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21. 发明授权

US4629542A Process for preparing 3-exomethylenecepham derivatives 失效
标题翻译： 3-甲磺酰头孢衍生物的制备方法
公开(公告)号：US4629542A
公开(公告)日：1986-12-16
申请号：US707767
申请日：1985-03-04
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
IPC分类号： C25B3/04 , A61K31/545 , C07D501/04 , C07D501/14 , C25B3/00
CPC分类号： C07D501/04 , A61K31/545 , C07D501/14 , C25B3/00 , Y02P20/55
摘要： This invention provides a process for preparing 3-exomethylenecepham derivatives represented by the formula ##STR1## wherein R.sup.1 is arylacetylamino, aryloxyacetylamino, heterocyclic acetylamino or imido, and R.sup.2 is a protective group for the carboxyl, the process being characterized in that a 3-halomethylcephem compound represented by the formula ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, and X is a halogen atom is electrolyzed in a mixture of a hydrophilic organic solvent and water.
摘要翻译：本发明提供了一种制备由下式表示的3-甲磺酰头孢烯衍生物的方法：其中R1是芳基乙酰基氨基，芳氧基乙酰氨基，杂环乙酰氨基或亚氨基，R2是羧基的保护基，该方法的特征在于3-卤代甲基头孢烯其中R1和R2如上所定义，X是卤素原子的式“IMAGE”表示的化合物在亲水性有机溶剂和水的混合物中电解。

22. 发明授权

US5929233A Cyclization for preparing halo-cephems 失效
标题翻译：用于制备晕圈的环化
公开(公告)号：US5929233A
公开(公告)日：1999-07-27
申请号：US732445
申请日：1996-11-06
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Isao Wada , Yasuhisa Amano
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Isao Wada , Yasuhisa Amano
IPC分类号： C07D205/09 , C07D205/095 , C07D501/00 , C07D501/08 , C07D513/04
CPC分类号： C07D513/04 , C07D205/09 , C07D205/095 , C07D501/00
摘要： The invention provides a process for preparing an allenyl .beta.-lactam of formula (4), by reacting the hydroxyl group of a .beta.-lactam of formula (1) with a reactive derivative of sulfonic acid of formula (2) to convert the compound of formula (1) to a .beta.-lactam of formula (3), thereafter reacting the resulting .beta.-lactam with a basic anion exchange resin of the type having a tertiary organic base fixed to the resin and isolating the allenyl .beta.-lactam of formula (4) with stability and high purity in a high yield.The invention also provides a process for preparing an allenyl .beta.-lactam of formula (4), by reacting the hydroxyl group of a .beta.-lactam compound of formula (1) with a reactive derivative of sulfonic acid of formula (2) to convert the compound of the formula (1) to a .beta.-lactam compound of formula (3), thereafter reacting the resulting .beta.-lactam of formula (3) with a tertiary organic base to convert the compound (3) to the allenyl .beta.-lactam of formula (4), thereafter causing two kinds of ion exchange resins, i.e., an acidic cation exchange resin and a basic anion exchange resin, to alternately or simultaneously act on the lactam of formula (4) and isolating the allenyl .beta.-lactam of formula (4).Further, the invention provides a process for preparing a 3-halogenated cephem of formula (6), characterized by causing a halogenating reagent to act on an allenyl .beta.-lactam of formula (4) in the presence of a sulfinate ion or thiolate ion capturing agent to obtain the 3-halogenated cephem.
摘要翻译： PCT No.PCT / JP96 / 00575 Sec。 371日期：1996年11月6日 102（e）日期1996年11月6日PCT 1996年3月8日PCT公布。公开号WO96 / 29334 日期1996年9月26日本发明提供通过使式（1）的β-内酰胺的羟基与式（2）的磺酸的反应性衍生物反应制备式（4）的烯丙基β-内酰胺的方法，将式（1）化合物转化成式（3）的β-内酰胺，然后将所得的β-内酰胺与具有叔有机碱类型的碱式阴离子交换树脂反应固定在树脂上并分离丙烯基β 式（4）的内酰胺，其产率稳定，纯度高。本发明还提供了通过使式（1）的β-内酰胺化合物的羟基与式（2）的磺酸的反应性衍生物反应来制备式（4）的烯丙基β-内酰胺的方法，以将式（1）的化合物与式（3）的β-内酰胺化合物反应，然后使得到的式（3）的β-内酰胺与叔有机碱反应，将化合物（3）转化为式（4），然后使两种离子交换树脂，即酸性阳离子交换树脂和碱性阴离子交换树脂交替或同时作用于式（4）的内酰胺，并分离式（4）。此外，本发明提供了制备式（6）的3-卤代头孢烯的方法，其特征在于，在亚磺酸根离子或硫醇盐离子捕获的存在下，使卤化试剂作用于式（4）的烯丙基β-内酰胺代理获得3卤代头孢烯。

