📜光气,三氯乙醛置于苄基三丁基氯化铵体系中,化学反应 1.0H,以70%的收率获得产物(+/-)-1,2,2,2-四氯乙基氯甲酸酯 参考文献:Alkyl 1-Chloroalkyl Carbonates: Reagents For The Synthesis Of Carbamates And Protection Of Amino Groups 标题:Alkyl 1-Chloroalkyl Carbonates: Reagents For The Synthesis Of Carbamates And Protection Of Amino Groups 摘要:描述了1-氯代烷基碳酸酯的合成及其与各种类型胺的反应.这一反应对于合成氨基甲酸酯类农药和保护包括氨基酸在内的各种氨基团具有重要作用. DOI:10.1055/s-1986-31724
专利号:US-4592874-A 优先权日:1980-05-14 标 题:Process for the synthesis of alpha-chlorinated chloroformates 发明人:CAGNON GUY C; PITEAU MARC D; SENET JEAN-PIERRE G; OLOFSON ROY A; MARTZ JONATHAN T 权利人:POUDRES & EXPLOSIFS STE NALE 摘要:Process for the synthesis of alpha -chlorinated chloroformates, and new alpha -chlorinated chloroformates. The invention relates to a new process for the manufacture of alpha -chlorinated chloroformates and, to new alpha -chlorinated chloroformates as new industrial products. The process according to the invention consists of a synthesis, by catalytic phosgenation, of alpha -chlorinated chloroformates of the formula: in which: R represents a substituted or unsubstituted hydrocarbon radical and m represents an integer superior or equal to one, this synthesis consisting in reacting phosgene with the aldehyde R-CHO)m, in the presence of a catalyst which is an organic or inorganic substance which is capable in a medium containing an aldehyde of the formula R-CHO)m, phosgene and, possibly, a solvent, of generating a pair of ions one of which is an halogenide anion and the other is a cation which is sufficiently separated from said halogenide anion so as to give to the latter a nucleophilic power enabling it to react with the function(s) aldehyde of the molecule R-CHO)m.
专利号:US-4891430-A 优先权日:1984-12-04 标 题:Process for synthesizing active esters of carboxylic acids, new alpha-halogenated carbonates which are useful for this synthesis and the method of producing them 发明人:BARCELO GERARD; CASTRO BERTRAND; JAOUADI MAHMOUD; MARTINEZ JEAN; SENET JEAN-PIERRE; SENNYEY GERARD 权利人:INT DES POUDRES ET EXPLOSIFS S 摘要:The invention relates to a new process for preparing active esters or carboyxlic acids, which consists in reacting a carboxylic acid, in the presence of an agent for binding hydrohalic acid, with a carbonate of formula: ##STR1## in which R 1 denotes either a radical of formula ##STR2## in which R 3 and R 4 , which may be identical or different, are not hydrogen atoms and denote organic radicals which may be substituted or unsubstituted and saturated or unsaturated, and may or may not be bound to a polymer, and which can be joined together to form a hetero-cyclic system with the nitrogen, atom, n or a substituted or unsubstituted aryl radical which may or may not be bound to a polymer, n R 2 denotes a hydrogen atom, an aliphatic or cycloaliphatic radical which may be substituted or unsubstituted and saturated or unsaturated, or a substituted or unsubstituted aromatic radical, n and X denotes a halogen atom. n This process is especially useful for the synthesis of active esters of N-protected amino acids. The invention also relates to the new carbonates described above and the method of producing them, which consists in reacting an alpha-halogenated chloroformate of formula: n n R.sup.2 --CHX--O--COCl n n with an alcohol of formula R 1 OH in an inert solvent medium in the presence of an organic or inorganic base.
专利号:US-2005214310-A1 优先权日:2004-01-23 标 题 :Melphalan prodrugs 发明人:TOKI BRIAN E; SENTER PETER D 权利人:SEATTLE GENETICS INC 摘要:Shown and described are the synthesis of more potent forms of C-Mel, a prodrug used in Antibody-Directed Enzyme Prodrug Therapy, that releases the clinically used anticancer alkylating agent melphalan extracellularly. Shown and described are the synthesis of a variety of melphalan analogues with the intention to promote facile intracellular drug access. Esters, amides, and peptides of melphalan are shown. Cephalosporin prodrugs of the most interesting melphalan derivatives were synthesized and evaluated for potency, toxicity, therapeutic window, plasma stability, and solubility.
专利号:FR-2574075-A1 优先权日:1984-12-04 标 题 :PROCESS FOR THE SYNTHESIS OF ACTIVE ESTERS OF CARBOXYLIC ACIDS, NOVEL ALPHA-HALOGEN CARBONATES USEFUL FOR THIS SYNTHESIS AND THEIR METHOD OF OBTAINING
专利号:US-4960881-A 优先权日:1984-02-16 标 题 :α-chlorinated carbonates, their method of manufacture and application in the protection of the amine functions of amino acids 发明人:BARCELO GERARD; SENET JEAN-PIERRE; SENNYEY GERARD 权利人:POUDRES & EXPLOSIFS STE NALE 摘要:The invention relates to carbonates of formula: ##STR1## in which X is a fluorine, chlorine or bromine atom and R 1 is different from the ##STR2## group and represents: a substituted or non-substituted, saturated or unsaturated, aliphatic, araliphatic, primary, secondary, tertiary or cycloaliphatic radical. These α-chlorinated carbonates are prepared by the action of a compound of formula R 1 OH on a chloroformate of formula: ##STR3## in a solvent medium in the presence of an acid scavenger which is added after the two preceding compounds. They are used to block the amine function of amino acids. The α-chlorinated carbonate and amino acid are reacted in a solvent medium at a temperature of -5° to 100° C. in the presence of an acid scavenger. Blocked amines are very useful in peptide synthesis.
专利号:US-4592872-A 优先权日:1980-05-14 标题 :Process for the synthesis of α-chlorinated chloroformates