专利号:US-6025492-A 优先权日:1996-08-30 标 题 :Synthesis of a hydrazone β-keto ester by the reaction with a diazo ester 发明人:SHAH AJIT S; CLARK JERRY D; MA YINONG; PETERSON JAMES C; PATELIS LEFTERIS 权利人:MONSANTO CO 摘要:The present invention relates to the synthesis of a hydrazone β-keto ester by the reaction of an alkyl diazoester with a hydrazone aldehyde in the presence of a Lewis acid In a preferred embodiment, the hydrazone β-keto ester is then converted into a pyridazinone compound by the reaction with an alkyl acid chloride in the presence of a base, followed by acidification. A process for the production of a hydrazone aldehyde, which comprises contacting a hydrazine and glyoxal, is also described.
专利号:EP-0923540-B1 优先权日:1996-08-30 标题 :Synthesis of a hydrazone beta-keto ester by the reaction with a diazo ester 发明人:SHAH AJIT S; CLARK JERRY D; MA YINONG; PETERSON JAMES C; PATELIS LEFTERIS 权利人:MONSANTO TECHNOLOGY LLC 摘要:The present invention relates to the synthesis of a hydrazone β-keto ester by the reaction of an alkyl diazo ester with a hydrazone aldehyde in the presence of a Lewis acid. In a preferred embodiment, the hydrazone β-keto ester is then converted into a pyridazinone compound by the reaction with an alkyl acid chloride in the presence of a base, followed by acidification. The present invention also relates to a continuous process for the production of a hydrazone aldehyde comprising contacting a hydrazine and glyoxal, wherein the hydrazine and the glyoxal are added simultaneously to a reactor at a controlled rate.
专利号:US-3950389-A 优先权日:1968-10-04 标 题 :Stereospecific total steroidal synthesis via substituted C/D-trans indanones 发明人:HAJOS ZOLTAN GEORGE 权利人:HOFFMANN LA ROCHE 摘要:Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula ##SPC1## n Wherein m is an integer having a value of 1 or 2; R 4 is hydrogen or lower alkyl; Z is lower alkylenedioxymethylene CH(OR 2 ) and carbonyl; R 8 when taken alone is hydrogen; R 9 when taken alone is lower alkoxycarbonyl, aryloxy-carbonyl, lower cycloalkyloxycarbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is carbonyl R 8 when taken alone is hydrogen; R 9 when taken alone is carbonyl halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R 2 is hydrogen, lower alkyl, lower alkoxy-lower alkyl, phenyl-lower alkyl, tetrahydropyranyl, lower alkanoyl, benzoyl, nitrobenzoyl, carboxy-lower alkanoyl, carboxybenzoyl, trifluoroacetyl and camphorsulfonyl n And reacting them in the case where R 8 and R 9 taken together are methylene or R 8 is hydrogen and R 9 is methylene-X with β-keto esters and other analogs of the formula ##EQU1## wherein R.sub. 6 is selected from the group CONSISTING OF ##EQU2## and LOWER ALKYL; R 7 is lower alkyl; R 15 is selected from the group consisting of oxo, lower alkylene-dioxy or (hydrogen and lower alkoxy); B is selected from the group consisting of lower alkoxy-carbonyl-methylene, lower-aryloxy-carbonyl-methylene, cyanomethylene, lower alkyl sulfinyl-methylene, lower alkyl sulfonyl-methylene, and R 25 and R 26 are independently selected from the group consisting of hydrogen, hydroxyl and lower alkyl.
专利号:US-4077983-A 优先权日:1974-06-24 标 题:Stereospecific total steroidal synthesis via substituted C/D-trans indanones 发明人:HAJOS ZOLTAN GEORGE 权利人:HOFFMANN LA ROCHE 摘要:Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula ##STR1## wherein m is an integer having a value of 1 or 2; R 4 is hydrogen or lower alkyl; Z is lower alkylenedioxy, CH(OR 2 ) and carbonyl; R 8 when taken alone is hydrogen; R 9 when taken alone is lower alkoxycarbonyl, aryloxy-carbonyl, lower cycloalkyloxycarbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is carbonyl R 8 when taken alone is hydrogen; R 9 when taken alone is carbonyl halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R 2 is hydrogen, lower alkyl, lower alkoxy-lower alkyl, phenyl-lower alkyl, tetrahydropyranyl, lower alkanoyl, benzoyl, nitrobenzoyl, carboxy-lower alkanoyl, carboxybenzoyl, trifluoroacetyl and camphorsulfonyl n And reacting then in the case where R 8 and R 9 taken together are methylene or R 8 is hydrogen and R 9 is methylene-X with β-keto esters and other analogs of the formula ##STR2## wherein R 6 is selected from the group consisting of ##STR3## lower alkyl; R 7 is lower alkyl; R 15 is selected from the group consisting of oxo, lower alkylenedioxy or (hydrogen and lower alkoxy); B is selected from the group consisting of lower alkoxy-carbonylmethylene, lower-aryloxy-carbonyl-methylene, cyanomethylene, lower alkyl sulfinyl-methylene, lower alkyl sulfonyl-methylene, and R 25 and R 26 are independently selected from the group consisting of hydrogen, hydroxyl and lower alkyl.