23. 发明授权

US4609438A Process for preparing thiosulfonate derivatives 失效
标题翻译：硫代磺酸衍生物的制备方法
公开(公告)号：US4609438A
公开(公告)日：1986-09-02
申请号：US673309
申请日：1984-11-20
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Seiryu Uto , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Seiryu Uto , Yutaka Kameyama
IPC分类号： C25B3/10 , C07D277/78 , C25B3/00
CPC分类号： C07D277/78 , C25B3/00
摘要： This invention provides a process for preparing a thiosulfonate derivative represented by the formulaR.sup.2 SO.sub.2 SR.sup.1 (III)wherein R.sup.1 is substituted or unsubstituted 2-benzothiazolyl, and R.sup.2 is substituted or unsubstituted phenyl, the process being characterized in that a compound represented by the formulaR.sup.1 SX (I)wherein R.sup.1 is as defined above, and X is hydrogen, alkali metal or SR.sup.1, and a sulfinic acid or a salt thereof represented by the formulaR.sup.2 SO.sub.2 Y (II)wherein R.sup.2 is as defined above, and Y is a hydrogen atom, alkali metal atom, alkaline earth metal atom or quaternary ammonium are subjected to an electrolytic reaction in a mixture of water and an organic solvent in the presence of a halogen salt.
摘要翻译：本发明提供一种制备由式R 2 SO 2 S R 1（III）表示的硫代磺酸酯衍生物的方法，其中R 1为取代或未取代的2-苯并噻唑基，R 2为取代或未取代的苯基，该方法的特征在于式R1SX I）其中R1如上所定义，X是氢，碱金属或SR1，以及由式R2SO2Y（Ⅱ）表示的亚磺酸或其盐，其中R2如上定义，Y是氢原子，碱金属原子，碱土金属原子或季铵在卤素盐存在下，在水和有机溶剂的混合物中进行电解反应。

24. 发明授权

US06197185B1 Process for preparing beta lactam compound 失效
标题翻译：制备β-内酰胺化合物的方法
公开(公告)号：US06197185B1
公开(公告)日：2001-03-06
申请号：US09457719
申请日：1999-12-10
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
IPC分类号： C25B300
CPC分类号： C07D205/09 , C07D499/00 , Y02P20/55
摘要： The present invention provides a process for preparing an exo-methylenepenam compound represented by the general formula (5) characterized in that a &bgr;-lactam halide compound represented by the general formula (2) is subjected to an electroreduction process to obtain the exo-methylenepenam compound.
摘要翻译：本发明提供一种制备由通式（5）表示的外亚甲基台哌麦德化合物的方法，其特征在于将通式（2）表示的β-内酰胺卤化物进行电解还原处理，得到外亚甲基台am 复合。

25. 发明授权

US6150519A Process for preparing .beta.-lactam derivatives 失效
标题翻译：烯丙基β-内酰胺化合物的制备方法
公开(公告)号：US6150519A
公开(公告)日：2000-11-21
申请号：US266584
申请日：1999-03-11
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Isao Wada , Yasuhisa Amano
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Isao Wada , Yasuhisa Amano
IPC分类号： C07D205/09 , C07D205/095 , C07D501/00 , C07D501/08 , C07D513/04
CPC分类号： C07D513/04 , C07D205/09 , C07D205/095 , C07D501/00
摘要： A process for preparing an allenyl .beta.-lactam compound represented by the formula (4), characterized by reacting the hydroxyl group of a .beta.-lactam compound represented by the formula (1) with a reactive functional group derivative of sulfonic acid represented by the formula (2) to convert the compound of the formula (1) to a .beta.-lactam compound represented by the formula (3), thereafter reacting the resulting .beta.-lactam compound with a basic anion exchange resin of the type having a tertiary organic base fixed to the resin and isolating the resulting allenyl .beta.-lactam compound of the formula (4) from the reaction mixture ##STR1##
摘要翻译：一种制备由式（4）表示的全烯丙基β-内酰胺化合物的方法，其特征在于使由式（1）表示的β-内酰胺化合物的羟基与由式（1）表示的磺酸的反应性官能团衍生物反应，（2）将式（1）的化合物转化为式（3）表示的β-内酰胺化合物，然后使得到的β-内酰胺化合物与具有叔有机碱固定的碱式阴离子交换树脂反应并从所述反应混合物中分离得到的所述式（4）的所有烯丙基β-内酰胺化合物

