公开(公告)号：US4159272A

公开(公告)日：1979-06-26

申请号：US829689

申请日：1977-09-01

申请人： Ta-Sen Chou

发明人： Ta-Sen Chou

IPC分类号： C07D205/08 ,  C07D205/09 ,  C07D501/10 ,  C07D333/24 ,  C07D333/38

CPC分类号： C07D205/08

摘要： Penicillin sulfoxide esters having the sulfoxide group in the .alpha.-configuration are reacted with an N-chloro halogenating agent at a temperature between about 70.degree. C. and about 120.degree. C. in the presence of an alkylene oxide and preferably also calcium oxide to produce 2-chlorosulfinyl-azetidin-4-one intermediates. The chlorosulfinyl intermediates are then treated with a Friedel-Crafts catalyst, for example, stannic chloride to provide a 3-exomethylenecepham .beta.-sulfoxide. The latter compounds are useful in the preparation of 3-alkoxy and 3-halo substituted cephalosporin antibiotic compounds.

摘要翻译： 在α-构型中具有亚砜基团的青霉素亚砜酯在N-环氧化物存在下，在约70℃至约120℃的温度下与N-氯卤化剂反应，优选还包括氧化钙，以产生 2-氯亚磺酰基 - 氮杂环丁烷-4-酮中间体。 然后用Friedel-Crafts催化剂（例如氯化锡）处理氯亚磺酰基中间体，得到3-异亚甲基脑嘧啶β-亚砜。 后一种化合物可用于制备3-烷氧基和3-卤素取代的头孢菌素类抗生素化合物。

公开(公告)号：US4093800A

公开(公告)日：1978-06-06

申请号：US768138

申请日：1977-02-14

申请人： Stjepan Kukolja

发明人： Stjepan Kukolja

IPC分类号： C07D277/70 ,  C07D205/08 ,  C07D205/095 ,  C07D417/14 ,  C07D499/00 ,  C07D501/08 ,  C07D501/10 ,  C07D501/16 ,  C07D501/22 ,  C07D501/59 ,  C07D501/02

CPC分类号： C07D499/00

摘要： A novel 4-(2'-benzothiazolyldithio)-3-imidoazetidin-2-one of the formula ##STR1## in which X is chloro or bromo and R.sub.2 is methylene or oxygen is ring-closed to the corresponding 3-exomethylenecepham or 3-"oxo" cepham by treatment with sodium or potassium iodide at a temperature of from about 40.degree. C. to about 80.degree. C.

摘要翻译： 其中X是氯或溴并且R 2是亚甲基或氧的式（IMA）中的新的4-（2'-苯并噻唑二硫代）-3-亚氨基氮杂环丁烷-2-酮与相应的3-异亚甲基脑炎或3- 通过在约40℃至约80℃的温度下用碘化钠或碘化钾处理“氧代”

公开(公告)号：US4066641A

公开(公告)日：1978-01-03

申请号：US707288

申请日：1976-07-21

申请人： Yoshio Hamashima ,  Mitsuru Yoshioka ,  Hiroshi Tanida ,  Teruji Tsuji ,  Masayuki Narisada ,  Taichiro Komeno ,  Wataru Nagata

发明人： Yoshio Hamashima ,  Mitsuru Yoshioka ,  Hiroshi Tanida ,  Teruji Tsuji ,  Masayuki Narisada ,  Taichiro Komeno ,  Wataru Nagata

IPC分类号： C07D205/095 ,  C07D501/08 ,  C07D501/10 ,  C07D501/59 ,  C07D501/60 ,  C07D501/02

CPC分类号： C07D501/10 ,  C07D205/095

摘要： A compound represented by ##STR1## is treated with a base to give an antibacterial cephem compound represented by ##STR2## (wherein A is amino or substituted amino;Cob is carboxy or protected carboxy;Rs is substituted thio;Y is an electron-attracting group selected from acyloxy, halogen, cyano, nitro, and nitroso; andThe dotted line shows .DELTA..sup.2 or .DELTA..sup.3).