专利号:US-4053486-A 优先权日:1974-06-24 标 题:Stereospecific total steroidal synthesis via substituted c/d-trans indanones 发明人:HAJOS ZOLTAN GEORGE 权利人:HOFFMANN LA ROCHE 摘要:Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula ##STR1## WHEREIN M IS AN INTEGER HAVING A VALUE OF 1 OR 2; R 4 is hydrogen or lower alkyl; Z is lower alkylenedioxy, CH(OR 2 ) and carbonyl; R 8 when taken alone is hydrogen; R 9 when taken alone is lower alkoxy-carbonyl, aryloxy-carbonyl, lower cycloalkyloxy-carbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is a carbonyl R 8 when taken alone is hydrogen; R 9 when taken alone is carbonyl-halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R 2 is hydrogen, lower alkyl, lower alkoxy-lower alkyl, phenyl-lower alkyl, tetrahydropyranyl, lower alkanoyl, benzoyl, nitrobenzoyl, carboxy-lower alkanoyl, carboxybenzoyl, trifluoroacetyl and camphorsulfonyl n And reacting them in the case where R 8 and R 9 taken together are methylene or R 8 is hydrogen and R 9 is methylene-X with β-keto esters and other analogs of the formula ##STR2## wherein R 6 is selected from the group consisting ##STR3## and lower alkyl; R 7 is lower alkyl; R 15 is selected from the group consisting of oxo, lower alkylenedioxy or (hydrogen and lower alkoxy); B is selected from the group consisting of lower alkoxy-carbonyl-methylene, lower-aryloxy-carbonyl-methylene, cyanomethylene, lower alkyl sulfinyl-methylene, lower alkyl sulfonyl-methylene, and R 25 and R 26 are independently selected from the group consisting of hydrogen, hydroxyl and lower alkyl.
专利号:US-3984473-A 优先权日:1968-10-04 标题 :Stereospecific total steroidal synthesis via substituted C/D-trans indanones 发明人:HAJOS ZOLTAN GEORGE 权利人:HOFFMANN LA ROCHE 摘要:Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula ##SPC1## n Wherein m is an integer having a value of 1 or 2; R 4 is hydrogen or lower alkyl; Z is lower alkylenedioxy, CH(OR 2 ) and carbonyl; R 8 when taken alone is hydrogen; R 9 when taken alone is lower alkoxy-carbonyl, aryloxy-carbonyl, lower cycloalkyloxy-carbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is carbonyl R 8 when taken alone is hydrogen; R 9 when taken alone is carbonyl halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R 2 is hydrogen, lower alkyl, lower alkoxy-lower alkyl, phenyl-lower alkyl, tetrahydropyranyl, lower alkanoyl, benzoyl, nitrobenzoyl, carboxy-lower alkanoyl, carboxy-benzoyl, trifluoroacetyl and camphorsulfonyl and reacting them in the case where R 8 and R 9 taken together are methylene or R 8 is hydrogen and R 9 is methylene-X with β-keto esters and other analogs of the formula ##EQU1## wherein R 6 is selected from the group consisting of ##EQU2## and lower alkyl; R 7 is lower alkyl; R 15 is selected from the group consisting of oxo, lower alkylene-dioxy or (hydrogen and lower alkoxy); B is selected from the group consisting of lower alkoxy-carbonyl-methylene, lower-aryloxy-carbonyl-methylene, cyanomethylene, lower alkyl sulfinyl-methylene, lower alkyl sulfonyl-methylene, and R 25 and R 26 are independently selected from the group consisting of hydrogen, hydroxyl and lower alkyl.
参考标题:Synthesis Of Functionalized 2-(Arylthio)Benzoates By Formal [3+3] Cyclizations Of 3-Arylthio-1-Silyloxy-1,3-Butadienes With 3-Silyloxy-2-En-1-Ones And 1,3-Diacylcyclopropanes 作者:Inam Iqbal,Muhammad Imran,Nasir Rasool,Muhammad A. Rashid,Munawar Hussain,Alexander Villinger,Christine Fischer,Peter Langer |发布日期:2009.9 摘要:Functionalized 2-(Arylthio)Benzoates Are Prepared By Formal [3+3] Cyclizations Of 3-Arylthio-1-Trimethylsilyloxy-1,3-Butadienes With 3-Silyloxy-2-En-1-Ones And 1,1-Diacylcyclopropanes.
合成参考文献
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