26. 发明授权

US6043356A Process for preparing .beta.-lactam compound 失效
标题翻译： β-内酰胺化合物的制备方法
公开(公告)号：US6043356A
公开(公告)日：2000-03-28
申请号：US233426
申请日：1999-01-20
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
IPC分类号： C07D205/09 , C07D499/00 , C07D499/06 , C25B3/04
CPC分类号： C07D499/00 , C07D205/09
摘要： The present invention provides a process for preparing an exo-methylenepenam compound represented by the general formula (5) characterized in that a .beta.-lactam halide compound represented by the general formula (2) is reduced with a metal having a standard oxidation-reduction potential of up to -0.3 (V/SCE) in an amount of at least one mole per mole of the halide compound and with a metal compound having a higher standard oxidation-reduction potential than the metal in an amount of 0.0001 to 10 moles per mole of the halide compound, or is subjected to an electroreduction process to obtain the exo-methylenepenam compound. ##STR1##
摘要翻译：本发明提供一种制备由通式（5）表示的外亚甲基间苯二酚化合物的方法，其特征在于用具有标准氧化还原电位的金属还原由通式（2）表示的β-内酰胺化合物（V / SCE），其量为每摩尔卤化物至少1摩尔，并且具有比金属更高的标准氧化还原电位的金属化合物，其量为0.0001至10摩尔/摩尔的卤化物化合物，或进行电还原处理，得到外亚甲基台am嗪化合物。

27. 发明授权

US6011151A Process for preparing .beta.-lactam halide compound 失效
标题翻译：制备β-内酰胺卤化物的方法
公开(公告)号：US6011151A
公开(公告)日：2000-01-04
申请号：US732444
申请日：1996-11-06
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Daisuke Suzuki
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama , Daisuke Suzuki
IPC分类号： C07D205/08 , C07D205/085 , C07D205/09 , C07D205/095
CPC分类号： C07D205/08 , C07D205/085 , C07D205/09 , C07D205/095 , Y02P20/55
摘要： A process for preparing a .beta.-lactam halide compound represented by the formula (2) characterized by halogenating the allenyl group of an allenyl .beta.-lactam compound represented by the formula (1) with a cupric halide and a metal halide to obtain the .beta.-lactam halide compound ##STR1## wherein R.sup.1 is a hydrogen atom or amino or protected amino, R.sup.2 is a hydrogen atom, halogen atom, lower alkoxyl, lower acyl, or lower alkyl having a hydroxyl group or protected hydroxyl group as a substituent, R.sup.3 is a hydrogen atom or carboxylic acid protecting group, and R.sup.4 is a hydrocarbon group which may have a substituent, or the group --S--S(O)n-Ar, n being 0 to 2, Ar being aryl which may have a substituent ##STR2## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same as defined above, X and Y are each halogen atom.
摘要翻译： PCT No.PCT / JP96 / 00489 Sec。 371日期：1996年11月6日 102（e）日期1996年11月6日PCT 1996年3月1日PCT公布。 WO96 / 28421 PCT出版物日本1996年9月19日制备式（2）表示的β-内酰胺化合物化合物的制备方法，其特征在于用卤化铜和金属卤化物卤化由式（1）表示的烯丙基β-内酰胺化合物的全烯基得到其中R1为氢原子或氨基或被保护的氨基，R2为氢原子，卤素原子，低级烷氧基，低级酰基或具有羟基或被保护的羟基作为取代基的低级烷基的β-内酰胺化合物， R3为氢原子或羧酸保护基，R4为可具有取代基的烃基，或-SS（O）n-Ar，n为0〜2，Ar为可具有取代基的芳基， R1，R2，R3和R4与上述定义相同，X和Y各自为卤素原子。

