JPS5917094B2 - Method for producing cyclopentanone derivatives - Google Patents
Method for producing cyclopentanone derivativesInfo
- Publication number
- JPS5917094B2 JPS5917094B2 JP2266576A JP2266576A JPS5917094B2 JP S5917094 B2 JPS5917094 B2 JP S5917094B2 JP 2266576 A JP2266576 A JP 2266576A JP 2266576 A JP2266576 A JP 2266576A JP S5917094 B2 JPS5917094 B2 JP S5917094B2
- Authority
- JP
- Japan
- Prior art keywords
- alkyl group
- aryl group
- formulas
- hydrogen
- group
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- -1 3-monosubstituted cyclobutanone Chemical class 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LXRXKBMERJLKJR-UHFFFAOYSA-N 2-butyl-2-hydroxy-4-phenylmethoxycyclopentan-1-one Chemical compound C1C(=O)C(CCCC)(O)CC1OCC1=CC=CC=C1 LXRXKBMERJLKJR-UHFFFAOYSA-N 0.000 description 1
- 238000006228 Dieckmann condensation reaction Methods 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001930 cyclobutanes Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RCCPEORTSYDPMB-UHFFFAOYSA-N hydroxy benzenecarboximidothioate Chemical compound OSC(=N)C1=CC=CC=C1 RCCPEORTSYDPMB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003180 prostaglandins Chemical class 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式
″ Ｒ□工Ｈ−（１、
Ｒ”
５（式中、Ｒは水素、アルキル基、アリール基またはア
ルコキシ基であり、Ｒ１ は水素、アルキル基またはア
リール基である。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula "R□techH-(1, R"5 (wherein R is hydrogen, an alkyl group, an aryl group, or an alkoxy group, and R1 is hydrogen, an alkyl group, or It is an aryl group.
）で表わされるシクロペンタノン誘導体を製造する方法
に関するものである。式中アルキル基、アリール基、ア
ルコキシ０ 基としては本発明の反応に直接関与しない
置換基を有する基も抱括するものである。前記一般式（
Ｉ）で表わされる化合物は脱水反応に附すことによつて
容易に相当するα・β一不飽和五員環ケトンに導くこと
ができる。) The present invention relates to a method for producing a cyclopentanone derivative represented by: In the formula, the alkyl group, aryl group, and alkoxy group include groups having substituents that do not directly participate in the reaction of the present invention. The general formula (
The compound represented by I) can be easily converted into the corresponding α/β monounsaturated five-membered ring ketone by subjecting it to a dehydration reaction.
これらの５ 化合物は医薬や香料等の製造に極めて重要
な原料物質となりうるもので、例えばプロスタグランジ
ン類の医薬〔Ａ、Ｆ、にｌｕｇｅｅｔａｌ、、Ｊ、Ａｍ
ｅｒ。Ｃｈｅｍ、Ｓｏｃ、、１１、９２５６（１９７２
）およびＣ、Ｊ、Ｓｉｈ、ｅｔａｌ、、Ｊ、Ａｍｅｒ、
Ｃｈｅｍ、Ｓｏｃ、、フ 旦１、８６５（１９７５）な
ど〕やジヤスモン等の香料〔Ｇ、ＢｈｃｈｉａｎｄＢ、
Ｅｇｇｅｒ、Ｊ、Ｏｒｇ。Ｃｈｅｍ、、３６、２０２１
（１９７１）〕としての用途を挙げることができる。該
α・β一不飽和五員環ケトンの従来の製造方５ 法とし
ては一般に五員環化合物を出発原料とするものと直鎖の
化合物を原料とするものとあり、例えば次の二方法が文
献に記載されている。These 5 compounds can be extremely important raw materials for the production of medicines, fragrances, etc. For example, prostaglandin medicines [A, F, lugeetal, J, Am]
Er. Chem, Soc, 11, 9256 (1972
) and C, J, Sih, etal,, J, Amer,
Chem, Soc, 1, 865 (1975), etc.] and fragrances such as diasmon [G, BhchiandB,
Egger, J., Org. Chem,, 36, 2021
(1971)]. Conventional methods for producing the α/β monounsaturated five-membered ring ketone 5 Generally, there are two methods, one using a five-membered ring compound as a starting material and the other using a linear compound as a starting material.For example, the following two methods are used. Described in the literature.
（１）シクロペンタジエンを出発原料として、アルキル
化ののちこれにいわゆる一重項酸素を反応させる方法〔
Ｇ．Ｊ．Ｓｉｈｅｔａｌ．、Ｊ．Ｃ．Ｓ．（２）アジピ
ン酸ジエチルにＤｉｅｃｋｍａｎｎ縮合を適用して五員
環化合物を経てこれを該α・β一不飽和五員環ケトンに
導く方法〔Ｌ．ＮＯｖａｋａｎｄＣ．Ｓｚａｎｔａｙ．
Ｓｙｎｔｈｅｓｉｓ、１９７４、３５３〕。(1) A method in which cyclopentadiene is used as a starting material, and after alkylation, it is reacted with so-called singlet oxygen [
G. J. Sihetal. , J. C. S. (2) A method of applying Dieckmann condensation to diethyl adipate to form a five-membered ring compound and then leading to the α/β monounsaturated five-membered ring ketone [L. NovakandC. Szantay.
