KR0183184B1 - Process for the preparation of 2-exomethylene cepham sulfoxide - Google Patents
Process for the preparation of 2-exomethylene cepham sulfoxide Download PDFInfo
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- KR0183184B1 KR0183184B1 KR1019950059738A KR19950059738A KR0183184B1 KR 0183184 B1 KR0183184 B1 KR 0183184B1 KR 1019950059738 A KR1019950059738 A KR 1019950059738A KR 19950059738 A KR19950059738 A KR 19950059738A KR 0183184 B1 KR0183184 B1 KR 0183184B1
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- Prior art keywords
- sulfoxide
- present
- complex
- nitrobenzyl
- general formula
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- -1 cepham sulfoxide Chemical class 0.000 title claims description 8
- 238000000034 method Methods 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title description 4
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 claims abstract description 12
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 claims abstract description 9
- 150000003462 sulfoxides Chemical class 0.000 claims abstract description 7
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KDXFMMHNGFNJFA-UHFFFAOYSA-N 4-oxoazetidine-2-sulfinyl chloride Chemical compound ClS(=O)C1CC(=O)N1 KDXFMMHNGFNJFA-UHFFFAOYSA-N 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical class O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 abstract 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- WDRFYIPWHMGQPN-UHFFFAOYSA-N 2-chloroisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Cl)C(=O)C2=C1 WDRFYIPWHMGQPN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 세파계 항생물질을 제조하는 데 중간물질로서 유용한 다음의 구조식(1)로 표시되는 3-액소메틸렌세팜설폭사이드를 제조하는 방법에 관한 것으로, 일반식 (3)의 2-클로로설피닐아제티딘-4-온 유도체와 오염화몰리브데늄 또는 육염화텅스텐을 반응시켜서 복합체를 생성하고 이를 분리, 분해시켜서 일반식(1)의 목적화합물을 제조한다.The present invention relates to a method for preparing 3-xomethylenecepam sulfoxide represented by the following structural formula (1) which is useful as an intermediate for preparing a cephaic antibiotic, and 2-chlorosulfinyl of the general formula (3) An azetidin-4-one derivative is reacted with molybdenum pentachloride or tungsten chloride to generate a complex, and is separated and decomposed to prepare a target compound of the general formula (1).
위 식에서 R1은 p-니트로벤질기 또는 2,2,2-트리클로에틸기이다.Wherein R 1 is a p-nitrobenzyl group or 2,2,2-trichloroethyl group.
본 발명의 방법은 종래에 비해 보다 수율이 높으며 별도의 정제과정이 필요없는 고순도의 3-액소메틸렌세팜설폭사이드의 제조방법을 제공한다.The method of the present invention provides a method of producing high-purity 3-isomethylenecepam sulfoxide which is higher in yield than the conventional method and does not require a separate purification process.
Description
본 발명은 세파계 항생물질을 제조하는 데 중간물질로서 유용한 다음의 구조식(1)로 표시되는 3-엑소메틸렌세팜설폭사이드를 고수율, 고순도로 간편하게 제조하는 방법에 관한 것이다.The present invention relates to a method for the simple production of high yield and high purity of 3-exomethylenecepam sulfoxide represented by the following structural formula (1), which is useful as an intermediate for preparing a cephaic antibiotic.
위 식에서 R1은 p-니트로벤질기 또는 2,2,2-트리클로에틸기이다.Wherein R 1 is a p-nitrobenzyl group or 2,2,2-trichloroethyl group.
상기 일반식(1)의 3-엑소메틸렌세팜설폭사이드는 하기한 다양한 방법으로 제조되고 있다. 미국특허 제4,052,387호에는 루이스 산 형태의 프리델 크라프트 촉매, 브론스테드 양성자 산 형태의 프리텔-크라프트 촉매를 사용한 3-엑소메틸렌세팜설폭사이드 에스테르의 생성이 기술되어 있다. 이 방법은 페니실린 설폭사이드 에스테르를 2-클로로설피닐아제티디논 중간체를 거쳐 3-엑소메틸렌세팜 에스테르 설폭사이드로 전환시키는 2단계 공정으로 유용한다.3-exomethylenecepam sulfoxide of the general formula (1) is prepared by the following various methods. US Pat. No. 4,052,387 describes the production of 3-exomethylenecepamsulfoxide esters using Friedel Kraft catalyst in Lewis acid form and Freetel-Craft catalyst in Bronsted proton acid form. This method is useful as a two step process in which the penicillin sulfoxide ester is converted to 3-exomethylenecepam ester sulfoxide via the 2-chlorosulfinylazetidinone intermediate.
