JPH11335316A - Production of cyclopentenone derivative and cyclopentenone derivative - Google Patents

Production of cyclopentenone derivative and cyclopentenone derivative

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Publication number
JPH11335316A
JPH11335316A JP14407698A JP14407698A JPH11335316A JP H11335316 A JPH11335316 A JP H11335316A JP 14407698 A JP14407698 A JP 14407698A JP 14407698 A JP14407698 A JP 14407698A JP H11335316 A JPH11335316 A JP H11335316A
Authority
JP
Japan
Prior art keywords
cyclopentenone
fluoro
phenyl
derivative
cdcl
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.)
Granted
Application number
JP14407698A
Other languages
Japanese (ja)
Other versions
JP4158228B2 (en
Inventor
Atsushi Ichikawa
淳士 市川
Eiji Yokoyama
誉治 横山
Tatsuo Okauchi
辰夫 岡内
Susumu Minami
享 南
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
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Priority to JP14407698A priority Critical patent/JP4158228B2/en
Publication of JPH11335316A publication Critical patent/JPH11335316A/en
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Publication of JP4158228B2 publication Critical patent/JP4158228B2/en
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Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PROBLEM TO BE SOLVED: To produce a cyclopentenone derivative useful as a manufacturing intermediate for various biologically active compounds such as prostaglandin derivatives at high selectivity and yield by reacting a specific divinyl=ketone derivative with a specific compound. SOLUTION: (A) A divinyl=ketone derivative of formula I (R<1> to R<3> are each a lower alkyl, phenyl or H) is made to react with (B) trimethylsilicone (+1)=chlorotris(trifluoromethanesulfonate)-borate(1-) or trimethylsilicone (1+)= tetrakis(trifluoromethanesulfonate)borate(1-) to obtain the objective derivative of formula II, e.g. 3,4-dibutyl-2fluoro-2-cyclopentenone. Further, the reaction is preferably carried out, for example, in an inert gas atmosphere in an inert solvent at a temperature of -80 to 100 deg.C for 0.1-30 hr.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はシクロペンテノン誘
導体の製造法及びシクロペンテノン誘導体に関する。TECHNICAL FIELD The present invention relates to a method for producing a cyclopentenone derivative and a cyclopentenone derivative.

【０００２】[0002]

【従来の技術】シクロペンテノン誘導体はプロスタグラ
ンジン誘導体等の種々の生理活性化合物の製造中間体と
なり得ることから、かかるシクロペンテノン誘導体の効
率の良い製造法の開発が望まれている。2. Description of the Related Art Since a cyclopentenone derivative can be used as an intermediate for the production of various physiologically active compounds such as a prostaglandin derivative, development of an efficient production method of such a cyclopentenone derivative has been desired.

【０００３】[0003]

【発明が解決しようとする課題】本発明は、シクロペン
テノン誘導体を高選択的に高収率で製造する製造法及び
シクロペンテノン誘導体を提供することを課題とする。An object of the present invention is to provide a process for producing a cyclopentenone derivative with high selectivity and high yield, and to provide a cyclopentenone derivative.

【０００４】[0004]

【課題を解決するための手段】本発明者等は鋭意検討し
た結果、下記、 一般式 化４で示されるジビニル＝ケ
トン誘導体に、トリメチルシリコン（１＋）＝クロロト
リス（トリフルオロメタンスルホナト）ボラート（１
−）（以下、ＴＭＳＢ（ＯＴｆ）3Ｃｌと記す）または
トリメチルシリコン（１＋）＝テトラキス（トリフルオ
ロメタンスルホナト）ボラート（１−）（以下、ＴＭＳ
Ｂ（ＯＴｆ）4と記す）を作用させることにより、下
記、一般式 化５で示される含フッ素シクロペンテノン
誘導体を高選択的に高収率で製造できることを見出し、
本発明に至った。即ち、本発明は一般式 化４Means for Solving the Problems As a result of diligent studies, the present inventors have found that a divinyl ketone derivative represented by the following general formula (4) is added to trimethylsilicon (1 +) = chlorotris (trifluoromethanesulfonato) borate (1).
−) (Hereinafter referred to as TMSB (OTf) 3 Cl) or trimethylsilicon (1 +) = tetrakis (trifluoromethanesulfonato) borate (1-) (hereinafter TMS)
B (OTf) 4 ), a fluorine-containing cyclopentenone derivative represented by the following general formula 5 can be produced with high selectivity and high yield.
The present invention has been reached. That is, the present invention provides a compound represented by the general formula:

【化４】 ［式中、Ｒ1、Ｒ2及びＲ3は同一もしくは相異なり、低
級アルキル基、フェニル基または水素原子を表す。］で
示されるジビニル＝ケトン誘導体に、ＴＭＳＢ（ＯＴ
ｆ）3ＣｌまたはＴＭＳＢ（ＯＴｆ）4を作用させる一般
式 化５Embedded image [In the formula, R 1 , R 2 and R 3 are the same or different and represent a lower alkyl group, a phenyl group or a hydrogen atom. ] To the divinyl ketone derivative represented by TMSB (OT
f) General formula for reacting 3 Cl or TMSB (OTf) 4

【化５】 ［式中、Ｒ1、Ｒ2及びＲ3は前記と同じ意味を表す。］
で示される含フッ素シクロペンテノン誘導体の製造法
（以下、本発明製造法と称す）を提供する。本発明は、
さらに一般式 化６Embedded image [Wherein, R 1 , R 2 and R 3 represent the same meaning as described above. ]
And a method for producing a fluorine-containing cyclopentenone derivative represented by the formula (hereinafter referred to as the production method of the present invention). The present invention
Further general formula 6

【化６】 ［式中、Ｒ2及びＲ3は前記と同じ意味を表す。］で示さ
れる含フッ素シクロペンテノン誘導体を提供する。Embedded image [Wherein, R 2 and R 3 represent the same meaning as described above. A fluorine-containing cyclopentenone derivative represented by the formula:

