JPH05163190A - Production of 5-methylene-2-substituted-2-cyclopentene-1-one - Google Patents
Production of 5-methylene-2-substituted-2-cyclopentene-1-oneInfo
- Publication number
- JPH05163190A JPH05163190A JP3331066A JP33106691A JPH05163190A JP H05163190 A JPH05163190 A JP H05163190A JP 3331066 A JP3331066 A JP 3331066A JP 33106691 A JP33106691 A JP 33106691A JP H05163190 A JPH05163190 A JP H05163190A
- Authority
- JP
- Japan
- Prior art keywords
- methylene
- hydroxy
- trialkylsilyl
- substituted
- 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.)
- Granted
Links
- -1 5-methylene-2-substituted-2-cyclopentene-1-one Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- PFVOBPQTROAWIL-UHFFFAOYSA-N 3-hydroxy-2-methylidene-5-phenyl-1-trimethylsilylpent-4-en-1-one Chemical compound C[Si](C)(C)C(=O)C(=C)C(O)C=CC1=CC=CC=C1 PFVOBPQTROAWIL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 2
- 239000002246 antineoplastic agent Substances 0.000 abstract description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract description 2
- 150000008280 chlorinated hydrocarbons Chemical group 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005828 desilylation reaction Methods 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IYWGFJJRSBJBDL-UHFFFAOYSA-N 3-hydroxy-2-methylidene-1,5-bis(trimethylsilyl)pent-4-en-1-one Chemical compound C[Si](C)(C)C=CC(O)C(=C)C(=O)[Si](C)(C)C IYWGFJJRSBJBDL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- RVKDYYVFOOCZNH-UHFFFAOYSA-N 3-hydroxy-2-methylidene-1,5-bis(tributylsilyl)pent-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C=CC(C(=C)C(=O)[Si](CCCC)(CCCC)CCCC)O RVKDYYVFOOCZNH-UHFFFAOYSA-N 0.000 description 1
- GDPQWRGCSQXVKY-UHFFFAOYSA-N 3-hydroxy-2-methylidene-1,5-bis(triethylsilyl)pent-4-en-1-one Chemical compound CC[Si](CC)(CC)C=CC(C(=C)C(=O)[Si](CC)(CC)CC)O GDPQWRGCSQXVKY-UHFFFAOYSA-N 0.000 description 1
- UPRLKKBQMYKAPW-UHFFFAOYSA-N 3-hydroxy-2-methylidene-1-tributylsilyl-5-triethylsilylpent-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C(=O)C(=C)C(C=C[Si](CC)(CC)CC)O UPRLKKBQMYKAPW-UHFFFAOYSA-N 0.000 description 1
- PXICNZXHGIIFOS-UHFFFAOYSA-N 3-hydroxy-2-methylidene-1-tributylsilyl-5-trimethylsilylpent-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C(=O)C(=C)C(C=C[Si](C)(C)C)O PXICNZXHGIIFOS-UHFFFAOYSA-N 0.000 description 1
- SXMVNOHXDFOOBV-UHFFFAOYSA-N 3-hydroxy-2-methylidene-5-phenyl-1-tributylsilylpent-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C(=O)C(=C)C(C=CC1=CC=CC=C1)O SXMVNOHXDFOOBV-UHFFFAOYSA-N 0.000 description 1
- GDSGXRUXCNAXNN-UHFFFAOYSA-N 3-hydroxy-2-methylidene-5-phenyl-1-triethylsilylpent-4-en-1-one Chemical compound CC[Si](CC)(CC)C(=O)C(=C)C(C=CC1=CC=CC=C1)O GDSGXRUXCNAXNN-UHFFFAOYSA-N 0.000 description 1
- MLHSASBBPIOWLO-UHFFFAOYSA-N 3-hydroxy-2-methylidene-5-tributylsilyl-1-trimethylsilylpent-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C=CC(C(=C)C(=O)[Si](C)(C)C)O MLHSASBBPIOWLO-UHFFFAOYSA-N 0.000 description 1
