JPH01228927A - Gamma-fluoroalcohol and production thereof - Google Patents
Gamma-fluoroalcohol and production thereofInfo
- Publication number
- JPH01228927A JPH01228927A JP5688588A JP5688588A JPH01228927A JP H01228927 A JPH01228927 A JP H01228927A JP 5688588 A JP5688588 A JP 5688588A JP 5688588 A JP5688588 A JP 5688588A JP H01228927 A JPH01228927 A JP H01228927A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fluoroalcohol
- alkyl
- hydrogen atom
- phenyl
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 6
- -1 oxetane compound Chemical class 0.000 claims abstract description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000003682 fluorination reaction Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- LREAZWJEBORMTB-UHFFFAOYSA-N bis(2-methylpropyl)phosphane Chemical compound CC(C)CPCC(C)C LREAZWJEBORMTB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WDIIYWASEVHBBT-UHFFFAOYSA-N di(propan-2-yl)phosphane Chemical compound CC(C)PC(C)C WDIIYWASEVHBBT-UHFFFAOYSA-N 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OENLNEZGRPNQDR-UHFFFAOYSA-N n,n-di(propan-2-yl)hexan-1-amine Chemical compound CCCCCCN(C(C)C)C(C)C OENLNEZGRPNQDR-UHFFFAOYSA-N 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- HHDLJTLPOGOXLR-UHFFFAOYSA-N propan-2-ylphosphane Chemical compound CC(C)P HHDLJTLPOGOXLR-UHFFFAOYSA-N 0.000 description 1
- NNOBHPBYUHDMQF-UHFFFAOYSA-N propylphosphine Chemical compound CCCP NNOBHPBYUHDMQF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- 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、新規なＴ−フルオロアルコールおよびその製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel T-fluoroalcohol and a method for producing the same.
高い歪を持つオキシラン類、オキセタン類に対する求核
反応は、その位置および立体選択性について多くの研究
がなされている。しかし、フッ素を求核剤とする環開裂
の例は少なく、特にオキセタンの開通フッ素化について
は全く報告されていない。本発明者らは先に、オキシラ
ンに四フッ化ケイ素を反応させて開環し、立体選択的に
フルオロヒドリンを合成する方法を開発した（特願昭６
２−２３８３６９号明細書）。Many studies have been conducted on the regioselectivity and stereoselectivity of nucleophilic reactions with highly strained oxiranes and oxetanes. However, there are few examples of ring cleavage using fluorine as a nucleophile, and in particular, there have been no reports on open fluorination of oxetane. The present inventors previously developed a method for stereoselectively synthesizing fluorohydrin by reacting oxirane with silicon tetrafluoride to open the ring (Patent application No. 6
2-238369).
本発明者は更に研究を進め、オキセタンに四フッ化ケイ
素を反応させてこれを開環し、立体選択的にＴ−フルオ
ロアルコールを合成しうろことを見出し本発明を完成す
るに至った。The present inventor conducted further research and discovered that a T-fluoroalcohol can be stereoselectively synthesized by reacting oxetane with silicon tetrafluoride to open the ring, thereby completing the present invention.
本発明の目的は、新規なＴ−フルオロアルコールおよび
その製造法を提供することである。An object of the present invention is to provide a new T-fluoroalcohol and a method for producing the same.
本発明は、下記の一般式（Ｉ）で表されるｒ −フルオ
ロアルコールに関する。The present invention relates to an r-fluoroalcohol represented by the following general formula (I).
１゛
Ｒ２−１−ＣＨ２ＣＨ２０Ｈ（Ｉ ’）（式中、Ｒ’お
よびＲ２は同一でも異なっていてもよく、水素原子、フ
ェニル基、炭素原子数１〜５のアルキル基、またはシク
ロプロピル基を示す。但しＲ１およびＲ２が同時に水素
原子を示すことはない。）
また本発明は、下記の一般式（■）：
（式中、Ｒ３およびＲ４は同一でも異なっていてもよく
、水素原子、アリール基、アルキル基またはシクロアル
キル基を示す。但し Ｒ３およびＲ４が同時に水素原子
を示すことはない。）で表されるオキセタン化合物を、
添加剤の存在下、四フッ化ケイ素と反応させることを特
徴とする、一般式（■）：
１゜
Ｒ４−冒ＣＨ２ＣＨ２０）１ （Ｉ［［）で
表されるＴ−フルオロアルコールの製造法に関する。1゛R2-1-CH2CH20H(I') (wherein R' and R2 may be the same or different and represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 5 carbon atoms, or a cyclopropyl group) (However, R1 and R2 do not represent a hydrogen atom at the same time.) The present invention also provides the following general formula (■): (In the formula, R3 and R4 may be the same or different, and represent a hydrogen atom, an aryl group , represents an alkyl group or a cycloalkyl group.However, R3 and R4 do not simultaneously represent a hydrogen atom.
