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    • 3. 发明申请
    • METHOD OF PRODUCING DL-'alpha'-TOCOPHEROL OR DL-'alpha'-TOCOPHERYL ACETATE
    • 用于生产DL的α-生育酚或DL-α生育酚乙酸酯
    • WO1997028151A1
    • 1997-08-07
    • PCT/EP1997000324
    • 1997-01-24
    • BASF AKTIENGESELLSCHAFTJAEDICKE, HagenGRAFEN, PaulLAAS, Harald
    • BASF AKTIENGESELLSCHAFT
    • C07D311/72
    • C07D311/72
    • A method is disclosed of producing d1- alpha -tocopherol or d1- alpha -tocopheryl acetate by acid catalysed reaction of 2,3,5-trimethyl hydroquinone (TMH) with phytol or isophytol (IP) in a solvent at raised temperature and, where appropriate, subsequent esterification of the tocopherol thus obtained with acetic anhydride. The method is characterised in that the reaction is carried out in an optionally substituted cyclic five-ring carbonate such as 1,2-propylene carbonate, or in an optionally substituted five-ring lactone such as gamma -butyrolactone, as the solvent at temperatures of between 50 and 200 DEG C. The reaction works particularly well if, following the reaction of TMH and phytol or IP, the tocopherol which separates out as an upper phase as the reaction mixture cools and/or the reaction mixture is extracted using a suitable aliphatic hydrocarbon, the tocopherol is isolated by distillation from the extract, and the separated cyclic carbonate or gamma -lactone which can contain excess TMH and acidic catalyst is reused as solvent. In many cases, it has been shown to be advantageous to carry out the reaction of TMH with phytol or IP with removal of the water as azeotrope, using a suitable hydrocarbon and/or in the presence of a mixture of ortho-boric acid with oxalic acid, tartaric acid or citric acid, or alternatively in the presence of BF3 etherate as the acidic catalyst. Surprisingly, the five-ring carbonates and five-ring lactones prove to have sufficient stability under the reaction conditions and suitable solvent characteristics to permit the process to be carried out continuously.
    • 一种用于在升高的温度下在溶剂中通过2,3,5-三甲基对苯二酚(TMH)与叶绿醇或异植醇(IP)的酸催化反应制备DL-α-生育酚或DL-α-生育酚乙酸酯和,如果必要的话,随后的酯化过程 用乙酸酐将所得的生育酚,其特征在于,所述反应在任选取代的环5-环碳酸酯进行,如1,2-丙二醇碳酸酯,或任选取代的5元环内酯,如γ-丁内酯的 执行如在50的温度下,以200℃的溶剂 该反应发生时,它被TMH和叶绿醇的反应之后,从提取物中分离或IP沉淀作为上层相的反应混合物生育酚的冷却和/或用合适的脂族烃中提取反应混合物,将生育酚分离通过蒸馏和分离的特别有利 ,也可有过量TMH和酸催化剂含有环状碳酸酯或重新用作溶剂的γ-内酯。 在许多情况下,已被证明是有利的,如果TMH的反应用下除去反应与合适的烃的共沸物过程中形成的水​​的植醇或IP,和/或在原硼酸的一方面和草酸的混合物的存在下,酒石酸 在另一方面或柠檬酸,或者如BF3醚合物的存在下,酸性催化剂进行。 出人意料的是,5元环状碳酸酯,和5-元环内酯合适,即使是连续执行的方法的发现可能与反应条件下以及在对它们的溶液行为方面相对于它们的稳定性。
    • 8. 发明申请
    • PROCESS FOR PRODUCING ISOMER MIXTURES FROM O-PHENOXYALKYLHYDROXYL AMINES OR O-PHENOXYALKYLOXIMES
    • 用于生产的异构体混合物ØPHENOXYALKYLHYDROXYLAMINEN或o phenoxyalkyloximes
    • WO1995030648A1
    • 1995-11-16
    • PCT/EP1995001581
    • 1995-04-26
    • BASF AKTIENGESELLSCHAFTRANG, HaraldGÖTZ, NorbertHARREUS, AlbrechtBORCHERS, DirkHARTMANN, HorstMAYWALD, VolkerHEIMANN, FrankBUSCHULTE, Thomas
    • BASF AKTIENGESELLSCHAFT
    • C07C239/20
    • C07C239/20C07C249/12C07C309/66
    • A process is disclosed for producing isomer mixtures from O-phenoxyalkylhydroxyl amines Ia: H2N-O-CH2-CH(R )-O-Ar and Ib: H2N-O-CH(R )-CH2-O-Ar (wherein R represents alkyl, Ar where appropriate a substituted phenyl) and the corresponding salt mixtures. This process involves the following steps: (a) an isomer mixture of O-(2-hydroxyethyl)-oximes (IIa) and (IIb) (in which R is an alkyl and R is an alkyl or alkoxy, or R and R together with the common C atom form a 5-7 member ring) is converted by reaction with a sulphonyl halogenide of formula (III): Hal-SO2-R (wherein R represents an organic group and Hal is a halogen) in the presence of a base to form the corresponding sulphonate mixture of (IVa) and (IVb); (b) this sulphonate mixture is reacted in the presence of a base with a phenol of formula (V): HO-Ar to produce a mixture of O-phenoxyalkyloximes of general formulae (VIa) and (VIb); (c) the mixture is hydrolysed in the presence of an acid and, if required, (d) the O-phenoxyalkylhydroxyl amines (Ia) and (Ib) are released from the resulting salts using a mineral base. The O-phenoxyalkylhydroxyl amines (Ia/Ib) and their precursors (VIa/VIb) are important intermediate products for plant protective agents and drugs.
    • 的异构体的混合物的制备O型Phenoxyalkylhydroxylaminen(Ia)中:H 2 N-O-CH2-CH(R <1>) - O-Ar和(Ib)中:H 2 N-O-CH(R <1>) - CH2-O-氩 (R <1> =烷基; Ar为SUBST GEG苯基..)以及相应的盐的混合物,通过一)肟的异构体混合物O-(2-羟基乙基)(IIa)和(IIb)的(R <2> = 烷基,并且R <3> =烷基,烷氧基,或R <2>和R <3>使用通用C原子= 5-至7-元环)化合物与式(III)的磺酰卤一起:哈尔-SO 2 -R <4> <4>是且其中R是有机基团,Hal是卤素,在碱存在下的成的(IVa)的磺酸盐的相应的混合物和(IVb)中被转换,b)磺酸酯的混合物在碱的存在下与酚 式(V):HO-氩气,于通式(VIA)和(VIb)的O- phenoxyalkyloximes的混合物反应,c)中将该混合物水解在酸的存在下和,如果需要的话,d)从所述发生的盐,所述O- phenoxyalkylhydroxylamines(Ia)和(Ib)的装置矿工芭 Ë版本。 O型phenoxyalkylhydroxylamines(IA / IB)及其前体(VIA /ⅥB)是作物保护剂和药物的重要中间体。