2단계 공정에 따른 2-클로로 설피닐 아제티디논의 제조 및 그 사용이 미국특허 제4,057,203호에 기술되어 있고, 미국특허 제960,347호, 제49,266호에는 에폭사이드 또는 에폭사이드-산화 칼슘 혼합물 대신에 염화수소 결합제로서 불용성 폴리비닐 피리딘 가교-결합된 공중합체를 사용한다.The preparation and use of 2-chloro sulfinyl azetidinone according to a two-step process is described in US Pat. No. 4,057,203, and US Pat. Nos. 960,347, 49,266 in the presence of hydrogen chloride instead of epoxide or epoxide-calcium oxide mixtures. As the binder, an insoluble polyvinyl pyridine cross-linked copolymer is used.
그러나 이와 같은 종래의 방법으로 생산된 3-엑소메틸렌세팜설폭사이드는 좋은 색상의 제품을 얻기 어렵고 순도가 높지 못하며 수율이 낮다는 문제점이 있다.However, 3-exomethylenecepam sulfoxide produced by such a conventional method has a problem that it is difficult to obtain a good color product, the purity is not high, and the yield is low.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위하여 안출된 것으로서 본 발명의 목적은 상기한 공지의 제조방법들의 문제점을 개선하여 수율이 높으며 별도의 정제과정이 필요없는 고순도의 3-엑소메틸렌세팜설폭사이드의 제조방법을 제공하는 것을 목적으로 한다.The present invention has been made to solve the problems of the prior art as described above is an object of the present invention is to improve the problems of the above known production method is high yield and does not require a separate purification process of high purity 3-exomethylenecepam It is an object to provide a method for producing sulfoxide.
상기와 같은 발명의 목적을 달성하기 위하여 본 발명은 하기한 다음 반응도식으로 설명된다.In order to achieve the object of the invention as described above the present invention is described by the following scheme.
식에서, R1은 앞에서 정의한 바와 같다.In the formula, R 1 is as defined above.
이때, 본 발명의 방법은, 무수 조건하 불활성 유기용매중에서 일반식(3)의 2-클로로설피닐아제티딘-4-온과 촉매로서 오염화몰리브데늄 또는 육염화텅스텐을 옥소 화합물 존재하에 반응시킴으로써 보다 간편히 고수율로 목접화합물을 제조하는 것을 특징으로 한다.At this time, the method of the present invention is made by reacting 2-chlorosulfinylazetidin-4-one of general formula (3) with molybdenum chloride or tungsten chloride in the presence of an oxo compound as a catalyst in an inert organic solvent under anhydrous conditions. It is characterized in that the preparation of the neck compound more easily in a high yield.
본 발명을 보다 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
17.3%로 수화된 몰레큘러 시브를 톨루엔에 넣고 공비하여 딘-스톡(Dean-stock)장치로 수분을 제거한 후 구조식(2)의 화합물[즉, p-니트로벤질 6-페녹시 아세트아미도-2,2-디메틸펜암-3-카복실레이트-1-옥사이드 또는 2,2,2-트리클로로에틸 6-페녹시 아세트아미도-2,2-디메틸펜암-3-카복실레이트-1-옥사이드]을 1.1몰 당량의 N-클로로 프탈이미드와 반응 시킨다. 반응을 환류온도에서 약 2시간 진행시킨 뒤 반응 현탁액을 여과하여 몰레큘러 시브와 프탈이미드를 제거하고 구조식(3)의 화합물[즉, p-니트로 벤질 3-메틸-2-(2-클로로설피닐-4-옥소-3-페녹시아세트아미도-아제티디닐)-3-부테노에이트 또는 2,2,2-트리클로로에틸 3-메틸-2-(2-클로로설피닐-4-옥소-3-페녹시 아세트아미도-아제티디닐)-3-부테노에이트]를 함유하는 여액을 약 0 내지 10℃로 냉각한다. 냉각한 여액에 약 1몰 당량의 디에틸에테르를 가하고 이어서 약 1 내지 3몰당량의 오염화 몰리브데늄 또는 육염화 텅스텐을 가한다. 오염화 몰리브데늄을 가하면 설피닐클로라이드-오염화 몰리브데늄(또는 육염화 텅스텐)-옥소리간드 복합체가 냉각된 여액으로부터 침전되는데 이를 용매중에서 약 2내지 48시간 교반하여 복합체의 생성을 완결짓는다.Molecular sieve hydrated to 17.3% in toluene and azeotropically removed water using a Dean-stock apparatus, followed by the compound of formula (2) [i.e. p-nitrobenzyl 6-phenoxy acetamido-2 , 2-dimethylphenam-3-carboxylate-1-oxide or 2,2,2-trichloroethyl 6-phenoxy acetamido-2,2-dimethylphenam-3-carboxylate-1-oxide] 1.1 React with molar equivalents of N-chloro phthalimide. After the reaction was conducted at reflux for about 2 hours, the reaction suspension was filtered to remove molecular sieve and phthalimide, and the compound of formula (3) [ie, p-nitrobenzyl 3-methyl-2- (2-chlorosulpy) Nyl-4-oxo-3-phenoxyacetamido-azetidinyl) -3-butenoate or 2,2,2-trichloroethyl 3-methyl-2- (2-chlorosulfinyl-4-oxo 3-phenoxy acetamido-azetidinyl) -3-butenoate] is cooled to about 0-10 ° C. To the cooled filtrate is added about 1 molar equivalent of diethyl ether followed by about 1-3 molar equivalents of molybdenum contaminated or tungsten hexachloride. Addition of the molybdenum contaminated precipitates the sulfinylchloride-molybdenum-chloride (or tungsten hexachloride) -oxoriganate complex from the cooled filtrate, which is stirred in the solvent for about 2 to 48 hours to complete the formation of the complex.