公开(公告)号：US4056521A

公开(公告)日：1977-11-01

申请号：US648492

申请日：1976-12-01

申请人： Takashi Kamiya ,  Tsutomu Teraji ,  Masashi Hashimoto ,  Osamu Nakaguti ,  Teruo Oku

发明人： Takashi Kamiya ,  Tsutomu Teraji ,  Masashi Hashimoto ,  Osamu Nakaguti ,  Teruo Oku

IPC分类号： C07D205/095 ,  C07D499/00 ,  C07D499/06 ,  C07D499/21 ,  C07D499/44 ,  C07D501/08 ,  C07D501/10

CPC分类号： C07D205/095 ,  C07D499/00

摘要： Disclosed are antibacterial penicillins of the formula ##STR1## wherein Y" is a residue of a strong nucleophile and processes for preparing same.

公开(公告)号：US4003894A

公开(公告)日：1977-01-18

申请号：US574365

申请日：1975-05-05

申请人： Jan Verweij ,  Hong Sheng Tan ,  Hermanus Jacobus Kooreman

发明人： Jan Verweij ,  Hong Sheng Tan ,  Hermanus Jacobus Kooreman

IPC分类号： C07D501/10

CPC分类号： C07D501/10

摘要： Process for the preparation of 7-substituted amino-desacetoxycephalosporanic derivatives comprising converting a 6-substituted amino-penicillanic acid sulfoxide into an anhydride of a 6-substituted amino-penicillanic acid sulfoxide, heating the said acid anhydride intermediate at a temperature up to at most 160.degree. C in a dry inert organic solvent with an anhydrous acid which is capable of causing ring expansion of the penam ring to a .DELTA..sup.3 -cephem ring, in the presence of a silicon-containing compound capable of (a) removing water formed during the ring enlargement of the penam structure fast enough to prevent water hydrolysis of the acid anhydride moiety present and (b) forming neutral or basic products on hydrolysis, the aforesaid acid being strong enough not to be, or not to a substantial extent to be, silylated under the reaction conditions employed, and hydrolyzing the resulting compound in situ to form the .DELTA..sup.3 -7-substituted amino-desacetoxycephalosporanic acid as such or as a salt, such as alkali metal, alkaline earth metal or amine salt and to the novel sulfoxide acid anhydrides formed therein.

摘要翻译： 用于制备7-取代的氨基 - 脱乙酰氧基头孢烷衍生物的方法，包括将6-取代的氨基 - 青霉烷酸亚砜转化为6-取代的氨基 - 青霉烷酸亚砜的酸酐，将所述酸酐中间体加热至多至多 160℃在干燥惰性有机溶剂中与无水酸反应，该无水酸能够在含硅化合物的存在下使Penam环环化为DELTA 3-头孢烯环，所述含硅化合物能够（a）除去在 阳离子结构的环扩大足够快以防止存在的酸酐部分的水解，和（b）在水解时形成中性或碱性产物，上述酸足够强，不大或不在很大程度上是 在所用的反应条件下甲硅烷基化，并原位水解所得化合物，形成DELTA 3-7-取代的氨基 - 脱乙酰氧基头孢烷酸，或者如 盐，如碱金属，碱土金属或胺盐，以及其中形成的新的亚砜酸酐。