【０００５】[0005]

【発明の実施の形態】以下、本発明製造法について詳細
に説明する。本発明製造法は、前記、一般式 化４で示
されるジビニル＝ケトン誘導体に、ＴＭＳＢ（ＯＴｆ）
3ＣｌまたはＴＭＳＢ（ＯＴｆ）4を作用させることによ
り行われる。該反応は、通常、不活性ガス雰囲気下、不
活性溶媒中で行われる。反応温度の範囲は−８０℃〜１
００℃であり、反応時間の範囲は０．１時間〜３０時間
である。反応に供される試剤の量は、一般式 化４で示
されるジビニル＝ケトン誘導体１モルに対し、ＴＭＳＢ
（ＯＴｆ）3ＣｌまたはＴＭＳＢ（ＯＴｆ）4の量は、
０．８〜１．５モルの割合である。不活性ガスとして
は、例えば、窒素ガス、アルゴン等があげられる。溶媒
としては、例えば、ジクロロメタン等のハロゲン化炭化
水素類、トルエン、ヘキサン、シクロヘキサン等の炭化
水素類、ジエチルエ−テル、テトラヒドロフラン（以
下、ＴＨＦと記す。）等のエ−テル類、またはそれらの
混合溶媒があげられる。反応終了後の反応液は、水また
は飽和重曹水溶液を加えた後、有機溶媒抽出、濃縮等の
後処理操作を行うことにより、目的とする化合物を得る
ことができる。該化合物は、クロマトグラフィ−、蒸留
等の操作により、さらに精製することもできる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method of the present invention will be described below in detail. According to the production method of the present invention, the divinyl ketone derivative represented by the general formula (4) is added to TMSB (OTf)
This is performed by reacting 3 Cl or TMSB (OTf) 4 . The reaction is generally performed in an inert solvent under an inert gas atmosphere. The reaction temperature range is -80 ° C to 1
00 ° C., and the reaction time ranges from 0.1 hour to 30 hours. The amount of the reagent used in the reaction is determined by adding TMSB to 1 mol of the divinyl ketone derivative represented by the general formula (4).
The amount of (OTf) 3 Cl or TMSB (OTf) 4
0.8 to 1.5 moles. Examples of the inert gas include nitrogen gas and argon. Examples of the solvent include halogenated hydrocarbons such as dichloromethane, hydrocarbons such as toluene, hexane and cyclohexane, ethers such as diethyl ether and tetrahydrofuran (hereinafter referred to as THF), and mixtures thereof. Solvents. After completion of the reaction, the target compound can be obtained by adding post-treatment operations such as extraction with an organic solvent and concentration after adding water or a saturated aqueous solution of sodium bicarbonate to the reaction solution. The compound can be further purified by operations such as chromatography and distillation.

【０００６】一般式 化４で示されるジビニル＝ケトン
誘導体は、例えば、Bull.Chem.Soc.Jpn.,1992,65,2800-
2806等に記載の方法に準じて製造することができる。ま
た、ＴＭＳＢ（ＯＴｆ）3Ｃｌ及びＴＭＳＢ（ＯＴｆ）4
は、例えば、Angew.Chem.,Int.Ed.Engl.,1992,31,470-4
71、Tetrahedron Letters,1996,37,9401-9402等に記載
の方法に準じて製造することができる。The divinyl ketone derivative represented by the general formula (4) is disclosed, for example, in Bull. Chem. Soc. Jpn., 1992, 65, 2800-
It can be produced according to the method described in 2806 and the like. In addition, TMSB (OTf) 3 Cl and TMSB (OTf) 4
Is, for example, Angew.Chem., Int.Ed.Engl., 1992, 31, 470-4
71, Tetrahedron Letters, 1996, 37, 9401-9402 and the like.

【０００７】本発明製造法により得られる一般式 化５
で示される含フッ素シクロペンテノン誘導体としては、
例えば、 ３，４−ジブチル−２−フルオロ−２−シクロペンテノ
ン ３−エチル−２−フルオロ−４−フェニル−２−シクロ
ペンテノン ２−フルオロ−３−イソプロピル−４−フェニル−２−
シクロペンテノン ２−フルオロ−４−フェニル−２−シクロペンテノン ３，５−ジエチル−２−フルオロ−４−プロピル−２−
シクロペンテノン ２−フルオロ−３，４−ジフェニル−２−シクロペンテ
ノン 等が挙げられる。また、本発明製造法において用いられ
る、一般式 化４で示されるジビニル＝ケトン誘導体と
しては、例えば、 ６−フルオロ−５，８−トリデカジエン−７−オン ４−フルオロ−１−フェニル−１，４−ヘプタジエン−
３−オン ４−フルオロ−6−メチル−１−フェニル−１，４−ヘ
プタジエン−３−オン ４−フルオロ−１−フェニル−１，４−ペンタジエン−
３−オン ６−エチル−４−フルオロ−３，６−デカジエン−５−
オン １，５−ジフェニル−２−フルオロ−１，４−ペンタジ
エン−３−オン 等が挙げられる。The general formula (5) obtained by the production method of the present invention
As the fluorine-containing cyclopentenone derivative represented by
For example, 3,4-dibutyl-2-fluoro-2-cyclopentenone 3-ethyl-2-fluoro-4-phenyl-2-cyclopentenone 2-fluoro-3-isopropyl-4-phenyl-2-phenyl
Cyclopentenone 2-fluoro-4-phenyl-2-cyclopentenone 3,5-diethyl-2-fluoro-4-propyl-2-
Cyclopentenone 2-fluoro-3,4-diphenyl-2-cyclopentenone and the like. Examples of the divinyl ketone derivative represented by the general formula 4 used in the production method of the present invention include 6-fluoro-5,8-tridecadien-7-one 4-fluoro-1-phenyl-1,4 -Heptadiene-
3-one 4-fluoro-6-methyl-1-phenyl-1,4-heptadien-3-one 4-fluoro-1-phenyl-1,4-pentadiene-
3-one 6-ethyl-4-fluoro-3,6-decadiene-5
On 1,5-diphenyl-2-fluoro-1,4-pentadien-3-one and the like.