이후에 복합체를 여과하여 필터상에서 펜탄 또는 헥산 등의 탄화수소 용매같은 적절한 용매로 세척한 뒤 메틸알코올에 서서히 가해 복합체를 분해시켜 구조식(1)의 목적화합물[즉, p-니트로벤질 7-페녹시아세트아미드-3-엑소메틸렌세팜-4-카복실레이트-1-옥사이드 또는 2,2,2-트리클로로에틸 7-페녹시아세트아미도-3-엑소메틸렌세팜-4-카복실레이트-1-옥사이드]을 생성시킨다. 생성물 현탁액을 약 2 내지 4시간 교반하고 여과한 후 생성물을 필터상에서 세척하여 건조시킨다.Thereafter, the complex was filtered, washed with a suitable solvent such as a hydrocarbon solvent such as pentane or hexane on a filter, and then slowly added to methyl alcohol to decompose the complex to obtain a target compound of formula (1) [ie, p-nitrobenzyl 7-phenoxyacet. Amide-3-exomethylenecepam-4-carboxylate-1-oxide or 2,2,2-trichloroethyl 7-phenoxyacetamido-3-exomethylenecepam-4-carboxylate-1-oxide] Create The product suspension is stirred for about 2-4 hours, filtered and the product is washed on a filter and dried.
본 발명의 공정에서 생성된 화합물은 수율이 높으며 일반적으로 항상제 화합물의 제조에 사용하기 전에 더 정제해야 할 필요가 없다. 그러나 필요하면 적절한 용매로 재결정시켜 그 순도를 더욱 높일 수 있다.The compounds produced in the process of the present invention are high in yield and generally do not need to be further purified prior to use in the preparation of ophthalmic compounds. However, if necessary, the purity can be further increased by recrystallization with an appropriate solvent.
이하 실시예에서 본 발명의 구체적인 제조방법을 상술하지만, 본 발명이 이들 예로만 한정되는 것은 아니다.In the following Examples, the specific production method of the present invention will be described in detail, but the present invention is not limited only to these examples.
[실시예 1]Example 1
1리터의 시약용 톨루엔에 4.6g의 17.3%로 수화된 몰레큘러 시브를 넣고 딘-스톡(Dean-stock)트랩하에서, 트랩으로부터 100ml의 액체가 제거될 때까지 1시간 환류시켰다. 증류기로부터 딘-스톡 장치를 제거하고 50g의 p-니트로벤질 6-페녹시아세트아미도-2,2-디메틸펜암-3-카복실레이트-1-옥사이드와 31.5g의 N-클로로프탈이디드를 가했다. 현탁액을 환류온도로 신속히 재가열하고 교반하면서 약 2시간 환류를 계속하였다. 반응 혼합물을 약 0℃로 냉각하고 10분간 교반한 후 현탁액을 여과하여 몰레큘러 시브와 프탈이미드를 제거하고 p-니트로벤질 3-메틸-2-(2-클로로설피닐-4-옥소-3-페녹시아세트아미도-아제티디닐)-3-부테노에이트를 함유한 냉각된 여액을 50ml의 클로로벤젠 중에 30.0g의 오염화 몰리브데늄을 녹인 용액을 가했다. 생성된 홍적색의 복합체를 -10℃에서 1시간, 상온에서 12시간 교반한 후 복합체를 여과하여 100ml의 헥산으로 세척하고 건조시켰다. 이어서 복합체를 -10℃의 300ml의 메틸알코올에 서서히 가하면 생성물인 p-니트로벤질 7-페녹시아세트아미도-3-엑소 메틸렌팜-4-카복실레이트-1-옥사이드의 현탁액이 생성된다. 현탁액을 -10℃에서 4시간 교반하고 여과한 후 생성물을 50ml의 메틸알코올, 50ml의 디메틸에테르로 세척하고 건조시켜 융점이 194.5-195℃인 p-니트로벤질 7-페녹시아세트아미도-3-엑소메틸렌세팜-4-카복실레이트-1-옥사이드의 고체 생성물 45.8g(92%수율)을 얻었다.To 1 liter of toluene for reagent, 4.6 g of 17.3% hydrated molecular sieves were added and refluxed under a Dean-stock trap for 1 hour until 100 ml of liquid was removed from the trap. Remove the Dean-Stock device from the distiller and remove 50 g of p-nitrobenzyl 6-phenoxyacetamido-2,2-dimethylphenam-3-carboxylate-1-oxide and 31.5 g of N-chlorophthalide. Added. The suspension was quickly reheated to reflux and continued