- CZAPVBVKMIKTAW-UHFFFAOYSA-N 3-hydroxy-2-methylidene-5-triethylsilyl-1-trimethylsilylpent-4-en-1-one Chemical compound CC[Si](CC)(CC)C=CC(C(=C)C(=O)[Si](C)(C)C)O CZAPVBVKMIKTAW-UHFFFAOYSA-N 0.000 description 1
- BDPKWFSJTXKXAA-UHFFFAOYSA-N 3-hydroxy-2-methylidene-6-phenyl-1-tributylsilylhex-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C(=O)C(=C)C(C=CCC1=CC=CC=C1)O BDPKWFSJTXKXAA-UHFFFAOYSA-N 0.000 description 1
- WCAWQOAGTFAERE-UHFFFAOYSA-N 3-hydroxy-2-methylidene-6-phenyl-1-trimethylsilylhex-4-en-1-one Chemical compound C[Si](C)(C)C(=O)C(=C)C(C=CCC1=CC=CC=C1)O WCAWQOAGTFAERE-UHFFFAOYSA-N 0.000 description 1
- YLUQBEXTDBCKLT-UHFFFAOYSA-N 3-hydroxy-2-methylidene-7-phenyl-1-tributylsilylhept-4-en-1-one Chemical compound CCCC[Si](CCCC)(CCCC)C(=O)C(=C)C(C=CCCC1=CC=CC=C1)O YLUQBEXTDBCKLT-UHFFFAOYSA-N 0.000 description 1
- SLKGGGFRNMNBIO-UHFFFAOYSA-N 3-hydroxy-2-methylidene-7-phenyl-1-triethylsilylhept-4-en-1-one Chemical compound CC[Si](CC)(CC)C(=O)C(=C)C(C=CCCC1=CC=CC=C1)O SLKGGGFRNMNBIO-UHFFFAOYSA-N 0.000 description 1
- DJFDDAAZBIFGIL-UHFFFAOYSA-N 3-hydroxy-2-methylidene-7-phenyl-1-trimethylsilylhept-4-en-1-one Chemical compound C[Si](C)(C)C(=O)C(=C)C(C=CCCC1=CC=CC=C1)O DJFDDAAZBIFGIL-UHFFFAOYSA-N 0.000 description 1
- KYPJODYLZIOMTO-UHFFFAOYSA-N 3-trimethylsilylprop-2-enal Chemical compound C[Si](C)(C)C=CC=O KYPJODYLZIOMTO-UHFFFAOYSA-N 0.000 description 1
- QUMSUJWRUHPEEJ-UHFFFAOYSA-N 4-Pentenal Chemical compound C=CCCC=O QUMSUJWRUHPEEJ-UHFFFAOYSA-N 0.000 description 1
- DVKNGRMASNMREJ-UHFFFAOYSA-N 5-methylidene-2-phenylcyclopent-2-en-1-one Chemical compound O=C1C(=C)CC=C1C1=CC=CC=C1 DVKNGRMASNMREJ-UHFFFAOYSA-N 0.000 description 1
- JHHIAPHEROGYEL-UHFFFAOYSA-N 5-methylidene-2-trimethylsilylcyclopent-2-en-1-one Chemical compound C[Si](C)(C)C1=CCC(=C)C1=O JHHIAPHEROGYEL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CFSRMTBEUXWRPS-UHFFFAOYSA-N CC[Si](CC)(CC)C(=O)CCC=C Chemical compound CC[Si](CC)(CC)C(=O)CCC=C CFSRMTBEUXWRPS-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- NSVJBZMOOQTNJZ-UHFFFAOYSA-N trimethyl(1-methylsulfanylpropa-1,2-dienyl)silane Chemical compound CSC(=C=C)[Si](C)(C)C NSVJBZMOOQTNJZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/673—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 by change of size of the carbon skeleton
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は５−メチレン−２−置換
−２−シクロペンテン−１−オンの製造方法の改良に関
する。５−メチレン−２−置換−２−シクロペンテン−
１−オンは各種の農薬、医薬、特にシクロペンテノイド
系抗生物質や制癌剤等の中間体として有用な化合物であ
る。FIELD OF THE INVENTION The present invention relates to an improvement in a method for producing 5-methylene-2-substituted-2-cyclopenten-1-one. 5-methylene-2-substituted-2-cyclopentene-
1-one is a compound useful as an intermediate for various agricultural chemicals, pharmaceuticals, particularly cyclopentenoid antibiotics, anticancer agents and the like.