公开(公告)号：US3966720A

公开(公告)日：1976-06-29

申请号：US423187

申请日：1973-12-10

申请人： Tatsuo Tomioka ,  Yasuo Hoshide ,  Hirosi Ogawa ,  Kenichi Suzuki

发明人： Tatsuo Tomioka ,  Yasuo Hoshide ,  Hirosi Ogawa ,  Kenichi Suzuki

IPC分类号： C07C381/00 ,  C07C381/12 ,  C07D213/89 ,  C07D215/60 ,  C07D333/46 ,  C07D501/10 ,  C07D501/57

CPC分类号： C07D213/89 ,  C07C381/00 ,  C07C381/12 ,  C07D215/60 ,  C07D333/46

摘要： A process for producing a desacetoxy cephalosporanic acid represented by formula (III), ##SPC1##wherein R.sub.1 is acyl, and R.sub.2 is alkyl, aryl or arylalkyl, which comprises: heating a penicillin sulfoxide of the formula (I), ##SPC2##wherein R.sub.1 and R.sub.2 are the same as hereinbefore defined at 50.degree. to 160.degree.C in an inert organic solvent in the presence of a sulfonate represented by formula (II), ##EQU1## wherein A is R.sub.5 --N--R.sub.6, R.sub.5 --N--O--R.sub.6, S--R.sub.6, R.sub.5 --S.fwdarw.O, and R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are lower alkyl, phenyl, benzyl or phenethyl, R.sub.7 is 1-12C alkyl, phenyl, 1-12C alkyl-substituted-phenyl, naphthyl, 1-12C alkyl-substituted naphthyl, halogen-substituted phenyl and wherein when A is R.sub.5 --N--R.sub.6 or R.sub.5 --N--O--R.sub.6, R.sub.3, R.sub.4 and R.sub.5 may form a heterocyclic ring together with the nitrogen atom, and when A is S--R.sub.6, R.sub.3 and R.sub.4 may form a heterocyclic 4-5C polymethylene ring or R.sub.6 and R.sub.7 may bond to form a polymethylene link.

摘要翻译： 一种制备由式（III）表示的脱乙酰氧基头孢菌酸的方法，其中R1是酰基，R2是烷基，芳基或芳烷基，其包括：加热式（I）的青霉素亚砜，其中R1和R2相同 在式（II）表示的磺酸盐存在下，在惰性有机溶剂中，在50-160℃下定义R 3 ANGLE A + - - - SO 3 - （II）R 4，其中A是 R5-N-R6，R5-NO-R6，S-R6，R5-S-> O，R3，R4，R5和R6是低级烷基，苯基，苄基或苯乙基，R7是1-12C烷基， 1-12C烷基取代的苯基，萘基，1-12C烷基取代的萘基，卤素取代的苯基，其中当A是R5-N-R6或R5-NO-R6时，R3，R4和R5可以形成杂环 与氮原子一起，当A为S-R6时，R3和R4可以形成杂环的4-5C多亚甲基环，或者R6和R7可以键合形成多亚甲基连接。

公开(公告)号：US3962277A

公开(公告)日：1976-06-08

申请号：US619843

申请日：1975-10-06

申请人： Jan Verwey ,  Hong Sheng Tan

发明人： Jan Verwey ,  Hong Sheng Tan

IPC分类号： C07D209/34 ,  C07D501/10

CPC分类号： C07D501/10

摘要： A new azetidine derivative of the formula: ##EQU1## wherein R.sub.1 represents a penicillin- or cephalosporin-amido group, R.sub.2 represents one of the groups of the following formulae: ##EQU2## wherein R.sub.4, R.sub.5 and R.sub.6 are the same or different and each represents a hydrogen atom or a lower alkyl or alkenyl group, n represents 2 or 3 and - in case formula IIB represents a phenyl group - this group may carry one to four further substituents selected from the group consisting of halogen atoms and lower alkyl, lower alkenyl and phenyl groups,R.sub.3 represents an amino group of the formula ##EQU3## wherein R.sub.7 represents a hydrogen atom or a lower alkyl group and R.sub.8 represents a lower alkyl group, orR.sub.3 represents a N,N'-disubstituted hydrazino group wherein the substituents are lower alkyl groups, e.g. the N,N'-diisopropylhydrazino group, orR.sub.3 represents the group --OR.sub.9, wherein R.sub.9 represents a hydrogen atom, a lower alkyl group, which group may be substituted by 1 to 3 halogen atoms or by 1 or 2 phenyl groups, werein the phenyl groups may be substituted by a methoxy or a nitro group, or R.sub.9 represents a phenacyl group or a salt-forming cation,And corresponding azetidine derivatives of formula I wherein the double bond in the propenyl side chain has been shifted from the 2- to the 1-position, which are versatile intermediates in the process of preparing cephalosporanic and penicillanic derivative.