at reflux for about 2 hours with stirring. The reaction mixture was cooled to about 0 ° C. and stirred for 10 minutes, and then the suspension was filtered to remove molecular sieve and phthalimide, and p-nitrobenzyl 3-methyl-2- (2-chlorosulfinyl-4-oxo-3 -A cooled filtrate containing phenoxyacetamido-azetidinyl) -3-butenoate was added to a solution of 30.0 g of contaminated molybdenum in 50 ml of chlorobenzene. The resulting red-red complex was stirred at -10 ° C. for 1 hour and at room temperature for 12 hours, and then the complex was filtered, washed with 100 ml of hexane, and dried. The complex is then slowly added to 300 ml of methyl alcohol at -10 [deg.] C. to produce a suspension of the product p-nitrobenzyl 7-phenoxyacetamido-3-exo methylene palm-4-carboxylate-1-oxide. The suspension was stirred at -10 [deg.] C. for 4 hours, filtered and the product was washed with 50 ml of methyl alcohol, 50 ml of dimethyl ether and dried to p-nitrobenzyl 7-phenoxyacetamido-3- having a melting point of 194.5-195 [deg.] C. 45.8 g (92% yield) of a solid product of exomethylenecepam-4-carboxylate-1-oxide were obtained.
[실시예 2]Example 2
실시예 1에서 프리델-크라프트 촉매로 오염화 몰리브데늄 대신 43.6g의 육염화 텅스텐으로 하고 반응을 시켰을 때 42.8g(86% 수율)의 상기 실시예 1의 목적화합물(구조식 (I) 화합물에서, R1이 p-니트로벤질기인 경우)을 얻었다.In Example 1, 42.8 g (86% yield) of the target compound of Example 1 (Formula (I) compound) when reacted with Friedel-Craft catalyst with 43.6 g of tungsten chloride instead of molybdenum contaminated R 1 is a p-nitrobenzyl group).
[실시예 3]Example 3
실시예 1에서 반응물로 p-니트로벤질 6-페녹시아세트아미도-2,2-디메틸펜암-3-카복실레이트-1-옥사이드 대신 52.0g의 2,2,2-트리클로로에틸 6-페녹시아세트아미도-2,2-디메틸펜암-3-카복실레이트-1-옥사이드로 하고 반응을 시켰을 때 48.7g(94% 수율)의 2,2,2-트리클로로에틸 7-페녹시아세트아미도-3-엑소메틸렌세팜-4-카복실레이트-1-옥사이드 고체를 얻었다. 결정상 고체인 이 물질의 융점은 143.5-144℃이다.52.0 g of 2,2,2-trichloroethyl 6-phenoxy instead of p-nitrobenzyl 6-phenoxyacetamido-2,2-dimethylphenam-3-carboxylate-1-oxide as a reaction in Example 1 48.7 g (94% yield) of 2,2,2-trichloroethyl 7-phenoxyacetamido- when reacted with cetamido-2,2-dimethylphenam-3-carboxylate-1-oxide 3-exomethylenecepam-4-carboxylate-1-oxide solid was obtained. The melting point of this material, which is a crystalline solid, is 143.5-144 ° C.
[실시예 4]Example 4
실시예 3에서 프리델-크라프트 촉매로 오염화 몰리브데늄 대신 43.6g의 육염화 텅스텐으로 하고 반응을 시켰을 때 43.0g(83% 수율)의 상기 실시예 3의 목적화합물(구조식(1) 화합물에서, R1이 2,2,2-트리클로로에틸인 경우)을 얻었다.In Example 3, when 43.6 g of tungsten chloride was used instead of molybdenum contaminated with Friedel-Crafts catalyst, 43.0 g (83% yield) of the target compound of Example 3 was used. When R 1 is 2,2,2-trichloroethyl).
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