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    • 6. 发明授权
    • Methods for preparing cephalosporins
    • 头孢菌素的制备方法
    • US4035362A
    • 1977-07-12
    • US672527
    • 1976-03-31
    • Paolo MasiMaurizio FoglioGiovanni FranceschiAntonino SuaratoGianfranco CainelliFederico Arcamone
    • Paolo MasiMaurizio FoglioGiovanni FranceschiAntonino SuaratoGianfranco CainelliFederico Arcamone
    • C07D205/08C07D205/095C07D501/08C07D501/10C07D501/20
    • C07D501/08C07D205/095
    • A process for preparing cephalosporins of the structure: ##STR1## where R is any of hydrogen, C.sub.1 to C.sub.4 alkyl, t-butoxy, benzyloxy, cyano-methyl, thienyl-methyl, furyl-methyl, naphthyl-methyl, phenyl-methyl, phenoxy-methyl, phenoxy-isopropyl, pyridyl-4-thiomethyl and tetrazolyl-1-methyl;R.sub.1 is any of hydroxyl, C.sub.1 to C.sub.4 alkoxy, benzyloxy, p-methoxy- (or nitro-) benzyloxy, benzhydryloxy, triphenylmethoxy, phenacyloxy, p-halophenacyloxy and trichloroethoxy;Z is any of hydrogen, hydroxyl, --O--CO--C.sub.1 -C.sub.4 alkyl, --O--C.sub.1 -C.sub.4 alkyl, --Br, --I, --Cl, --N.sub.3, --NH.sub.2, --O--CO--CH.sub.3, --O--CO--NH.sub.2 and an -S-mononuclear nitrogen heterocyclic ring,By reacting compounds of the structure: ##STR2## IN WHICH R, R.sub.1, and Z are as above defined; R.sub.2 and R.sub.3 are the same or different and represent a C.sub.1 to C.sub.4 alkyl, a mononuclear aryl ring, --CN, a mononuclear heterocyclic ring or the radicals --COR.sub.4, COOR.sub.4, --PO(OR.sub.4).sub.2, --CO--NHR.sub.4 or R.sub.2 and R.sub.3 together may represent: ##STR3## where T represents >CH.sub.2, -N--R.sub.4 ; and R.sub.4 is lower alkyl, a mononuclear aryl ring or a mononuclear heterocyclic ring,Alone or as mixtures with each other in a suitable solvent at a temperature between -100 and +120.degree. C with a strong base to give compounds of formula I that are a mixture of .DELTA..sub.2 and .DELTA..sub.3 cephem-derivatives from which the .DELTA..sub.3 cephem derivatives can be obtained.
    • 一种制备结构式头孢菌素的方法:其中R是氢,C1-C4烷基,叔丁氧基,苄氧基,氰基 - 甲基,噻吩基 - 甲基,呋喃基 - 甲基,萘基 - 甲基,苯基 - 甲基 ,苯氧基甲基,苯氧基 - 异丙基,吡啶基-4-硫代甲基和四唑基-1-甲基; R1是羟基,C1〜C4烷氧基,苄氧基,对甲氧基 - (或硝基)苄氧基,二苯甲氧基,三苯基甲氧基,苯甲酰氧基,对卤代苯氧基和三氯乙氧基中的任一个。 Z是氢,羟基,-O-CO-C 1 -C 4烷基,-O-C 1 -C 4烷基,-Br,-I,-Cl,-N 3,-NH 2,-O-CO-CH 3,-O -CO-NH 2和-S-单核氮杂环,通过反应结构的化合物:其中R,R 1和Z如上所定义;其中R,R 1和Z如上所定义; R2和R3相同或不同,表示C1至C4烷基,单核芳基环,-CN,单核杂环或基团-COR4,COOR4,-PO(OR4)2,-CO-NHR4或R2和 R3一起可以表示:其中T表示> CH 2,-N-R 4; 并且R 4为低级烷基,单核芳基环或单核杂环,单独或混合于适宜溶剂中的温度为-100℃和+120℃之间的强碱,得到式I化合物 可以获得DELTA 2和DELTA 3头孢烯衍生物的混合物,其中可以获得DELTA 3头孢烯衍生物。
    • 9. 发明授权
    • Process for preparing carboxylated organic compounds
    • 制备羧基有机化合物的方法
    • US4435575A
    • 1984-03-06
    • US279090
    • 1981-06-30
    • Gianfranco CainelliMarco Foa'Achille U. RonchiAndrea Gardano
    • Gianfranco CainelliMarco Foa'Achille U. RonchiAndrea Gardano
    • C07C69/614B01J31/00B01J31/20C07B31/00C07B41/08C07B41/10C07B41/12C07B61/00C07C51/00C07C51/10C07C57/32C07C67/00C07C67/36C07C69/38C07D307/54
    • C07C51/10C07D307/54
    • A process is herein described for preparing carboxylated organic compounds (acids, esters, alkaline salts) of formula ##STR1## wherein R is a hydrocarbyl group having up to 11 carbon atoms (an aliphatic, alicyclic, aryl- or heteroarylalkyl group), also substituted, in its turn, by groups inert under the reaction conditions (alkyl, aryl, etheric, thioetheric, halogen, nitrile, ester, amide, ketonic groups), and R' is a hydrogen atom or an alkyl C.sub.1 -C.sub.8 group, by reaction of carbon monoxide with the corresponding hydrocarbyl halides, having the halogen bound to a non-tertiary carbon atom, in the presence of catalysts which are salts of cobalt hydrocarbonyl, or precursors thereof, in a hydro-alcoholic or alcoholic solvent and in the presence of bases.The process is characterized in that the catalytic system composed by the salt of cobalt hydrocarbonyl is supported on an anion exchange resin. The process permits to operate also continuously, in any case allowing an easy recovery, recycle and regeneration of the catalysts.The products obtained, i.e. carboxylic acids, esters and alkaline salts thereof, are utilized as intermediates for organic syntheses particularly for fine chemistry (phytopharmaceuticals, pharmaceuticals, etc.).
    • 本文描述了制备式(IMAGE)的羧化有机化合物(酸,酯,碱性盐)的方法,其中R是具有至多11个碳原子的烃基(脂族,脂环族,芳基或杂芳基烷基),也被取代 (烷基,芳基,醚基,硫醚,卤素,腈,酯,酰胺,酮基)为惰性的基团,R'为氢原子或C1-C8烷基,通过反应 的一氧化碳与相应的烃基卤化物,其卤素与非叔碳原子结合,在催化剂存在下,在氢醇或醇溶剂中存在钴烃基或其前体的催化剂存在下, 基地 该方法的特征在于将由烃基烃基组成的催化体系负载在阴离子交换树脂上。 该方法允许连续操作,在任何情况下允许催化剂的容易回收,再循环和再生。 获得的产物,即羧酸,其酯和碱金属盐被用作有机合成的中间体,特别用于精细化学(植物药物,药物等)。