【０００８】[0008]

【実施例】以下、本発明を実施例にてさらに詳しく説明
するが、本発明はこれらの例に限定されない。 実施例１ ３，４−ジブチル−２−フルオロ−２−シク
ロペンテノンの製造 ６−フルオロ−５，８−トリデカジエン−７−オン５１
ｍｇ（０．２４ｍｍｏｌ）のジクロロメタン３ｍｌ溶液
に、窒素雰囲気下、室温で、ＴＭＳＢ（ＯＴｆ） 4のジ
クロロメタン溶液（濃度０．２９Ｍ）０．８２ｍｌ
（０．２４ｍｍｏｌ）を加えた。該混合物を１５分間攪
拌した後、飽和重曹水溶液を加えた。水層をジクロロメ
タンで３回抽出した後、該抽出液を合わせ、これを飽和
重曹水溶液、食塩水で順次洗浄した後、Ｎａ2ＳＯ4で乾
燥し、減圧下に溶媒を留去した後、残渣をシリカゲル薄
層クロマトグラフィー（展開溶媒：酢酸エチル：ヘキサ
ン＝１：５）に付し、３，４−ジブチル−２−フルオロ
−２−シクロペンテノン４５ｍｇ（０．２１ｍｍｏｌ）
を淡黄色液体として得た。収率８９％。1 H-NMR (500 MHz, CDCl3) δ 0.92 (3H, t, J = 7.3 H
z), 0.95 (3H, t, J = 7.3 Hz), 1.18-1.44 (7H, m),
1.44-1.54 (1H, m), 1.54-1.64 (1H, m), 1.73-1.82 (1
H, m), 2.09 (1H, d, J = 18.9 Hz), 2.19-2.28 (1H,
m), 2.54 (1H, dd, J= 18.9, 6.0 Hz), 2.53-2.62 (1H,
m), 2.69-2.75 (1H, m)19 F-NMR (471MHz, CDCl3/C6F6) 16.3 (1F, d, J = 5Hz)
ppm MS (70 eV) m/z 212 (M+; 81), 155 (61), 114 (100),
85 (59) HRMS calcd for C13H21OF 212.1576 (M+); found 212.1
563EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
However, the present invention is not limited to these examples. Example 1 3,4-dibutyl-2-fluoro-2-cycl
Preparation of Lopentenone 6-Fluoro-5,8-tridecadien-7-one 51
mg (0.24mmol) solution in dichloromethane 3ml
In a nitrogen atmosphere at room temperature, TMSB (OTf) FourNo
0.82 ml of chloromethane solution (concentration 0.29M)
(0.24 mmol) was added. The mixture is stirred for 15 minutes.
After stirring, a saturated aqueous solution of sodium bicarbonate was added. Dichlorometh
After three extractions with tan, the extracts are combined and saturated.
After successively washing with an aqueous solution of sodium bicarbonate and brine,TwoSOFourDry
After drying, the solvent was distilled off under reduced pressure.
Layer chromatography (developing solvent: ethyl acetate: hexa
3,4-dibutyl-2-fluoro)
-2-cyclopentenone 45mg (0.21mmol)
Was obtained as a pale yellow liquid. 89% yield.1 H-NMR (500 MHz, CDClThree) δ 0.92 (3H, t, J = 7.3 H
z), 0.95 (3H, t, J = 7.3 Hz), 1.18-1.44 (7H, m),
1.44-1.54 (1H, m), 1.54-1.64 (1H, m), 1.73-1.82 (1
H, m), 2.09 (1H, d, J = 18.9 Hz), 2.19-2.28 (1H,
m), 2.54 (1H, dd, J = 18.9, 6.0 Hz), 2.53-2.62 (1H,
 m), 2.69-2.75 (1H, m)19 F-NMR (471MHz, CDClThree/ C6F6) 16.3 (1F, d, J = 5Hz)
 ppm MS (70 eV) m / z 212 (M+; 81), 155 (61), 114 (100),
85 (59) HRMS calcd for C13Htwenty oneOF 212.1576 (M+); found 212.1
563

