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    • 25. 发明授权
    • Preparation of tocopheral carboxylates or tocotrienyl esters by acid-catalyzed reaction with carboxylic acids
    • 通过与羧酸的酸催化反应制备生育酚羧酸酯或生育三烯基酯
    • US06365758B1
    • 2002-04-02
    • US09013813
    • 1998-01-26
    • Joanna Linda von dem Bussche-HünnefeldHagen JaedickeGuido HarmsHarald Laas
    • Joanna Linda von dem Bussche-HünnefeldHagen JaedickeGuido HarmsHarald Laas
    • C07D31104
    • C07D311/72
    • A process for preparing tocopheryl esters or tocotrienyl esters by acid-catalyzed esterification of a tocopherol or a tocotrienol in a solvent while stirring at elevated temperature, which comprises a) carrying out the esterification with the appropriate carboxylic acid, b) carrying out the esterification with from 2.5 to 6 mol of the carboxylic acid in an aliphatic, cycloaliphatic or aromatic hydrocarbon boiling in the range from 80 to 200° C., or else with from 1.0 to 2.5 mol of the carboxylic acid in a mixture consisting of an aliphatic or cycloaliphatic hydrocarbon boiling in the range from 80 to 200° C. and a cyclic carbonate of the formula II or a &ggr;-lactone of the formula III  where R1, R2 and R3 are each H or lower alkyl, and R4 is H, lower alkyl, phenyl or methoxymethyl, as solvent, c) using a nonoxidizing strong inorganic or organic acid, preferably sulfuric acid, boroxalic acid or benzene- or toluenesulfonic acids, in catalytic amounts as acid catalyst, and d) continuously removing the water formed in the reaction by azeotropic distillation during the reaction.
    • 一种在高温下搅拌下在溶剂中通过酸催化酯化生育酚或生育三烯酚制备生育酚酯或生育三烯基酯的方法,该方法包括a)用合适的羧酸进行酯化,b)进行酯化反应 在80至200℃范围内沸腾的脂肪族,脂环族或芳族烃中的羧酸为2.5至6摩尔,或者由脂族或脂环族烃组成的混合物中的1.0至2.5摩尔羧酸 沸程在80至200℃的范围内,和式II的环状碳酸酯或式III的γ-内酯,其中R 1,R 2和R 3各自为H或低级烷基,且R 4为H,低级烷基,苯基 或甲氧基甲基,作为溶剂,c)使用非氧化的强无机或有机酸,优选硫酸,硼酸或苯或甲苯磺酸,催化量为酸催化剂,并且d)连续重新 在反应期间通过共沸蒸馏移动反应中形成的水​​。
    • 26. 发明授权
    • Process for preparing higher unsaturated ketones
    • 制备高级不饱和酮的方法
    • US06300524B1
    • 2001-10-09
    • US09440281
    • 1999-11-15
    • Carsten OostManfred StroezelHeinz EtzrodtDietmar WellerUdo RheudeGerd KaibelThomas KrugLuise SpiskeHagen Jaedicke
    • Carsten OostManfred StroezelHeinz EtzrodtDietmar WellerUdo RheudeGerd KaibelThomas KrugLuise SpiskeHagen Jaedicke
    • C07C4500
    • C07C45/676Y02P20/582C07C49/255C07C49/203
    • The present invention relates to an improved process for preparing higher unsaturated ketones by reacting the corresponding &agr;,&bgr;-unsaturated alcohols with alkyl acetoacetates in a Carroll reaction , in a reactor system with fitted fractionation column, wherein A the &agr;,&bgr;-unsaturated alcohol is introduced into the reaction vessel together with the organic aluminum compound in the absence of effective amounts of a solvent, and the alkyl acetoacetate is metered into this mixture, B a reaction temperature which is as constant as possible at between 175° C. and 220° C., preferably between 180° C. and 200° C., is adjusted and C during the reaction the content of alkyl acetoacetate in the reaction mixture is adjusted to a value which is as constant as possible at between 1 and 3% by weight. It is advantageous in this process for the reaction temperature defined under B to be controlled by suitable variation of the heat input and/or by variation of the rate of addition of the alkyl acetoacetate, and for adequate mixing of the reaction mixture in the reaction vessel to be ensured This can be achieved with the aid of a stirrer, by pumping the reaction mixture through an external liquid circulation, by introducing the alkyl acetoacetate by means of a mixing nozzle or else by passing in a stream of inert gas. The process according to the invention is particularly suitable for the Carroll reaction of higher alcohols such as 3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyl-1-octen-3-ol, 3,7,11-trimethyl-1,6,10-dodecatrien-3-ol (nerolidol), 3,7,11-trimethyl-1-dodecen-3-ol or 3,7,11-trimethyl-1,6-dodecadien-3-ol (dihydronerolidol).