A method for producing T-fluoroalcohol represented by the general formula (■): 1゜R4-CH2CH20)1 (I[[), which is characterized by reacting with silicon tetrafluoride in the presence of an additive. .
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
ｉ）原料
一般式（Ｉ［）で表されるオキセタン化合物としては、
次のようなものを例示することができる。i) Raw material The oxetane compound represented by the general formula (I[) is as follows:
Examples include the following:
ｌｉ）反応条件
イ）添加剤
本発明においては、式（ＩＩ）のオキセタン化合物に四
フッ化珪素を反応させるに際して、添加剤を用いる。添
加剤の例としては、次のようなものを挙げることが出来
る。li) Reaction Conditions i) Additives In the present invention, additives are used when reacting the oxetane compound of formula (II) with silicon tetrafluoride. Examples of additives include the following.
アルキル又はアリール基を有するスルフィド化合物とし
て、ジメチルスルフィド、ジベンジルスルフィド、ジフ
ェニルスルフィド；ホスフィンとして、メチルホスフィ
ン、エチルホスフィン、プロピルホスフィン、イソプロ
ピルホスフィン、イソブチルホスフィン、フェニルホス
フィン、ジメチルホスフィン、ジエチルホスフィン、ジ
イソプロピルホスフィン、ジイソブチルホスフィン、ジ
フェニルホスフィン、トリメチルホスフィン、トリエチ
ルホスフィン、トリフェニルホスフィン、メチルジフェ
ニルホスフィン、ジメチルフェニルホスフィン；
嵩高三級アミンとして、ジイソプロピルエチルアミン、
ジイソプロピルヘキシルアミン、トリシクロヘキシルア
ミン；
四級アンモニウムフルオリドとして、テトラ（ｎ−ブチ
ル）アンモニウムフルオリド、ベンジルトリメチルアン
モニウムフルオリド、テトラエチルアンモニウムフルオ
リド；その他、ピリジン、ＤＭＦ等を挙げることができ
る。Sulfide compounds having an alkyl or aryl group include dimethyl sulfide, dibenzyl sulfide, diphenyl sulfide; phosphines include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, Diisobutylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine; As bulky tertiary amines, diisopropylethylamine,
Diisopropylhexylamine, tricyclohexylamine; Examples of quaternary ammonium fluoride include tetra(n-butyl)ammonium fluoride, benzyltrimethylammonium fluoride, and tetraethylammonium fluoride; others include pyridine, DMF, and the like.
Ｏ）溶 媒
溶媒としては、ジクロロエタン、エーテル、ジクロロメ
タン、クロロホルム、ジオキサン等を用いることが出来
る。O) Solvent Dichloroethane, ether, dichloromethane, chloroform, dioxane, etc. can be used as the solvent.
ハ）温 度
反応温度は、−７８〜２５℃特に−１０〜０℃が好まし
い。c) Temperature The reaction temperature is preferably -78 to 25°C, particularly -10 to 0°C.
二）時 間 反応時間は、５〜３０分間でよい。Two hours The reaction time may be 5 to 30 minutes.
本発明によって、従来知られていなかったオキセタンの
開環フッ素化を、高い収率で行うことができる。According to the present invention, ring-opening fluorination of oxetane, which has not been previously known, can be performed in high yield.
本発明により製造されるＴ−フルオロアルコールは、医
薬、農薬等の合成中間体として有用である。T-fluoroalcohol produced according to the present invention is useful as a synthetic intermediate for pharmaceuticals, agricultural chemicals, and the like.
以下、実施例により、本発明を更に具体的に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
窒素雰囲気下、乾燥スリ付ナスフラスコ中、フッ化テト
ラブチルアンモニウム（２００ｍｇ０．６３ｍｍｏｌ）
、モレキュラーシーブス４Ａ（１，０ｇ）を入れ、エ
ーテル（３，Ｏｍｊ’）を加え０℃３０分撹拌の後、Ｓ
ｉＦ、入り風船を付けさらに１５分撹拌した。Example 1 Tetrabutylammonium fluoride (200 mg 0.63 mmol) in a dry-spotted eggplant flask under a nitrogen atmosphere
, Molecular Sieves 4A (1.0 g) was added, ether (3, Omj') was added, and after stirring for 30 minutes at 0°C, S
A balloon containing iF was attached and the mixture was further stirred for 15 minutes.