【０００２】[0002]
【従来の技術】５−メチレン−２−置換−２−シクロペ
ンテン−１−オンの製造法としてはスピロシクロペンテ
ノン類の熱分解による方法が知られている（ジャーナル
オブオーガニック ケミストリー： Journal of Orga
nic Chemistry (47) 599〜601(1982)）。2. Description of the Related Art As a method for producing 5-methylene-2-substituted-2-cyclopenten-1-one, a method by thermal decomposition of spirocyclopentenones is known (Journal of Organic Chemistry: Journal of Orga
nic Chemistry (47) 599-601 (1982)).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
方法は４００〜４５０℃の高温、かつ０．０５ｍｍＨｇ
の高真空下の反応であり、原料の入手を含めて、工業的
実施には難点がある。かかる事情に鑑み、５−メチレン
−２−置換−２−シクロペンテン−１−オンの製造方法
について鋭意検討した結果、５−置換−３−ヒドロキシ
−２−メチレン−１−トリアルキルシリル−４−ペンテ
ン−１−オンを過レニウム酸塩およびアリールスルホン
酸と処理することにより５−メチレン−２−置換−２−
シクロペンテン−１−オンが得られることを見出し、本
発明を完成するに至った。However, the conventional method has a high temperature of 400 to 450 ° C. and 0.05 mmHg.
It is a reaction under high vacuum, and there are difficulties in industrial implementation, including the acquisition of raw materials. In view of such circumstances, as a result of diligent study on a method for producing 5-methylene-2-substituted-2-cyclopenten-1-one, 5-substituted-3-hydroxy-2-methylene-1-trialkylsilyl-4-pentene was found. By treating -1-one with perrhenate and arylsulfonic acid, 5-methylene-2-substituted-2-
The inventors have found that cyclopenten-1-one can be obtained, and completed the present invention.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は一般
式（１）、 （式中、Ｒ1 はフェニル置換アルキル基、フェニル基ま
たはトリアルキルシリル基を、ＴＲＳはトリアルキルシ
リル基を表す）で示される５−置換−３−ヒドロキシ−
２−メチレン−１−トリアルキルシリル−４−ペンテン
−１−オンを過レニウム酸塩およびアリールスルホン酸
の存在下に環化脱シリル化させることを特徴とする一般
式（２）、 （式中、Ｒ1 は上記と同じ。）で示される５−メチレン
−２−置換−２−シクロペンテン−１−オンの製造方法
である。That is, the present invention is based on the general formula (1), (Wherein R 1 represents a phenyl-substituted alkyl group, a phenyl group or a trialkylsilyl group, and TRS represents a trialkylsilyl group).
General formula (2), characterized in that 2-methylene-1-trialkylsilyl-4-penten-1-one is cyclized and desilylated in the presence of perrhenate and arylsulfonic acid. (In the formula, R1 is the same as above.), And is a method for producing 5-methylene-2-substituted-2-cyclopenten-1-one.
【０００５】本発明に用いられる一般式（１）で示され
る５−置換−３−ヒドロキシ−２−メチレン−１−トリ
アルキルシリル−４−ペンテン−１−オンの置換基Ｒ1
として、具体的には２−フェニルエチル、ベンジル基等
のフェニル置換アルキル基、フェニル基およびトリメチ
ルシリル、トリエチルシリル、トリブチルシリル基等の
トリアルキルシリル基が挙げられる。またＴＲＳで示さ
れるトリアルキルシリル基としてもトリメチルシリル、
トリエチルシリル、トリブチルシリル基等が挙げられ
る。The substituent R 1 of the 5-substituted-3-hydroxy-2-methylene-1-trialkylsilyl-4-penten-1-one represented by the general formula (1) used in the present invention.