【０００９】実施例２ ３−エチル−２−フルオロ−４
−フェニル−２−シクロペンテノンの製造 ４−フルオロ−１−フェニル−１，４−ヘプタジエン−
３−オン６０ｍｇ（０．５１ｍｍｏｌ）のジクロロメタ
ン３ｍｌ溶液に、窒素雰囲気下、室温でＴＭＳＢ（ＯＴ
ｆ）4のジクロロメタン溶液（濃度０．４１Ｍ）１．２
５ｍｌ（０．５１ｍｍｏｌ）を加えた。該混合物を１５
分間攪拌した後、飽和重曹水溶液を加えた。水層をジク
ロロメタンで３回抽出した後、該抽出液を合わせ、これ
を飽和重曹水溶液、食塩水で順次洗浄した後、Ｎａ2Ｓ
Ｏ4で乾燥し、減圧下に溶媒を留去した後、残渣をシリ
カゲル薄層クロマトグラフィー（展開溶媒：酢酸エチ
ル：ヘキサン＝１：５）に付し、３−エチル−２−フル
オロ−４−フェニル−２−シクロペンテノン９０ｍｇ
（０．４４ｍｍｏｌ）を淡黄色液体として得た。収率８
８％。 IR (neat) 2980, 1725, 1665, 1455, 1355, 1105, 106
5, 705 cm-1 1 H-NMR (500 MHz, CDCl3) δ 1.05 (3H, t, J = 7.6 H
z), 2.02 (1H, br dq, J= 15.2, 7.6 Hz), 2.36 (1H,
d, J = 19.0 Hz), 2.47 (1H, dq, J = 15.2, 7.6Hz),
2.92 (1H, dd, J = 19.0, 6.1 Hz), 3.92 (1H, dd, J =
6.1 Hz, JHF = 6.1 Hz), 7.15 (2H, br d, J = 7.3 H
z), 7.28 (1H, br t, J = 7.3 Hz), 7.35 (2H, br t, J
= 7.3 Hz)13 C-NMR (126 MHz, CDCl3) δ 10.9 (d, JCF = 2 Hz),
19.9, 41.6 (d, JCF = 5Hz), 42.1 (d, JCF = 4 Hz), 1
27.2, 127.5, 129.1, 140.3 (d, JCF = 2 Hz),155.0
(d, JCF = 277 Hz), 156.9 (d, JCF = 4 Hz), 197.5
(d, JCF = 19 Hz)19 F-NMR (471 MHz, CDCl3/C6F6) 16.8 (1F, d, J = 5 H
z) ppm MS (70 eV) m/z 204 (M+; 40), 175 (100), 147 (29),
77 (26) HRMS calcd for C13H13OF 204.0950 (M+); found 204.0
950Example 2 3-ethyl-2-fluoro-4
Preparation of -Phenyl-2-cyclopentenone 4-Fluoro-1-phenyl-1,4-heptadiene-
TMSB (OT) was added to a solution of 60 mg (0.51 mmol) of 3-one in 3 ml of dichloromethane at room temperature under a nitrogen atmosphere.
f) dichloromethane solution of 4 (concentration 0.41M) 1.2
5 ml (0.51 mmol) were added. The mixture is
After stirring for minutes, a saturated aqueous solution of sodium bicarbonate was added. After the aqueous layer was extracted three times with dichloromethane, the extracts were combined, washed with a saturated aqueous solution of sodium bicarbonate and brine successively, and then extracted with Na 2 S.
After drying over O 4 and evaporating the solvent under reduced pressure, the residue was subjected to silica gel thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5) to give 3-ethyl-2-fluoro-4-. Phenyl-2-cyclopentenone 90mg
(0.44 mmol) as a pale yellow liquid. Yield 8
8%. IR (neat) 2980, 1725, 1665, 1455, 1355, 1105, 106
5, 705 cm -1 1 H-NMR (500 MHz, CDCl 3 ) δ 1.05 (3H, t, J = 7.6 H
z), 2.02 (1H, br dq, J = 15.2, 7.6 Hz), 2.36 (1H,
d, J = 19.0 Hz), 2.47 (1H, dq, J = 15.2, 7.6Hz),
2.92 (1H, dd, J = 19.0, 6.1 Hz), 3.92 (1H, dd, J =
6.1 Hz, J HF = 6.1 Hz), 7.15 (2H, br d, J = 7.3 H
z), 7.28 (1H, br t, J = 7.3 Hz), 7.35 (2H, br t, J
= 7.3 Hz) 13 C-NMR (126 MHz, CDCl 3 ) δ 10.9 (d, J CF = 2 Hz),
19.9, 41.6 (d, J CF = 5Hz), 42.1 (d, J CF = 4 Hz), 1
27.2, 127.5, 129.1, 140.3 (d, J CF = 2 Hz), 155.0
(d, J CF = 277 Hz), 156.9 (d, J CF = 4 Hz), 197.5
(d, J CF = 19 Hz) 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) 16.8 (1F, d, J = 5 H
z) ppm MS (70 eV) m / z 204 (M + ; 40), 175 (100), 147 (29),
77 (26) HRMS calcd for C 13 H 13 OF 204.0950 (M + ); found 204.0
950