ジイソプロピルエチルアミン（２５９ｍｇ２．０ｍｍｏ
ｌ）を加え５分撹拌したのち、２−メチル−２−フェニ
ルオキセクン〔化合物（１）］ （３０ｍｇ ０．２
ｍｍｏｌ）をエーテル（２，０ｍｌりの溶液として加
えた。５分後ＴＬＣにより原料の消失を確認したのち、
系をエーテルで希釈し、ＫＦ−水溶液を加え反応を停止
した。Diisopropylethylamine (259mg2.0mmo
l) and stirred for 5 minutes, 2-methyl-2-phenyloxecune [compound (1)] (30 mg 0.2
ether (2.0 ml) was added as a solution. After 5 minutes, the disappearance of the raw material was confirmed by TLC, and
The system was diluted with ether, and a KF-aqueous solution was added to stop the reaction.
エーテル抽出、飽和食塩水洗浄の後、乾燥、濃縮し、薄
層クロマトグラフィーによる分離精製を行すい、３−フ
ルオロ−３−フェニル−１−ブタノール〔化合物（６）
〕を収率６３％で得た。After extraction with ether and washing with saturated saline, it was dried, concentrated, and separated and purified by thin layer chromatography to obtain 3-fluoro-3-phenyl-1-butanol [compound (6)].
] was obtained in a yield of 63%.
ＮＭＲ［：化合物（社）〕
３−フルオロ−３−フェニル−１−／タノール１９Ｆδ
＝ １４９．５
６＝１．６９ ３Ｈ，ｄ、Ｊ＝２２．７δ＝２．０９
２ＨＳｄｔ、 Ｊ＝６．８．２．９δ＝２．３５ ２Ｈ
，ｔＳＪ＝６．８
δ＝３．６３ ３ＨＳｔ、ｂｓ、Ｊ＝６．８δ＝７．２
−７．４ ５Ｈ，ｍ
実施例２
乾燥スリ付ナスフラスコにエーテル（１，０ｍ１）ジメ
チルスルフィド（’３．７ ｍｇ ０．６ ｍｒｎｏｌ
）を加え、更にＳｉＦ、入り風船を付け０℃にて１５
分撹拌した。２．２−ジペンチルオキセクン〔化合物（
２）〕（４０ｍｇ、 ０．２ｍｍｏｌ）のエーテル溶液
（１，０−）を加えた。５分後ＴＬＣにより原料の消失
を確認したのち、系をエーテルで希釈し、実施例１と同
様の後処理により３−フルオロ−３−ペンチルー１−オ
クタツール〔化合物側〕を収率６８％で得た。NMR [: Compound (Inc.)] 3-fluoro-3-phenyl-1-/tanol 19Fδ
= 149.5 6=1.69 3H, d, J=22.7δ=2.09
2HSdt, J=6.8.2.9δ=2.35 2H
,tSJ=6.8 δ=3.63 3HSt, bs, J=6.8δ=7.2
-7.4 5H, m Example 2 Ether (1.0 ml) dimethyl sulfide ('3.7 mg 0.6 mrnol
), then added SiF and a balloon and heated at 0℃ for 15 minutes.
Stir for 1 minute. 2.2-Dipentyloxecune [Compound (
2)] (40 mg, 0.2 mmol) in ether (1,0-) was added. After 5 minutes, after confirming the disappearance of the raw material by TLC, the system was diluted with ether, and the same post-treatment as in Example 1 was performed to obtain 3-fluoro-3-pentyl-1-octatool [compound side] in a yield of 68%. Obtained.
ＮＭＲＣ化合物（２）〕
３−フルオロ−３−ペンチル−１−オクタツール
１９Ｆδ＝ １５０．７
δ＝０．９０ ６Ｈ，ｔ、Ｊ＝５．８
δ＝１．１−１．７ １５ＨＳｍ
δ＝１．８９ ２ＨＳｄｔ、Ｊ＝２１．２．６．５６＝
３．６−３．９ ２Ｈ，ｍ
実施例３〜１０
実施例１と同様の方法で実施例３及び実施例４を、実施
例２と同様の方法で実施例５〜１０を、溶媒及び添加剤
を種々に変化させて行った。NMRC compound (2)] 3-fluoro-3-pentyl-1-octatool
19Fδ= 150.7
δ=0.90 6H,t, J=5.8 δ=1.1-1.7 15HSm δ=1.89 2HSdt, J=21.2.6.56=
3.6-3.9 2H,m Examples 3 to 10 Examples 3 and 4 were prepared in the same manner as Example 1, Examples 5 to 10 were prepared in the same manner as Example 2, and the solvent and addition The experiment was conducted using various agents.