Specific examples thereof include phenyl-substituted alkyl groups such as 2-phenylethyl and benzyl groups, phenyl groups and trialkylsilyl groups such as trimethylsilyl, triethylsilyl and tributylsilyl groups. In addition, trimethylsilyl as a trialkylsilyl group represented by TRS,
Examples thereof include triethylsilyl and tributylsilyl groups.
【０００６】５−置換−３−ヒドロキシ−２−メチレン
−１−トリアルキルシリル−４−ペンテン−１−オンと
して更に具体的には、５−フェニル−３−ヒドロキシ−
２−メチレン−１−トリメチルシリル−４−ペンテン−
１−オン、５−フェニル−３−ヒドロキシ−２−メチレ
ン−１−トリエチルシリル−４−ペンテン−１−オン、
５−フェニル−３−ヒドロキシ−２−メチレン−１−ト
リブチルシリル−４−ペンテン−１−オン、５−ベンジ
ル−３−ヒドロキシ−２−メチレン−１−トリメチルシ
リル−４−ペンテン−１−オン、５−ベンジル−３−ヒ
ドロキシ−２−メチレン−１−トリエチルシリル−４−
ペンテン−１−オン、５−ベンジル−３−ヒドロキシ−
２−メチレン−１−トリブチルシリル−４−ペンテン−
１−オン、５−フェニルエチル−３−ヒドロキシ−２−
メチレン−１−トリメチルシリル−４−ペンテン−１−
オン、５−フェニルエチル−３−ヒドロキシ−２−メチ
レン−１−トリエチルシリル−４−ペンテン−１−オ
ン、５−フェニルエチル−３−ヒドロキシ−２−メチレ
ン−１−トリブチルシリル−４−ペンテン−１−オン、
５−トリメチルシリル−３−ヒドロキシ−２−メチレン
−１−トリメチルシリル−４−ペンテン−１−オン、５
−トリメチルシリル−３−ヒドロキシ−２−メチレン−
１−トリエチルシリル−４−ペンテン−１−オン、５−
トリメチルシリル−３−ヒドロキシ−２−メチレン−１
−トリブチルシリル−４−ペンテン−１−オン、５−ト
リエチルシリル−３−ヒドロキシ−２−メチレン−１−
トリメチルシリル−４−ペンテン−１−オン、５−トリ
エチルシリル−３−ヒドロキシ−２−メチレン−１−ト
リエチルシリル−４−ペンテン−１−オン、５−トリエ
チルシリル−３−ヒドロキシ−２−メチレン−１−トリ
ブチルシリル−４−ペンテン−１−オン、５−トリブチ
ルシリル−３−ヒドロキシ−２−メチレン−１−トリメ
チルシリル−４−ペンテン−１−オン、５−トリブチル
シリル−３−ヒドロキシ−２−メチレン−１−トリエチ
ルシリル−４−ペンテン−１−オン、５−トリブチルシ
リル−３−ヒドロキシ−２−メチレン−１−トリブチル
シリル−４−ペンテン−１−オン等が挙げられる。More specifically as 5-substituted-3-hydroxy-2-methylene-1-trialkylsilyl-4-penten-1-one, more specifically 5-phenyl-3-hydroxy-one
2-methylene-1-trimethylsilyl-4-pentene-
1-one, 5-phenyl-3-hydroxy-2-methylene-1-triethylsilyl-4-penten-1-one,
5-phenyl-3-hydroxy-2-methylene-1-tributylsilyl-4-penten-1-one, 5-benzyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one, 5 -Benzyl-3-hydroxy-2-methylene-1-triethylsilyl-4-
Penten-1-one, 5-benzyl-3-hydroxy-
2-Methylene-1-tributylsilyl-4-pentene-
1-one, 5-phenylethyl-3-hydroxy-2-
Methylene-1-trimethylsilyl-4-pentene-1-
On, 5-phenylethyl-3-hydroxy-2-methylene-1-triethylsilyl-4-penten-1-one, 5-phenylethyl-3-hydroxy-2-methylene-1-tributylsilyl-4-pentene- 1-on,
5-trimethylsilyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one, 5
-Trimethylsilyl-3-hydroxy-2-methylene-
1-triethylsilyl-4-penten-1-one, 5-
Trimethylsilyl-3-hydroxy-2-methylene-1
-Tributylsilyl-4-penten-1-one, 5-triethylsilyl-3-hydroxy-2-methylene-1-
Trimethylsilyl-4-penten-1-one, 5-triethylsilyl-3-hydroxy-2-methylene-1-triethylsilyl-4-penten-1-one, 5-triethylsilyl-3-hydroxy-2-methylene-1 -Tributylsilyl-4-penten-1-one, 5-tributylsilyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one, 5-tributylsilyl-3-hydroxy-2-methylene- Examples thereof include 1-triethylsilyl-4-penten-1-one and 5-tributylsilyl-3-hydroxy-2-methylene-1-tributylsilyl-4-penten-1-one.
