般式（II）、 ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿２は不飽和結合を含んでいても良い直鎖も
しくは枝分れしたアルキル基または芳香族基を、Ｒ＿３
は低級アルキル基を表す）で示されるトリフルオロメチ
ル基を有するカルボン酸エステル類を、リパーゼを用い
て加水分解することを特徴とする請求項１記載のカルボ
ン酸類の製造方法。[Claims] 1. The following general formula (I), ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1 is a straight chain or branched chain that may contain an unsaturated bond at the terminal. A novel carboxylic acid having a trifluoromethyl group represented by a branched alkyl group or an aromatic group. 2. The novel trifluoromethyl group-containing carboxylic acids according to claim 1, wherein the compound represented by formula (I) is optically active. 3. The following general formula (II), ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_2 is a straight chain or branched alkyl group that may contain an unsaturated bond, or an aromatic group. The group is R_3
2. The method for producing carboxylic acids according to claim 1, wherein the carboxylic acid ester having a trifluoromethyl group represented by (represents a lower alkyl group) is hydrolyzed using lipase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17258190A JPH0463598A (en) | 1990-07-02 | 1990-07-02 | Carboxylic acid having trifluoromethyl group and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17258190A JPH0463598A (en) | 1990-07-02 | 1990-07-02 | Carboxylic acid having trifluoromethyl group and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0463598A true JPH0463598A (en) | 1992-02-28 |
Family
ID=15944501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17258190A Pending JPH0463598A (en) | 1990-07-02 | 1990-07-02 | Carboxylic acid having trifluoromethyl group and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0463598A (en) |
-
1990
- 1990-07-02 JP JP17258190A patent/JPH0463598A/en active Pending
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