28. 发明授权

US5986091A Process for preparation of .beta.-lactam compounds 失效
标题翻译： β-内酰胺化合物的制备方法
公开(公告)号：US5986091A
公开(公告)日：1999-11-16
申请号：US952526
申请日：1997-11-12
申请人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Michio Sasaoka , Yutaka Kameyama
IPC分类号： C07D205/09 , C07D205/095 , C07D501/00 , C07D501/08 , C07D501/16 , C07D501/59
CPC分类号： C07D501/00 , C07D205/095 , Y02P20/55
摘要： The present invention provides a process for preparing an allenyl .beta.-lactam compound represented by the formula (II) or a process for preparing a 3-halocephem compound of the formula (III) by altering the reaction conditions with use of a .beta.-lactam halide compound represented by the formula (I) serving as the starting material ##STR1## wherein R.sub.1 is a hydrogen atom, amino or protected amino, R.sub.2 is aryl which may have a substituent, n is 0 to 2, R.sub.3 is a hydrogen atom or carboxylic acid protective group, X is a halogen atom, and Y is a halogen atom or a leaving group ##STR2## wherein R.sub.1, R.sub.2, n and R.sub.3 are as defined above ##STR3## wherein R.sub.1, R.sub.3 and X are as defined above.
摘要翻译： PCT No.PCT / JP97 / 00709 Sec。 371日期：1997年11月12日 102（e）日期1997年11月12日PCT 1996年3月7日PCT公布。 WO97 / 33891 PCT出版物日期：1997年9月18日本发明提供了制备由式（II）表示的烯丙基β-内酰胺化合物或通过使用下式（III）通过改变反应条件来制备式（III）的3-卤代头孢烯化合物的方法：作为起始原料的式（I）表示的β-内酰胺卤化物，其中R1是氢原子，氨基或被保护的氨基，R2是可以具有取代基的芳基，n是0-2，R3是氢原子或羧酸保护基，X是卤素原子，Y是卤素原子或离去基团，其中R 1，R 2，n和R 3如上所定义，其中R 1，R 3和X如上所定义。

29. 发明授权

US5204458A Process for preparing cephem derivatives 失效
标题翻译：制备CEPHEM衍生物的方法
公开(公告)号：US5204458A
公开(公告)日：1993-04-20
申请号：US849160
申请日：1992-03-10
申请人： Sigeru Torii , Hideo Tanaka , Masatoshi Taniguchi , Michio Sasaoka , Takashi Shiroi , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Masatoshi Taniguchi , Michio Sasaoka , Takashi Shiroi , Yutaka Kameyama
IPC分类号： C07D501/00 , C07D501/08 , C07D501/59
CPC分类号： C07D501/00 , Y02P20/55
摘要： The present invention provides a process for preparing a cephem derivative characterized in that an allenyl .beta.-lactam compound represented by the formula (1) ##STR1## wherein R.sup.1 is amino or protected amino, R.sup.2 is a hydrogen atom or lower alkoxyl, R.sup.3 is a hydrogen atom or carboxylic acid protecting group and X is the group --SO.sub.2 R.sup.4 or --SR.sup.4, R.sup.4 being substituted or unsubstituted aryl or substituted or unsubstituted nitrogen-containing aromatic heterocyclic group is reacted with a nucleophilic agent to obtain the derivative, the cephem derivative being represented by the formula (2) ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 are as defined above, and Y is the residue of the nucleophilic agent.

30. 发明授权

US5196530A Process for preparing 2-exo-methylenepenam derivatives 失效
标题翻译：制备2-异 - 甲基衍生物的方法
公开(公告)号：US5196530A
公开(公告)日：1993-03-23
申请号：US848939
申请日：1992-03-10
申请人： Sigeru Torii , Hideo Tanaka , Masatoshi Taniguchi , Michio Sasaoka , Takashi Shiroi , Yutaka Kameyama
发明人： Sigeru Torii , Hideo Tanaka , Masatoshi Taniguchi , Michio Sasaoka , Takashi Shiroi , Yutaka Kameyama
IPC分类号： C07D499/00 , C07D499/86 , C07D499/87
CPC分类号： C07D499/00
摘要： The present invention provides a process for preparing a 2-exo-methylenepenam derivative represented by the formula (2), the process being characterized by reacting an allenyl .beta.-lactum compound represented by the formula (1) with a metallic reducing agent, in which R.sup.1, R.sup.2, R.sup.3 and X are defined in the specification. ##STR1##

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