【０００７】本発明に用いられる過レニウム酸塩として
は、過レニウム酸テトラアンモニウム、過レニウム酸テ
トラメチルアンモニウム、過レニウム酸テトラエチルア
ンモニウム、過レニウム酸テトラプロピルアンモニウ
ム、過レニウム酸テトラブチルアンモニウム、過レニウ
ム酸テトラペンチルアンモニウム等が挙げられる。Examples of the perrhenate used in the present invention include tetraammonium perrhenate, tetramethylammonium perrhenate, tetraethylammonium perrhenate, tetrapropylammonium perrhenate, tetrabutylammonium perrhenate, and perrhenium. Acid tetrapentylammonium etc. are mentioned.
【０００８】本発明に用いられるアリールスルホン酸と
しては、ベンゼンスルホン酸、パラトルエンスルホン酸
およびメタニトロベンゼンスルホン酸等が挙げられる。Examples of the aryl sulfonic acid used in the present invention include benzene sulfonic acid, paratoluene sulfonic acid and metanitrobenzene sulfonic acid.
【０００９】本発明は通常、溶媒の存在下に行われる。
溶媒は特に限定されるものではないが、ジクロルメタ
ン、１，２−ジクロルエタン、１，１，２−トリクロル
エタンおよびクロロホルム等の塩素化炭化水素が好まし
く用いられる。The present invention is usually carried out in the presence of a solvent.
The solvent is not particularly limited, but chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane and chloroform are preferably used.
【００１０】反応は通常、５−置換−３−ヒドロキシ−
２−メチレン−１−トリアルキルシリル−４−ペンテン
−１−オンを溶媒に溶解した溶液と過レニウム酸塩とア
リールスルホン酸を溶解した溶液とを混合し、常温また
は必要により加熱し、攪拌して行われる。The reaction is usually 5-substituted-3-hydroxy-
A solution in which 2-methylene-1-trialkylsilyl-4-penten-1-one was dissolved in a solvent was mixed with a solution in which perrhenate and arylsulfonic acid were dissolved, and the mixture was heated at room temperature or if necessary, and stirred. Is done.
【００１１】[0011]
【発明の効果】本発明の方法によれば、５−置換−３−
ヒドロキシ−２−メチレン−１−トリアルキルシリル−
４−ペンテン−１−オンから一段反応で容易に、収率良
く５−メチレン−２−置換−２−シクロペンテン−１−
オンを製造することができる。According to the method of the present invention, 5-substituted-3-
Hydroxy-2-methylene-1-trialkylsilyl-
5-methylene-2-substituted-2-cyclopenten-1- with easy one-step reaction from 4-penten-1-one in a good yield
Can be manufactured on.