結果を第１表に示す。The results are shown in Table 1.
ＮＭＲＣ化合物αつ〕
１−シクロプロピル−１−フルオロ−１−フェニル−３
−プロパツール ＋９Ｆδ＝１６８．０６＝０．２−
０．８ ４Ｈ，ｍ
δ＝１．１−１．３ １Ｈ，ｍ
δ＝１．７２ ２８．ｔ、Ｊ＝５．８
δ＝３．３２ １８．ｂｓ
δ＝３．６８ ２Ｈ，ｔ、Ｊ＝５．８
δ＝７．０−７．５ ５Ｈ，ｍ
ＮＭＲ（化合物０荀〕
■−フルオロー１−フェニルー３−７’ロバ／−ル
１９Ｆδ＝１７９．４
δ＝１．５９ １Ｈ，ｂｓ
δ＝１．８−２．４ ２Ｈ，ｍ
δ＝３．８０ ２８．ｔ、Ｊ＝５．４
δ＝ ５．３８ ０．５ Ｈｌｄｄ、Ｊ＝３．９．７．
９６＝５．９２ ０．５Ｈ，ｄｄ、Ｊ＝６．１２．７，
９δ＝７．２−７．４ ５Ｈ，ｍNMRC compound α] 1-cyclopropyl-1-fluoro-1-phenyl-3
-Property tool +9Fδ=168.06=0.2-
0.8 4H, m δ=1.1-1.3 1H, m δ=1.72 28. t, J=5.8 δ=3.32 18. bs δ=3.68 2H,t,J=5.8 δ=7.0-7.5 5H,m NMR (Compound 0) ■-Fluoro-1-phenyl-3-7'Rova/-R
19Fδ=179.4
δ=1.59 1H, bs δ=1.8-2.4 2H, m δ=3.80 28. t, J=5.4 δ=5.38 0.5 Hldd, J=3.9.7.
96=5.92 0.5H, dd, J=6.12.7,
9δ=7.2-7.4 5H, m
Claims (2)
ルコール。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＾１およびＲ＾２は同一でも異なっていても
よく、水素原子、フェニル基、炭素原子数１〜５のアル
キル基、またはシクロプロピル基を示す。但しＲ＾１お
よびＲ＾２が同時に水素原子を示すことはない。）(1) γ-fluoroalcohol represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 and R^2 may be the same or different, and are a hydrogen atom, a phenyl group, an alkyl group having 1 to 5 carbon atoms, or Indicates a cyclopropyl group. However, R^1 and R^2 do not represent a hydrogen atom at the same time.)
よく、水素原子、アリール基、アルキル基またはシクロ
アルキル基を示す。但し、Ｒ＾３およびＲ＾４が同時に
水素原子を示すことはない。） で表されるオキセタン化合物を、添加剤の存在下、四フ
ッ化ケイ素と反応させることを特徴とする、一般式（I
II）： ▲数式、化学式、表等があります▼（III） で表されるγ−フルオロアルコールの製造法。(2) The following general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^3 and R^4 may be the same or different, and represent a hydrogen atom, an aryl group, An oxetane compound represented by (represents an alkyl group or a cycloalkyl group. However, R^3 and R^4 do not simultaneously represent a hydrogen atom) is reacted with silicon tetrafluoride in the presence of an additive. The general formula (I
II): ▲Mathematical formulas, chemical formulas, tables, etc. ▼(III) Production method of γ-fluoroalcohol represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5688588A JPH01228927A (en) | 1988-03-10 | 1988-03-10 | Gamma-fluoroalcohol and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5688588A JPH01228927A (en) | 1988-03-10 | 1988-03-10 | Gamma-fluoroalcohol and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01228927A true JPH01228927A (en) | 1989-09-12 |
Family
ID=13039878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5688588A Pending JPH01228927A (en) | 1988-03-10 | 1988-03-10 | Gamma-fluoroalcohol and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01228927A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005085171A1 (en) * | 2004-03-04 | 2005-09-15 | Mitsubishi Gas Chemical Company, Inc. | Process for producing optically active fluorochemical |
-
1988
- 1988-03-10 JP JP5688588A patent/JPH01228927A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005085171A1 (en) * | 2004-03-04 | 2005-09-15 | Mitsubishi Gas Chemical Company, Inc. | Process for producing optically active fluorochemical |
| US7307185B2 (en) | 2004-03-04 | 2007-12-11 | Mitsubishi Gas Chemical Company, Inc. | Process for producing optically active fluorochemical |
| JP4752759B2 (en) * | 2004-03-04 | 2011-08-17 | 三菱瓦斯化学株式会社 | Method for producing optically active fluoro compound |
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