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    • 8. 发明授权
    • Synthesis of triconjugated dienones and novel intermediates used in said
process
    • 三氯联二烯酮的合成和所述方法中使用的新型中间体
    • US4623749A
    • 1986-11-18
    • US620163
    • 1984-08-17
    • William J. EversGilbert StorkBraja D. MookherjeeHoward H. Heinsohn, Jr.
    • William J. EversGilbert StorkBraja D. MookherjeeHoward H. Heinsohn, Jr.
    • C07C45/67C07C49/203C07C69/145C07C69/157C11B9/00C11D3/50
    • C11D3/50C07C45/673C07C45/676C07C49/203C07C67/293C11B9/0015C11B9/0061
    • Described is a process for preparing triconjugated dienones defined according to the structure: ##STR1## wherein R.sub.1 represents C.sub.1 -C.sub.8 alkyl, phenyl or phenyl methyl and wherein R.sub.2 represents hydrogen or C.sub.1 -C.sub.5 lower alkyl; and wherein the wavy lines are indicative of a "cis" or a "trans" juxtaposition of the R.sub.2, methyl, acyl or vinyl moieties about one or both of the carbon-carbon double bonds which process involves the reaction of an acyl halide with a substituted or unsubstituted prenyl ester having the structure: ##STR2## wherein R.sub.3 represents C.sub.1 -C.sub.5 alkyl in the presence of an aluminum chloride catalyst and a methylene dichloride solvent in order to form a halogen-ester intermediate defined according to the structure: ##STR3## then dehydrohalogenating said halogen-ester intermediate using an alkali metal carbonate and a dimethylformamide solvent in order to form a ketoester having the structure: ##STR4## wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; and then dehydroacyloxylating the ketoester in the presence of an alkali metal carbonate and dimethylformamide solvent in order to form the triconjugated dienone.
    • 描述了根据以下结构定义的三结合双酮的方法:其中R 1表示C 1 -C 8烷基,苯基或苯基甲基,并且其中R 2表示氢或C 1 -C 5低级烷基; 并且其中波浪线表示R2,甲基,酰基或乙烯基部分在一个或两个碳 - 碳双键上的“顺式”或“反式”并置,该方法涉及酰卤与 具有以下结构的取代或未取代的异戊二烯基酯:其中R 3在氯化铝催化剂和二氯甲烷溶剂的存在下代表C 1 -C 5烷基,以形成根据以下结构定义的卤素 - 酯中间体: 然后使用碱金属碳酸盐和二甲基甲酰胺溶剂将所述卤代酯中间体脱卤化氢,以形成具有以下结构的酮酯:其中虚线中的一条代表碳 - 碳双键,另一条虚线表示 碳 - 碳单键; 然后在碱金属碳酸盐和二甲基甲酰胺溶剂的存在下,使酮酯脱羟基酰化,以形成三羟甲基封端的二烯酮。
    • 10. 发明授权
    • Synthesis of triconjugated dienones and intermediates used in said
process
    • 在所述方法中使用的三氯联二烯酮和中间体的合成
    • US4560791A
    • 1985-12-24
    • US551480
    • 1983-11-14
    • William J. EversGilbert StorkBraja D. MookherjeeHoward H. Heinsohn, Jr.
    • William J. EversGilbert StorkBraja D. MookherjeeHoward H. Heinsohn, Jr.
    • C07C45/67C07C49/203C07C69/157C11B9/00C11D3/50
    • C11D3/50C07C45/673C07C45/676C07C49/203C07C67/293C07C67/297C07C69/63C11B9/0015C11B9/0061
    • Described is a process for preparing triconjugated dienones defined according to the structure: ##STR1## wherein R.sub.1 represents C.sub.1 -C.sub.8 alkyl, phenyl or phenyl methyl and wherein R.sub.2 represents hydrogen or C.sub.1 -C.sub.5 lower alkyl; and wherein the wavy lines are indicative of a "cis" or a "trans" juxtaposition of the R.sub.2, methyl, acyl or vinyl moieties about one or both of the carbon-carbon double bonds which process involves the reaction of an acyl halide having the structure: ##STR2## (wherein X represents chloro) with a substituted or unsubstituted prenyl ester having the structure: ##STR3## wherein R.sub.3 represents C.sub.1 -C.sub.5 alkyl in the presence of an aluminum chloride catalyst and a methylene dichloride solvent in order to form the novel intermediate genus defined according to the structure: ##STR4## then dehydrohalogenating the compound defined according to the structure: ##STR5## using an alkali metal carbonate and a dimethylformamide solvent in order to form the novel compound genus having the structure: ##STR6## wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; and then dehydroacyloxylating the compound having the structure: ##STR7## in order to form the compound having the structure: ##STR8## the dehydroacyloxylation step taking place in the presence of an akali metal carbonate and dimethylformamide solvent.
    • 描述了根据以下结构定义的三结合双酮的方法:其中R 1表示C 1 -C 8烷基,苯基或苯基甲基,并且其中R 2表示氢或C 1 -C 5低级烷基; 并且其中波浪线表示R2,甲基,酰基或乙烯基部分在一个或两个碳 - 碳双键上的“顺式”或“反式”并置,该方法涉及具有 结构:其中X表示氯,具有以下结构的取代或未取代的异戊二烯基酯:其中R 3表示C 1 -C 5烷基,在氯化铝催化剂和二氯甲烷溶剂的存在下,形成 根据以下结构定义的新型中间体:然后使用碱金属碳酸盐和二甲基甲酰胺溶剂将根据结构定义的化合物脱卤化氢,以形成具有以下结构的新颖化合物:其中 虚线中的一条代表碳 - 碳双键,另一条虚线表示碳 - 碳单键; 然后将具有以下结构的化合物脱氢酰化氧化:为了形成具有以下结构的化合物:在碱金属碳酸盐和二甲基甲酰胺溶剂存在下进行脱氢甲酰氧基化步骤。