    • 本发明涉及一种改进的制备高级不饱和酮的方法,该方法通过在具有合适分馏塔的反应器系统中,在卡罗尔反应中使相应的α,β-不饱和醇与烷基乙酰乙酸酯反应,其中引入α,β-不饱和醇 在没有有效量的溶剂的情况下,将有机铝化合物与有机铝化合物一起加入到反应容器中,并将乙酰乙酸烷基酯计量加入到该混合物中,B在175℃和220℃之间的反应温度尽可能恒定 在反应过程中,优选在180℃和200℃之间调节和C,将反应混合物中乙酰乙酸烷基酯的含量调节至1至3重量%之间尽可能恒定的值。 在该方法中,通过适当变化的热输入和/或通过烷基的加成速率的变化来控制在B下限定的反应温度, 乙酰乙酸酯,并使反应混合物在反应容器中充分混合以确保这可以借助于搅拌器,通过泵送反应混合物通过外部液体循环,通过引入烷基乙酰乙酸酯通过混合喷嘴 或者通过流入惰性气体流。根据本发明的方法特别适用于高级醇如3,7-二甲基-1,6-辛二烯-3-醇(芳樟醇),3, 7,7-二甲基-1-辛烯-3-醇,3,7,11-三甲基-1,6,10-十二碳三烯-3-醇(橙花叔醇),3,7,11-三甲基-1-十二碳烯-3-醇 或3,7,11-三甲基-1,6-十二碳二烯-3-醇(二氢吗啉醇)。
    • 28. 发明授权
    • Preparation of cyclic acetals of 3-formyl-2-butenyltriphenylphosphonium
chloride
    • 制备3-甲酰基-2-丁烯基三苯基氯化鏻的环状缩醛
    • US5344995A
    • 1994-09-06
    • US85903
    • 1993-07-06
    • Wolfgang KrauseJoachim PaustWalter DoblerHagen Jaedicke
    • Wolfgang KrauseJoachim PaustWalter DoblerHagen Jaedicke
    • C07F9/54C07D319/06C07F9/655C07C43/305C07C43/313
    • C07F9/6552C07D319/06
    • An improved process for preparing cyclic acetals of 3-formyl-2-butenyltriphenylphosphonium chloride by acetalization of 3-formyl-2-butenyl acetate with an aliphatic 1,3-diol, conversion of the resulting 4-acetoxy acetal into the corresponding 4-hydroxy acetal, Vilsmeier chlorination to give the corresponding 4-chloro acetal and subsequent reaction with triphenylphosphine entails carrying out the first 3 steps in an aliphatic or cycloaliphatic hydrocarbon or mixture of hydrocarbons with 6-8 carbons and the reaction with triphenylphosphine in an alkanol with 1-3 carbons and/or in aliphatic or cycloaliphatic hydrocarbon with 6-8 carbons or a corresponding mixture of hydrocarbons. The process is particularly advantageous when conversion of the 4-acetoxy acetal into the 4-hydroxy acetal is carried out with an aqueous alkali metal hydroxide solution in the presence of phase-transfer catalysts, and the first three, or all four, reaction stages are carried out in the same C.sub.6 -C.sub.8 -hydrocarbon.
    • 通过用脂肪族1,3-二醇缩醛化3-甲酰基-2-丁烯基乙酸酯与3-甲酰基-2-丁烯基三苯基氯化鏻的环状缩醛的改进方法,将得到的4-乙酰氧基缩醛转化为相应的4-羟基 缩醛,Vilsmeier氯化,得到相应的4-氯缩醛,随后与三苯基膦反应需要在脂族或脂环族烃或碳原子数为6〜8的混合物中进行前3个步骤,并与三苯基膦在链烷醇中与1- 3个碳原子和/或具有6-8个碳原子的脂族或脂环族烃或相应的烃混合物。 当在相转移催化剂存在下,用碱金属氢氧化物水溶液进行4-乙酰氧基缩醛转化为4-羟基缩醛时,该方法是特别有利的,而前三个或所有四个反应阶段是 在相同的C6-C8-烃中进行。