【００１０】実施例３ ２−フルオロ−３−イソプロピ
ル−４−フェニル−２−シクロペンテノンの製造 4−フルオロ−６−メチル−１−フェニル−１，４−ヘ
プタジエン−３−オン５２ｍｇ（０．２３ｍｍｏｌ）の
ジクロロメタン３ｍｌ溶液に、窒素雰囲気下、室温で、
ＴＭＳＢ（ＯＴｆ）4のジクロロメタン溶液（濃度０．
５５Ｍ）０．４３ｍｌ（０．２４ｍｍｏｌ）を加えた。
該混合物を１５分間攪拌した後、飽和重曹水溶液を加え
た。水層をジクロロメタンで３回抽出した後、該抽出液
を合わせ、これを飽和重曹水溶液、食塩水で順次洗浄し
た後、Ｎａ2ＳＯ4で乾燥し、減圧下に溶媒を留去した
後、残渣をシリカゲル薄層クロマトグラフィー（展開溶
媒：酢酸エチル：ヘキサン＝１：５）に付し、２−フル
オロ−３−イソプロピル−４−フェニル−２−シクロペ
ンテノン３８ｍｇ（０．１８ｍｍｏｌ）を淡黄色液体と
して得た。収率７４％。 IR (neat) 2971, 1724, 1658, 1456, 1315, 1070, 701
cm-1 1 H-NMR (500 MHz, CDCl3) δ 1.05 (3H, d, J = 7.0 H
z), 1.12 (3H, dd, J = 7.0 Hz, JHF = 1.5 Hz), 2.35
(1H, d, J = 19.0 Hz), 2.48 (1H, sept, J = 7.0Hz),
2.90 (1H, dd, J = 19.0, 7.0 Hz), 3.94 (1H, br dd,
J = 7.0 Hz, JHF= 7.0 Hz), 7.17 (2H, br d, J = 7.3
Hz), 7.25-7.31 (1H, m), 7.34 (2H, brt, J = 7.3 Hz)13 C-NMR (126 MHz, CDCl3) δ 19.7 (d, JCF = 3 Hz),
20.6 (d, JCF = 2 Hz),28.4 (d, JCF = 2 Hz), 41.9
(d, JCF = 6 Hz), 42.3 (d, JCF = 4 Hz), 127.4,127.
6, 129.0, 140.8 (d, JCF = 2 Hz), 154.9 (d, JCF = 2
77 Hz), 160.3, 198.0 (d, JCF = 20 Hz)19 F-NMR (471 MHz, CDCl3/C6F6) 19.4 (1F, d, J = 5 H
z) ppm MS (70 eV) m/z 218 (M+; 64), 175 (100), 140 (81) HRMS calcd for C14H15OF 218.1107 (M+); found 218.1
087Example 3 Preparation of 2-fluoro-3-isopropyl-4-phenyl-2-cyclopentenone 52 mg of 4-fluoro-6-methyl-1-phenyl-1,4-heptadien-3-one (0.5 mg). 23 mmol) in 3 ml of dichloromethane at room temperature under a nitrogen atmosphere.
TMSB (OTf) 4 in dichloromethane (concentration 0.
0.43 ml (0.24 mmol) of 55M) was added.
After the mixture was stirred for 15 minutes, a saturated aqueous solution of sodium bicarbonate was added. After the aqueous layer was extracted three times with dichloromethane, the extracts were combined, washed with a saturated aqueous solution of sodium bicarbonate and brine in that order, dried over Na 2 SO 4 , and the solvent was distilled off under reduced pressure. Was subjected to silica gel thin layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5), and 38 mg (0.18 mmol) of 2-fluoro-3-isopropyl-4-phenyl-2-cyclopentenone was added to a pale yellow liquid. As obtained. Yield 74%. IR (neat) 2971, 1724, 1658, 1456, 1315, 1070, 701
cm -1 1 H-NMR (500 MHz, CDCl 3 ) δ 1.05 (3H, d, J = 7.0 H
z), 1.12 (3H, dd, J = 7.0 Hz, J HF = 1.5 Hz), 2.35
(1H, d, J = 19.0 Hz), 2.48 (1H, sept, J = 7.0Hz),
2.90 (1H, dd, J = 19.0, 7.0 Hz), 3.94 (1H, br dd,
J = 7.0 Hz, J HF = 7.0 Hz), 7.17 (2H, br d, J = 7.3
Hz), 7.25-7.31 (1H, m), 7.34 (2H, brt, J = 7.3 Hz) 13 C-NMR (126 MHz, CDCl 3 ) δ 19.7 (d, J CF = 3 Hz),
20.6 (d, J CF = 2 Hz), 28.4 (d, J CF = 2 Hz), 41.9
(d, J CF = 6 Hz), 42.3 (d, J CF = 4 Hz), 127.4,127.
6, 129.0, 140.8 (d, J CF = 2 Hz), 154.9 (d, J CF = 2
77 Hz), 160.3, 198.0 (d, J CF = 20 Hz) 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) 19.4 (1F, d, J = 5 H
z) ppm MS (70 eV) m / z 218 (M +; 64), 175 (100), 140 (81) HRMS calcd for C 14 H 15 OF 218.1107 (M +); found 218.1
087

【００１１】実施例４ ２−フルオロ−４−フェニル−
２−シクロペンテノンの製造 ４−フルオロ−1−フェニル−１，４−ペンタジエン−
３−オン４２ｍｇ（０．２４ｍｍｏｌ）のジクロロメタ
ン３ｍｌ溶液に、窒素雰囲気下、室温で、ＴＭＳＢ（Ｏ
Ｔｆ）4のジクロロメタン溶液（濃度０．２９Ｍ）０．
８１ｍｌ（０．２４ｍｍｏｌ）を加えた。該混合物を１
５分間攪拌した後、飽和重曹水溶液を加えた。水層をジ
クロロメタンで３回抽出した後、該抽出液を合わせ、こ
れを飽和重曹水溶液、食塩水で順次洗浄した後、Ｎａ2
ＳＯ4で乾燥し、減圧下に溶媒を留去した後、残渣をシ
リカゲル薄層クロマトグラフィー（展開溶媒：酢酸エチ
ル：ヘキサン＝１：５）に付し、２−フルオロ−４−フ
ェニル−２−シクロペンテノン３３ｍｇ（０．１９ｍｍ
ｏｌ）を無色固体として得た。収率７９％。 IR (KBr disk) 2929, 1731, 1648, 1340, 1078, 765, 7
01 cm-1 1 H-NMR (500 MHz, CDCl3) δ 2.40 (1H, dd, J = 19.4,
1.8 Hz), 2.99 (1H, dd, J = 19.4, 6.4 Hz), 4.03-4.
09 (1H, m), 7.00 (1H, d, J = 2.8 Hz), 7.18 (2H, d
t, J = 7.3, 1.6 Hz), 7.29 (1H, tt, J = 7.3, 1.6 H
z), 7.36 (2H, br t, J = 7.3 Hz)13 C-NMR (126 MHz, CDCl3) δ 38.7 (d, JCF= 6 Hz), 4
2.5 (d, JCF = 4 Hz),126.9, 127.6, 129.1, 138.8 (d,
JCF = 6 Hz), 140.9 (d, JCF = 2 Hz), 158.8 (d, J
CF = 284 Hz), 198.3 (d, JCF = 19 Hz)19 F-NMR (471 MHz, CDCl3/C6F6) 23.1 (1F, d, J = 6 H
z) ppm MS (70 eV) m/z 176 (M+; 100), 147 (58), 133 (44)Example 4 2-Fluoro-4-phenyl-
Production of 2-cyclopentenone 4-Fluoro-1-phenyl-1,4-pentadiene-
To a solution of 42 mg (0.24 mmol) of 3-one in 3 ml of dichloromethane was added TMSB (O
Tf) 4 dichloromethane solution (concentration 0.29 M)
81 ml (0.24 mmol) were added. The mixture is
After stirring for 5 minutes, a saturated aqueous solution of sodium bicarbonate was added. After the aqueous layer was extracted three times with dichloromethane, the extracts were combined, washed with a saturated aqueous sodium bicarbonate solution and brine in that order, and extracted with Na 2 O 3.
After drying over SO 4 and evaporating the solvent under reduced pressure, the residue was subjected to silica gel thin layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5) to give 2-fluoro-4-phenyl-2- 33 mg of cyclopentenone (0.19 mm
ol) as a colorless solid. 79% yield. IR (KBr disk) 2929, 1731, 1648, 1340, 1078, 765, 7
01 cm -1 1 H-NMR (500 MHz, CDCl 3 ) δ 2.40 (1H, dd, J = 19.4,
1.8 Hz), 2.99 (1H, dd, J = 19.4, 6.4 Hz), 4.03-4.
09 (1H, m), 7.00 (1H, d, J = 2.8 Hz), 7.18 (2H, d
t, J = 7.3, 1.6 Hz), 7.29 (1H, tt, J = 7.3, 1.6 H
z), 7.36 (2H, brt, J = 7.3 Hz) 13 C-NMR (126 MHz, CDCl 3 ) δ 38.7 (d, J CF = 6 Hz), 4
2.5 (d, J CF = 4 Hz), 126.9, 127.6, 129.1, 138.8 (d,
J CF = 6 Hz), 140.9 (d, J CF = 2 Hz), 158.8 (d, J
CF = 284 Hz), 198.3 (d, J CF = 19 Hz) 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) 23.1 (1F, d, J = 6 H
z) ppm MS (70 eV) m / z 176 (M + ; 100), 147 (58), 133 (44)