【００１２】[0012]
【実施例】以下、本発明を実施例でさらに詳細に説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１３】実施例１ ５−フェニル−３−ヒドロキシ−２−メチレン−１−ト
リメチルシリル−４−ペンテン−１−オン（８５．９ｍ
ｇ，０．３３ｍｍｏｌ）のジクロルメタン（２ｍｌ）溶
液と、過レニウム酸テトラブチルアンモニウム（インオ
ーガニック シンセシス：Inorganic Synthesis 26,391
(1989)に記載の方法により合成した。）（１６．６ｍ
ｇ，０．０３３ｍｍｏｌ）とパラトルエンスルホン酸一
水和物（６．６ｍｇ，０．０３３ｍｍｏｌ）のジクロル
メタン（１．５ｍｌ）溶液を混合し、室温で２時間攪拌
して反応を行った。Example 1 5-Phenyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one (85.9 m)
g, 0.33 mmol) in dichloromethane (2 ml) and tetrabutylammonium perrhenate (Inorganic Synthesis 26,391)
(1989). ) (16.6m
g, 0.033 mmol) and para-toluenesulfonic acid monohydrate (6.6 mg, 0.033 mmol) in dichloromethane solution (1.5 ml) were mixed and stirred at room temperature for 2 hours for reaction.
【００１４】反応液に飽和炭酸水素ナトリウム溶液とジ
エチルエーテルを加えて攪拌した。有機層を塩水で洗
い、無水硫酸ナトリウムで乾燥した。次いで溶媒のジク
ロルメタンを真空に引いて除き、得られた粗生成物を薄
層クロマトグラフ（シリカゲル、展開液はヘキサンと酢
酸エチルが５：１の溶液）で生成物を分離した。生成物
の分析値は以下のとおりであり、５−メチレン−２−フ
ェニル−２−シクロペンテン−１−オンと同定された。 ＩＲ（ｎｅａｔ） 1689, 1645, 1593, 1491, 1444, 1417 ｃｍ-1 1Ｈ−ＮＭＲ(500MHz,CDCl3 ) 3.32(2H,d,J=1.2Hz), 5.53(1H,d,J=0.9Hz) 6.24(1H,d,J=0.9Hz), 7.34〜7.42(3H,m), 7.75〜7.79(3H,m); 13Ｃ−ＮＭＲ(125MHz,CDCl3 ) 31.74, 117.70, 126.97, 128.43, 128.53, 131.89, 142.09, 144.73, 152.30, 193.90 生成量は３７．６ｍｇ（０．２２ｍｍｏｌ）で、収率は
６７％であった。A saturated sodium hydrogen carbonate solution and diethyl ether were added to the reaction solution and the mixture was stirred. The organic layer was washed with brine and dried over anhydrous sodium sulfate. Then, the solvent dichloromethane was removed by drawing a vacuum, and the obtained crude product was separated by thin layer chromatography (silica gel, the developing solution was a solution of hexane and ethyl acetate of 5: 1). The analytical values of the product are as follows and were identified as 5-methylene-2-phenyl-2-cyclopenten-1-one. IR (neat) 1689, 1645, 1593, 1491, 1444, 1417 cm -1 1 H-NMR (500MHz, CDCl 3 ) 3.32 (2H, d, J = 1.2Hz), 5.53 (1H, d, J = 0.9Hz ) 6.24 (1H, d, J = 0.9Hz), 7.34〜7.42 (3H, m), 7.75〜7.79 (3H, m); 13 C-NMR (125MHz, CDCl 3 ) 31.74, 117.70, 126.97, 128.43, 128.53 , 131.89, 142.09, 144.73, 152.30, 193.90 The production amount was 37.6 mg (0.22 mmol), and the yield was 67%.
【００１５】参考例１ ３−トリメチルシリル−２−プロペンアール（１４４．
８０ｍｇ、１．１３ｍｍｏｌ）、１−メチルチオ−１−
トリメチルシリル−１，２−プロパジエン（６７２．９
０ｍｇ、４．２４ｍｍｏｌ）のジクロロメタン６ｍｌ溶
液に−４５℃で三弗化硼素エーテラート（ＢＦ3 ・ＯＥ
ｔ2 ）（３１０．５５ｍｇ、２．１９ｍｍｏｌ）のジク
ロロメタン溶液４ｍｌを一滴ずつ滴下した。−４５℃で
１６０分攪拌後、反応液に炭酸水素ナトリウム水溶液を
加え反応を停止した。水相をジクロロメタンで２回抽出
し、有機相を合わせ、無水硫酸ナトリウムで乾燥した。Reference Example 1 3-trimethylsilyl-2-propenal (144.