Synthesis, 1974, 353].
しかしながら（１）の方法は一重項酸素の反応が二種の
異性体の混合体を与えるので工業的に不利な方法である
。さらに（２）の方法は工程数が長く、また該α・β一
不飽和五員環ケトンの４−位に置換基を導入することが
困難である。本発明の方法は工業的に入手の容易な四員
環ケトンを出発原料とし、且つ４一位に各種の置換基の
導入が可能であることを特長とする画期的な方法である
。However, method (1) is industrially disadvantageous because the reaction of singlet oxygen gives a mixture of two isomers. Furthermore, method (2) requires a long number of steps, and it is difficult to introduce a substituent into the 4-position of the α/β monounsaturated five-membered ring ketone. The method of the present invention is an epoch-making method characterized in that it uses an industrially easily available four-membered ring ketone as a starting material and allows the introduction of various substituents at the 41-position.
本発明の方法で原料として用いる一般式
（式中、Ｒは水素、アルキル基、アリール基またはアル
コキシ基であり、Ｒ１は水素、アルキル基またはアリー
ル基であり、Ｒ２はアルキル基またはアリール基である
。The general formula used as a raw material in the method of the present invention (wherein R is hydrogen, an alkyl group, an aryl group, or an alkoxy group, R1 is hydrogen, an alkyl group, or an aryl group, and R2 is an alkyl group or an aryl group) .
）で表わされるシクロブタン誘導体は本発明者等が開発
した方法により容易に製造できる化合物である〔特開昭
４９１３１１９号参照〕。The cyclobutane derivative represented by ) is a compound that can be easily produced by the method developed by the present inventors [see JP-A-4913119].
即ち、２一置換−１・３ジハロプロパンとホルムアルデ
ヒドジメチルメルカプタールＳ−オキシドにより容易に
合成できる３一置換シクロブタノン〔Ｋ．Ｏｇｕｒａ．
Ｍ．Ｙａｍａｓｈｉｔａ，．Ｍ．Ｓｕｚｌｌｋｉａｎｄ
Ｇ．ＴｓｕｃｈｉｈａｓｈｉｌＴｅｔｒａｈｅｄｒＯｎ
ＬｅＴｔ．、３６５３（１９７４）〕とアルデヒドメル
カプタールＳ−オキシドのリチウム塩との反応によつて
好収率かつ高純度に製造できるものである。本発明の方
法は前記一般式（）で表わされる化合物を鉱酸による分
解反応に附することを必須要件とするものである。That is, 3-monosubstituted cyclobutanone [K. Ogura.
M. Yamashita,. M. Suzllkiand
G. TsuchihashilTetrahedrOn
LeTt. , 3653 (1974)] and a lithium salt of aldehyde mercaptal S-oxide, it can be produced in good yield and with high purity. The method of the present invention requires that the compound represented by the general formula () be subjected to a decomposition reaction with a mineral acid.
鉱酸としては塩酸、硫酸などが用いられる。好ましい鉱
酸は硫酸である。酸の使用量はいわゆる接触量で十分で
ある。本発明の実施に当つては溶媒は必らずしも必要と
しないが、所望ならばエーテル、テトラヒドロフラン、
ジオキサン、ベンゼン、塩化メチレン、クロロホルム等
の反応に直接関与しない溶媒を用いることができる。反
応温度は特別な加熱または冷却手段を要しない観点から
室温が好ましい。以下実施例により本発明を更に詳細に
説明する。実施例 １３−ベンジルオキシ−１−（１′
−メチルスルフイニル一１′−メチルチオ−ｎ−ペンチ
ル）−１一シクロブタノール６９９ｍ９をエーテル３０
ｍ１にとかし、１Ｎ希硫酸２ｍ１を加えて室温で２０時
間攪拌した。Hydrochloric acid, sulfuric acid, etc. are used as mineral acids. A preferred mineral acid is sulfuric acid. The amount of acid used is sufficient to be the so-called contact amount. Solvents are not necessarily required in the practice of this invention, but if desired, ether, tetrahydrofuran,
Solvents that do not directly participate in the reaction, such as dioxane, benzene, methylene chloride, and chloroform, can be used. The reaction temperature is preferably room temperature from the viewpoint of not requiring special heating or cooling means. The present invention will be explained in more detail with reference to Examples below. Example 13-benzyloxy-1-(1'
-Methylsulfinyl-1'-methylthio-n-pentyl)-1-cyclobutanol (699 m9) with ether (30 m)
ml, 2 ml of 1N dilute sulfuric acid was added, and the mixture was stirred at room temperature for 20 hours.