【００１２】実施例５ ３，５−ジエチル−２−フルオ
ロ−４−プロピル−２−シクロペンテノンの製造 ６−エチル−４−フルオロ−３，６−デカジエン−５−
オン６０ｍｇ（０．３０ｍｍｏｌ）のジクロロメタン３
ｍｌ溶液に、窒素雰囲気下、室温で、ＴＭＳＢ（ＯＴ
ｆ）4のジクロロメタン溶液（濃度０．２６Ｍ）１．２
ｍｌ（０．３１ｍｍｏｌ）を加えた。該混合物を１５分
間攪拌した後、飽和重曹水溶液を加えた。水層をジクロ
ロメタンで３回抽出した後、該抽出液を合わせ、これを
飽和重曹水溶液、食塩水で順次洗浄した後、Ｎａ2ＳＯ4
で乾燥し、減圧下に溶媒を留去した後、残渣をシリカゲ
ル薄層クロマトグラフィー（展開溶媒：酢酸エチル：ヘ
キサン＝１：５）に付し、３，５−ジエチル−２−フル
オロ−４−プロピル−２−シクロペンテノン３９ｍｇ
（０．２０ｍｍｏｌ）を淡黄色液体として得た。収率６
５％。 IR (neat) 2962, 2933, 2875, 1722, 1688, 1461, 138
0, 1355, 1116, 1022cm-1 13 C-NMR (126 MHz, CDCl3) major isomer: δ 10.8, 1
1.2 (d, JCF = 2 Hz), 14.3, 19.5, 19.9, 24.8, 34.9
(d, JCF = 2 Hz), 41.3 (d, JCF = 3 Hz), 49.8 (d, J
CF = 4 Hz), 153.6 (d, JCF = 277 Hz), 157.4 (d, JCF
= 3 Hz), 200.5 (d, JCF = 17 Hz)19 F-NMR (471 MHz, CDCl3/C6F6) for 8/2 mixture 14.9
(0.2F, d, J = 5 Hz),16.0 (0.8F, d, J = 6 Hz) ppmExample 5 Preparation of 3,5-diethyl-2-fluoro-4-propyl-2-cyclopentenone 6-ethyl-4-fluoro-3,6-decadiene-5
60 mg (0.30 mmol) of dichloromethane 3
ml of TMSB (OT) under nitrogen atmosphere at room temperature.
f) A dichloromethane solution of 4 (concentration 0.26M) 1.2
ml (0.31 mmol) was added. After the mixture was stirred for 15 minutes, a saturated aqueous solution of sodium bicarbonate was added. After the aqueous layer was extracted three times with dichloromethane, the extracts were combined, washed with an aqueous saturated sodium bicarbonate solution and brine successively, and then extracted with Na 2 SO 4.
After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel thin layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5) to give 3,5-diethyl-2-fluoro-4-. 39 mg of propyl-2-cyclopentenone
(0.20 mmol) as a pale yellow liquid. Yield 6
5%. IR (neat) 2962, 2933, 2875, 1722, 1688, 1461, 138
0, 1355, 1116, 1022cm -1 13 C-NMR (126 MHz, CDCl 3 ) major isomer: δ 10.8, 1
1.2 (d, J CF = 2 Hz), 14.3, 19.5, 19.9, 24.8, 34.9
(d, J CF = 2 Hz), 41.3 (d, J CF = 3 Hz), 49.8 (d, J
CF = 4 Hz), 153.6 (d, J CF = 277 Hz), 157.4 (d, J CF
= 3 Hz), 200.5 (d, J CF = 17 Hz) 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) for 8/2 mixture 14.9
(0.2F, d, J = 5 Hz), 16.0 (0.8F, d, J = 6 Hz) ppm