80 mg, 1.13 mmol), 1-methylthio-1-
Trimethylsilyl-1,2-propadiene (672.9
0 mg, 4.24 mmol) in 6 ml of dichloromethane was added at -45 ° C. to boron trifluoride etherate (BF 3 · OE).
4 ml of a dichloromethane solution of t 2 ) (310.55 mg, 2.19 mmol) was added dropwise. After stirring at -45 ° C for 160 minutes, an aqueous sodium hydrogen carbonate solution was added to the reaction solution to stop the reaction. The aqueous phase was extracted twice with dichloromethane, the organic phases were combined and dried over anhydrous sodium sulfate.
【００１６】溶媒を減圧下留去後、粗生成物を薄層クロ
マトグラフィー（ヘキサン：酢酸エチル＝７：１）にて
分離精製した。生成物の分析値は以下のとおりであり、
５−トリメチルシリル−３−ヒドロキシ−２−メチレン
−１−トリメチルシリル−４−ペンテン−１−オンと同
定された。 ＩＲ（ｎｅａｔ） 1597, 1250, 989, 842, 757 ｃｍ-1 1Ｈ−ＮＭＲ(500MHz,CDCl3 ) 0.04(9H,s), 0.26(s,9H), 2.94(1H,d,J=5.6Hz) 4.89-4.92(1H,m), 5.89(1H,dd,J=18.8,1.4Hz) 6.04(1H,dd,J=18.8, 4.7Hz), 6.06(1H,s) 6.14(1H,d,J=0.8Hz) 13Ｃ−ＮＭＲ(125MHz,CDCl3 ) -1.47, 1.38, 72.90, 128.6, 130.46, 145.19, 152.99, 239.66 生成量は１４８．１０ｍｇで、収率は４９％であった。After the solvent was distilled off under reduced pressure, the crude product was separated and purified by thin layer chromatography (hexane: ethyl acetate = 7: 1). The analytical values of the product are as follows,
It was identified as 5-trimethylsilyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one. IR (neat) 1597, 1250, 989, 842, 757 cm -1 1 H-NMR (500MHz, CDCl 3) 0.04 (9H, s), 0.26 (s, 9H), 2.94 (1H, d, J = 5.6Hz ) 4.89-4.92 (1H, m), 5.89 (1H, dd, J = 18.8,1.4Hz) 6.04 (1H, dd, J = 18.8, 4.7Hz), 6.06 (1H, s) 6.14 (1H, d, J = 0.8 Hz) 13 C-NMR (125 MHz, CDCl 3 ) -1.47, 1.38, 72.90, 128.6, 130.46, 145.19, 152.99, 239.66 The amount produced was 148.10 mg, and the yield was 49%.
【００１７】実施例２ 参考例１で合成した５−トリメチルシリル−３−ヒドロ
キシ−２−メチレン−１−トリメチルシリル−４−ペン
テン−１−オン２３．４０ｍｇ（０．０９ｍｍｏｌ）の
ジクロロメタン溶液４ｍｌに過レニウム酸テトラブチル
アンモニウム５００ｍｇ（０．０１０ｍｍｏｌ）、パラ
トルエンスルホン酸一水和物４．６０ｍｇ（０．０２４
ｍｍｏｌ）を加え、室温で３日間攪拌した。反応液に炭
酸水素ナトリウム水溶液を加え反応を停止させ後、有機
物をジクロロメタンで２回抽出した。有機相を合わせ、
無水硫酸ナトリウムで乾燥した。Example 2 Perrhenium was added to 4 ml of a dichloromethane solution of 23.40 mg (0.09 mmol) of 5-trimethylsilyl-3-hydroxy-2-methylene-1-trimethylsilyl-4-penten-1-one synthesized in Reference Example 1. Acid tetrabutylammonium acid 500 mg (0.010 mmol), paratoluenesulfonic acid monohydrate 4.60 mg (0.024
mmol) was added and the mixture was stirred at room temperature for 3 days. Aqueous sodium hydrogen carbonate solution was added to the reaction solution to stop the reaction, and the organic matter was extracted twice with dichloromethane. Combine the organic phases,
It was dried over anhydrous sodium sulfate.