有機層を分離したのち水層を塩化メチレン（３０ｍ１×
３回）で抽出した。有機層をあわせて炭酸水素ナトリウ
ム一硫酸マグネシウムで乾燥したのち減圧濃縮した。残
留物をカラムクロマトグラフイ一（シリカゲル、酢酸エ
チル）で手早く分離することによつて４−ベンジルオキ
シ−２（ｎ−ブチル）−２−ヒドロキシシクロペンタノ
ン２７２ηを淡黄色油状物質として得た。収率５３％。
実施例 ２
３〜ベンジル−１−〔メチルスルフイニル（メチルチオ
）メチル〕−１−シクロブタノール８３１ηをエーテル
３４ｍ１にとかし、９Ｎ希硫酸０．６８ｍ１を加えて室
温で４０．５時間撹拌した。After separating the organic layer, the aqueous layer was diluted with methylene chloride (30ml
3 times). The organic layers were combined, dried over sodium bicarbonate and magnesium monosulfate, and then concentrated under reduced pressure. The residue was quickly separated by column chromatography (silica gel, ethyl acetate) to obtain 272η of 4-benzyloxy-2(n-butyl)-2-hydroxycyclopentanone as a pale yellow oil. Yield 53%.
Example 2 831 η of 3-benzyl-1-[methylsulfinyl(methylthio)methyl]-1-cyclobutanol was dissolved in 34 ml of ether, 0.68 ml of 9N diluted sulfuric acid was added, and the mixture was stirred at room temperature for 40.5 hours.
炭酸水素ナトリウムで中和したのち硫酸マグネシウムを
加えて乾燥した。不溶物を濾別したのち濾液を減圧濃縮
した。残留物をカラムクロマトグラフイ一（シリカゲル
、ベンゼン、クロロホルムおよび酢酸エチル）で分離し
て４−ベンジル−２−ヒドロキシシクロペンタノン１３
７Ｗｆｉ１を無色油状物質として得た。収率２５％ｏ実
施例 ３
３−ベンジル−１−（１′−メチルスルフイニルー１′
−メチルチオ−ｎ−ペンチル）−１−シクロブタノール
８７３即をエーテル３０ｍ１にとかし、９Ｎ希硫酸０．
６ｍ１を加えて室温で１９時間攪拌した。After neutralizing with sodium hydrogen carbonate, magnesium sulfate was added and dried. After insoluble matter was filtered off, the filtrate was concentrated under reduced pressure. The residue was separated by column chromatography (silica gel, benzene, chloroform and ethyl acetate) to give 4-benzyl-2-hydroxycyclopentanone 13
7Wfi1 was obtained as a colorless oil. Yield 25% o Example 3 3-benzyl-1-(1'-methylsulfinyl-1'
-Methylthio-n-pentyl)-1-cyclobutanol (873ml) was dissolved in 30ml of ether, and 0.0ml of 9N dilute sulfuric acid was dissolved.
6ml of the mixture was added and stirred at room temperature for 19 hours.
炭酸水素ナトリウムを加えて中和、さらに硫酸マグネシ
ウムを加えて乾燥したのち不溶物を濾別した。濾液を減
圧濃縮したのちカラムクロマトグラフイ一（シリカゲル
、ベンゼン）により分離して４−ベンジル−２−（ｎ−
ブチル）−２−ヒドロキシシクロペンタノン３３２ｍ９
（５３％）を得た。としての計算値：２４６、１６１８
）．
このものは常法によりセミカルバゾン誘導体に導いた。After neutralizing by adding sodium hydrogen carbonate and drying by adding magnesium sulfate, insoluble matter was filtered off. After concentrating the filtrate under reduced pressure, it was separated by column chromatography (silica gel, benzene) to give 4-benzyl-2-(n-
butyl)-2-hydroxycyclopentanone 332m9
(53%). Calculated value as: 246, 1618
). This product was converted into a semicarbazone derivative by a conventional method.
Claims (1)
に附することを特徴とする、一般式▲数式、化学式、表
等があります▼ で表わされるシクロペンタノン誘導体の製造方法〔式中
、Ｒは水素、アルキル基、アリール基またはアルコキシ
基であり、Ｒ＾１は水素、アルキル基またはアリール基
であり、Ｒ＾２はアルキル基またはアリール基である。 〕。[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ There are general formulas ▲ Numerical formulas, chemical formulas, tables, etc. characterized in that the cyclobutane derivative represented by is subjected to a decomposition reaction with a mineral acid. ▼ Method for producing a cyclopentanone derivative represented by [wherein, R is hydrogen, an alkyl group, an aryl group, or an alkoxy group, R^1 is hydrogen, an alkyl group, or an aryl group, and R^2 is an alkyl group] or an aryl group. ].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266576A JPS5917094B2 (en) | 1976-03-04 | 1976-03-04 | Method for producing cyclopentanone derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266576A JPS5917094B2 (en) | 1976-03-04 | 1976-03-04 | Method for producing cyclopentanone derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52106839A JPS52106839A (en) | 1977-09-07 |
| JPS5917094B2 true JPS5917094B2 (en) | 1984-04-19 |
Family
ID=12089134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2266576A Expired JPS5917094B2 (en) | 1976-03-04 | 1976-03-04 | Method for producing cyclopentanone derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5917094B2 (en) |
-
1976
- 1976-03-04 JP JP2266576A patent/JPS5917094B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52106839A (en) | 1977-09-07 |
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