【００１３】実施例６ ２−フルオロ−３，４−ジフェ
ニル−２−シクロペンテノンの製造 １，５−ジフェニル−２−フルオロ−１，４−ペンタジ
エン−３−オン６２ｍｇ（０．２５ｍｍｏｌ）のジクロ
ロメタン３ｍｌ溶液に、窒素雰囲気下、室温で、ＴＭＳ
Ｂ（ＯＴｆ）4のジクロロメタン溶液（濃度０．５５
Ｍ）０．４５ｍｌ（０．２５ｍｍｏｌ）を加えた。該混
合物を１５分間攪拌した後、飽和重曹水溶液を加えた。
水層をジクロロメタンで３回抽出した後、該抽出液を合
わせ、これを飽和重曹水溶液、食塩水で順次洗浄した
後、Ｎａ2ＳＯ4で乾燥し、減圧下に溶媒を留去した後、
残渣をシリカゲル薄層クロマトグラフィー（展開溶媒：
酢酸エチル：ヘキサン＝１：５）に付し、２−フルオロ
−３，４−ジフェニル−２−シクロペンテノン３６ｍｇ
（０．１４ｍｍｏｌ）を無色固体として得た。収率４８
％。 IR (KBr disk) 1716, 1635, 1361, 1078, 701, 688 cm
-1 19 F-NMR (471 MHz, CDCl3/C6F6) 25.1 (1F, d, J = 6 H
z) ppm MS (70 eV) m/z 252 (M+; 100), 223 (63), 146 (58),
120 (50)Example 6 Preparation of 2-fluoro-3,4-diphenyl-2-cyclopentenone 62 mg (0.25 mmol) of 1,5-diphenyl-2-fluoro-1,4-pentadien-3-one in dichloromethane TMS in 3 ml solution under nitrogen atmosphere at room temperature
B (OTf) 4 in dichloromethane (concentration 0.55
M) 0.45 ml (0.25 mmol) was added. After the mixture was stirred for 15 minutes, a saturated aqueous solution of sodium bicarbonate was added.
After the aqueous layer was extracted three times with dichloromethane, the extracts were combined, washed successively with a saturated aqueous solution of sodium bicarbonate and brine, dried over Na 2 SO 4 and the solvent was distilled off under reduced pressure.
The residue was subjected to silica gel thin layer chromatography (developing solvent:
Ethyl acetate: hexane = 1: 5) and 36 mg of 2-fluoro-3,4-diphenyl-2-cyclopentenone.
(0.14 mmol) was obtained as a colorless solid. Yield 48
%. IR (KBr disk) 1716, 1635, 1361, 1078, 701, 688 cm
-1 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) 25.1 (1F, d, J = 6 H
z) ppm MS (70 eV) m / z 252 (M + ; 100), 223 (63), 146 (58),
120 (50)

【００１４】参考製造例１ ４−フルオロ−１−フェニ
ル−１，４−ヘプタジエン−３−オンの製造 ４−フルオロ−１−フェニル−４−（フェニルスルフィ
ニル）１−ヘプテン−３−オン１．２５ｇ（３．８ｍｍ
ｏｌ）のベンゼン１０ｍｌ溶液を、１時間加熱還流し
た。減圧下に溶媒を留去した後、残渣をシリカゲル薄層
クロマトグラフィー（展開溶媒：酢酸エチル：ヘキサン
＝１：２０）に付し、４−フルオロ−１−フェニル−
１，４−ヘプタジエン−３−オン４３１ｍｇ（２．０ｍ
ｍｏｌ）を黄色液体として得た。収率５６％。 IR (neat) 2960, 1650, 1600, 1570, 1450, 1330, 120
0, 1010, 760 cm-1 1 H-NMR (500 MHz, CDCl3) δ 1.11 (3H, t, J = 7.5 H
z), 2.33 (2H, dquint, J= 7.6, 2.1 Hz), 6.18 (1H, d
t, J = 34.7, 7.8 Hz), 7.23 (1H, dd, J = 15.6, 2.1
Hz), 7.38-7.43 (3H, m), 7.58-7.64 (2H, m), 7.80 (1
H, d, J = 16.0 Hz)13 C-NMR (126 MHz, CDCl3) δ 13.0 (d, JCF = 2 Hz),
17.9 (d, JCF = 4 Hz),119.6, 121.4 (d, JCF = 13 H
z), 128.6, 128.9, 130.8, 134.5, 145.1 (d, JCF = 2 H
z), 155.5 (d, JCF = 260 Hz), 182.7 (d, JCF = 31 H
z)19 F-NMR (471 MHz, CDCl3 / C6F6) 31.3 (1F, JFH = 3
1.3 Hz) ppm MS (70 eV) m/z 204 ( M+; 44), 131 (69), 103 (100),
77 (57) HRMS calcd for C13H13OF 204.0950 (M+); found 204.0
959Reference Production Example 1 4-Fluoro-1-phenyl
Preparation of 1,4-heptadien-3-one 4-fluoro-1-phenyl-4- (phenylsulfur
Nil) 1-hepten-3-one (1.25 g, 3.8 mm)
ol) in 10 ml of benzene under reflux for 1 hour.
Was. After the solvent was distilled off under reduced pressure, the residue was
Chromatography (developing solvent: ethyl acetate: hexane
= 1: 20) to give 4-fluoro-1-phenyl-
431 mg of 1,4-heptadien-3-one (2.0 m
mol) was obtained as a yellow liquid. 56% yield. IR (neat) 2960, 1650, 1600, 1570, 1450, 1330, 120
0, 1010, 760 cm-1 1 H-NMR (500 MHz, CDClThree) δ 1.11 (3H, t, J = 7.5 H
z), 2.33 (2H, dquint, J = 7.6, 2.1 Hz), 6.18 (1H, d
t, J = 34.7, 7.8 Hz), 7.23 (1H, dd, J = 15.6, 2.1
Hz), 7.38-7.43 (3H, m), 7.58-7.64 (2H, m), 7.80 (1
(H, d, J = 16.0 Hz)13 C-NMR (126 MHz, CDClThree) δ 13.0 (d, JCF= 2 Hz),
17.9 (d, JCF= 4 Hz), 119.6, 121.4 (d, JCF= 13 H
z), 128.6, 128.9, 130.8, 134.5, 145.1 (d, JCF = 2H
z), 155.5 (d, JCF= 260 Hz), 182.7 (d, JCF= 31 H
z)19 F-NMR (471 MHz, CDClThree / C6F6) 31.3 (1F, JFH= 3
1.3 Hz) ppm MS (70 eV) m / z 204 (M+; 44), 131 (69), 103 (100),
 77 (57) HRMS calcd for C13H13OF 204.0950 (M+); found 204.0
959