【００１８】減圧下、溶媒を留去後、粗生成物を薄層ク
ロマトグラフィー（ヘキサン：酢酸エチル＝１０：１）
にて分離精製した。生成物の分析値は以下のとおりであ
り、５−メチレン−２−トリメチルシリル−２−シクロ
ペンテン−１−オンと同定された。 ＩＲ(soln,Cell) 1689, 1643 ｃｍ-1 1Ｈ−ＮＭＲ(500MHz,CDCl3 ) 0.19(9H,s), 3.23-3.24(2H,m), 5.40(1H,bs) 6.04(1H,bs), 7.70(1H,bs) 13Ｃ−ＮＭＲ(125MHz,CDCl3 ) -1.99, 35.33, 116.40, 142.16, 149.25, 165.62, 199.60 生成量は９．６０ｍｇで、収率は６３％であった。After the solvent was distilled off under reduced pressure, the crude product was subjected to thin layer chromatography (hexane: ethyl acetate = 10: 1).
Separated and purified in. The analytical values of the product are as follows and were identified as 5-methylene-2-trimethylsilyl-2-cyclopenten-1-one. IR (soln, Cell) 1689, 1643 cm -1 1 H-NMR (500MHz, CDCl 3 ) 0.19 (9H, s), 3.23-3.24 (2H, m), 5.40 (1H, bs) 6.04 (1H, bs) , 7.70 (1H, bs) 13 C-NMR (125MHz, CDCl 3 ) -1.99, 35.33, 116.40, 142.16, 149.25, 165.62, 199.60 The amount produced was 9.60 mg, and the yield was 63%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 45/67 Ｃ０７Ｆ 7/08 Ｈ 8018−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 45/67 C07F 7/08 H 8018-4H
Claims (1)
たはトリアルキルシリル基を、ＴＲＳはトリアルキルシ
リル基を表す）で示される５−置換−３−ヒドロキシ−
２−メチレン−１−トリアルキルシリル−４−ペンテン
−１−オンを過レニウム酸塩およびアリールスルホン酸
の存在下に環化脱シリル化させることを特徴とする一般
式（２）、 （式中、Ｒ1 は上記と同じ。）で示される５−メチレン
−２−置換−２−シクロペンテン−１−オンの製造方
法。1. The general formula (1), (Wherein R 1 represents a phenyl-substituted alkyl group, a phenyl group or a trialkylsilyl group, and TRS represents a trialkylsilyl group).
General formula (2), characterized in that 2-methylene-1-trialkylsilyl-4-penten-1-one is cyclized and desilylated in the presence of perrhenate and arylsulfonic acid. (In the formula, R1 is the same as above.) A method for producing 5-methylene-2-substituted-2-cyclopenten-1-one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3331066A JP3055273B2 (en) | 1991-12-16 | 1991-12-16 | Method for producing 5-methylene-2-substituted-2-cyclopenten-1-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3331066A JP3055273B2 (en) | 1991-12-16 | 1991-12-16 | Method for producing 5-methylene-2-substituted-2-cyclopenten-1-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163190A true JPH05163190A (en) | 1993-06-29 |
| JP3055273B2 JP3055273B2 (en) | 2000-06-26 |
Family
ID=18239479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3331066A Expired - Fee Related JP3055273B2 (en) | 1991-12-16 | 1991-12-16 | Method for producing 5-methylene-2-substituted-2-cyclopenten-1-one |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3055273B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008519827A (en) * | 2004-11-11 | 2008-06-12 | フイルメニツヒ ソシエテ アノニム | Synthesis of cyclopentenone |
-
1991
- 1991-12-16 JP JP3331066A patent/JP3055273B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008519827A (en) * | 2004-11-11 | 2008-06-12 | フイルメニツヒ ソシエテ アノニム | Synthesis of cyclopentenone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3055273B2 (en) | 2000-06-26 |
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