公开(公告)号：US3852295A

公开(公告)日：1974-12-03

申请号：US32321373

申请日：1973-01-12

申请人： GLAXO LAB LTD

发明人： GRAHAM W ,  WETHERILL L

IPC分类号： C07D501/10 ,  C07F9/12 ,  C07D31/28

CPC分类号： C07F9/12

摘要： The invention relates to a process for the preparation of 7 Beta -acylamido-3-methylceph-3-em-4-carboxylic acid esters from compounds of the penicillin type, in particular, 6 Beta acylamido penicillanic acid 1-oxide esters, in the presence of a catalyst selected fron a mono-O-substituted orthophosphoric acid, an O,O-di(aryl substituted) orthophosphoric acid, a salt or complex formed from a nitrogen base having a pKb of not less than 4 and a mono-O-substituted orthophosphoric acid or an O,O-di(aryl substituted) orthophosphoric acid. The salt or complex may be formed in situ in the reaction mixture.

摘要翻译： 本发明涉及一种从青霉素型特别是6β-酰氨基青霉烷酸1-氧化物酯类化合物制备7β-酰氨基-3-甲基头孢-3-烯-4-羧酸酯的方法， 存在选自单O取代正磷酸，O，O-二（芳基取代）正磷酸，由pKb不小于4的氮碱形成的盐或络合物的催化剂， O-取代正磷酸或O，O-二（芳基取代）正磷酸。 盐或络合物可以在反应混合物中原位形成。

公开(公告)号：US3843639A

公开(公告)日：1974-10-22

申请号：US33077073

申请日：1973-02-08

申请人： BRISTOL MYERS CO

发明人： SAPINO C ,  RUGGERI M

IPC分类号： C07D499/32 ,  C07D499/00 ,  C07D499/08 ,  C07D499/60 ,  C07D501/10 ,  C07D501/22 ,  C07D99/24

CPC分类号： C07D499/00

摘要： Cephalexin was produced by hydrolysis of its methoxymethyl ester which in turn was produced by reaction of 2-phenylglycine chloride hydrochloride with an imino ether of methoxymethyl 7phenoxyacetamido-3-methyl-ceph-3-em-4-carboxylate which had been prepared by reaction of an alcohol with the corresponding iminochloride made by treatment with PCl5 of methoxy-methyl 7phenoxyacetamido-3-methylceph-3-em-4-carboxylate. The last was made by thermal rearrangement of the methoxymethyl ester of phenoxymethylpenicillin sulfoxide.

公开(公告)号：US3681380A

公开(公告)日：1972-08-01

申请号：US3681380D

申请日：1971-02-03

申请人： LILLY CO ELI

发明人： COOPER ROBIN D G ,  FUKUDA DAVID S

IPC分类号： C07D513/06 ,  C07D501/10 ,  C07D513/04 ,  C07D99/10

CPC分类号： C07D513/04

摘要： Novel 2-substituted thiazoline azetidinones are obtained from 2,6-disubstituted thiazoline azetidinones by treatment with lead tetraacetate followed by hydrolysis. The novel 2-substituted thiazoline azetidinones are reduced by treatment with aluminum amalgam or sodium borohydride to the corresponding thiazolidine azetidinones which are useful in the synthesis of penicillins and cephalosporins.

摘要翻译： 通过用四乙酸铅处理然后水解，由2,6-二取代噻唑啉氮杂环丁酮获得新的2-取代噻唑啉氮杂环丁酮。 通过用铝汞齐或硼氢化钠处理到可用于合成青霉素和头孢菌素的相应的噻唑烷氮杂环丁酮来还原新的2-取代噻唑啉氮杂环丁酮。