【００１５】参考製造例２ ４−フルオロ−１−フェニ
ル−１，４−ペンタジエン−３−オンの製造 ４−フルオロ−１−フェニル−４−（フェニルスルフィ
ニル）１−ペンテン−３−オン２３０ｍｇ（０．７６ｍ
ｍｏｌ）のベンゼン４ｍｌ溶液を、１時間加熱還流し
た。減圧下に溶媒を留去した後、残渣をシリカゲル薄層
クロマトグラフィー（展開溶媒：酢酸エチル：ヘキサン
＝１：５）に付し、４−フルオロ−１−フェニル−１，
４−ペンタジエン−３−オン１２９ｍｇ（０．７３ｍｍ
ｏｌ）を淡黄色液体として得た。収率９６％。 IR (KBr disk) 3103, 3030, 1660, 1640, 1610, 1450,
1360, 1070, 940, 900 cm-1 1 H-NMR (500 MHz, CDCl3) δ 5.30 (1H, dd, J = 14.6,
3.4 Hz), 5.70 (1H, dd, J = 45.8, 3.4 Hz), 7.23 (1
H, dd, J = 5.9, 2.1 Hz), 7.397.46 (3H, m), 7.46 (2
H, dd, J = 36.6, 3.1 Hz), 7.84 (1H, dd, J = 15.9 H
z)13 C-NMR (126 MHz, CDCl3) δ 101.6 (d, JCF = 15 H
z), 119.2, 128.2, 129.0,131.2, 134.3, 146.2 (d, J
CF = 2 Hz), 160.6 (d, JCF = 269 Hz), 182.9 (d,JCF
= 31 Hz)19 F-NMR (471 MHz, CDCl3/C6F6) 44.5 (1F, dd, JFH =
45.7, 14.6 Hz) ppm MS (70 eV) m/z 176 ( M+; 67), 103 (100), 77 (70) HRMS calcd for C11H9OF 176.0637 (M+); found 176.06
09.Reference Production Example 2 Production of 4-fluoro-1-phenyl-1,4-pentadien-3-one 230 mg of 4-fluoro-1-phenyl-4- (phenylsulfinyl) 1-penten-3-one .76m
(mol) of benzene was heated under reflux for 1 hour. After evaporating the solvent under reduced pressure, the residue was subjected to silica gel thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5) to give 4-fluoro-1-phenyl-1,4.
129 mg of 4-pentadien-3-one (0.73 mm
ol) as a pale yellow liquid. 96% yield. IR (KBr disk) 3103, 3030, 1660, 1640, 1610, 1450,
1360, 1070, 940, 900 cm -1 1 H-NMR (500 MHz, CDCl 3 ) δ 5.30 (1H, dd, J = 14.6,
3.4 Hz), 5.70 (1H, dd, J = 45.8, 3.4 Hz), 7.23 (1
H, dd, J = 5.9, 2.1 Hz), 7.397.46 (3H, m), 7.46 (2
H, dd, J = 36.6, 3.1 Hz), 7.84 (1H, dd, J = 15.9 H
z) 13 C-NMR (126 MHz, CDCl 3 ) δ 101.6 (d, J CF = 15 H
z), 119.2, 128.2, 129.0, 131.2, 134.3, 146.2 (d, J
CF = 2 Hz), 160.6 (d, J CF = 269 Hz), 182.9 (d, J CF
= 31 Hz) 19 F-NMR (471 MHz, CDCl 3 / C 6 F 6 ) 44.5 (1F, dd, J FH =
45.7, 14.6 Hz) ppm MS ( 70 eV) m / z 176 (M +; 67), 103 (100), 77 (70) HRMS calcd for C 11 H 9 OF 176.0637 (M +); found 176.06
09.

【００１６】[0016]

【発明の効果】本発明製造法によれば、含フッ素シクロ
ペンテノン誘導体を高選択的に高収率で製造することが
できる。According to the production method of the present invention, a fluorine-containing cyclopentenone derivative can be produced with high selectivity and high yield.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 南 享 福岡県宗像市大字自由ヶ丘９丁目８番９号 ──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Minami Kyo 9-9-8 Jiyugaoka, Munakata-shi, Fukuoka

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】一般式 化１ 【化１】 ［式中、Ｒ1、Ｒ2及びＲ3は同一もしくは相異なり、低
級アルキル基、フェニル基または水素原子を表す。］で
示されるジビニル＝ケトン誘導体に、トリメチルシリコ
ン（１＋）＝クロロトリス（トリフルオロメタンスルホ
ナト）ボラート（１−）またはトリメチルシリコン（１
＋）＝テトラキス（トリフルオロメタンスルホナト）ボ
ラート（１−）を作用させることを特徴とする、一般式
化２ 【化２】 ［式中、Ｒ1、Ｒ2及びＲ3は前記と同じ意味を表す。］
で示されるシクロペンテノン誘導体の製造法。1. A compound represented by the general formula: Wherein R 1 , R 2 and R 3 are the same or different and represent a lower alkyl group, a phenyl group or a hydrogen atom. To the divinyl ketone derivative represented by the formula (1), chlorotris (trifluoromethanesulfonato) borate (1-) or trimethylsilicon (1
+) = General formula characterized by reacting tetrakis (trifluoromethanesulfonato) borate (1-) [Wherein, R 1 , R 2 and R 3 represent the same meaning as described above. ]
A method for producing a cyclopentenone derivative represented by the formula: 【請求項２】一般式 化３ 【化３】 ［式中、Ｒ2及びＲ3は前記と同じ意味を表す。］で示さ
れるシクロペンテノン誘導体。2. A compound represented by the general formula: [Wherein, R 2 and R 3 represent the same meaning as described above. And a cyclopentenone derivative represented by the formula:
JP14407698A 1998-05-26 1998-05-26 Process for producing cyclopentenone derivative and cyclopentenone derivative Expired - Fee Related JP4158228B2 (en)

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