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    • 8. 发明授权
    • Process for the preparation of isochroman-3-ones
    • 异苯并二氢吡喃-3-酮的制备方法
    • US06348603B1
    • 2002-02-19
    • US09668915
    • 2000-09-25
    • Holger GeisslerRalf Pfirmann
    • Holger GeisslerRalf Pfirmann
    • C07D40700
    • C07D311/76
    • The present invention relates to a process for the preparation of an isochroman-3-one of the formula (I) by reaction of a 1,2-bishalomethylbenzene of the formula (II) in which X is chlorine, bromine or iodine, with carbon monoxide and a compound of the formula (III) R5R6R7C—OH  (III) at a CO pressure of 0.1 to 50 MPa and a temperature of 20 to 200° C. in the presence or absence of an ionic halide, in the presence of a palladium catalyst and of a dipolar aprotic solvent, with addition of water or without addition of water, where in the formulae (I) and (II) the radicals R1, R2, R3 and R4 independently of one another are: a hydrogen or fluorine atom; an NC or F3C group; an alkyl, alkoxy or acyloxy radical, in each case having 1 to 18 carbon atoms; or a C6-C18-aryloxy, aryl or heteroaryl radical, where 1 to 3 atoms from the group consisting of O, N and/or S are present as heteroatoms; or in which at least two of the radicals R1, R2, R3 and R4 are linked to one another and form at least one aliphatic or aromatic ring having 5 to 18 carbon atoms, and in formula (III) the radicals R5, R6 and R7 are identical or different and are a C1-C18-alkyl, an HOC(═O)—, H3CC(═O)CH2— or (C6-C18-aryl)-CH2— radical or at least two of the radicals R5, R6 and R7 are linked to one another and form at least one aliphatic or aromatic ring having 5 to 18 carbon atoms.
    • 本发明涉及一种制备式(I)的异苯并二氢吡喃-3-酮的方法,其中X为氯,溴或碘的式(Ⅱ)的1,2-二沙甲基苯与碳 一氧化碳和式(III)化合物在CO 2压力为0.1〜50MPa,温度为20〜200℃的条件下,在钯催化剂存在或不存在下,在钯催化剂和偶极 非质子溶剂,加入水或不加入水,其中在式(I)和(II)中,基团R 1,R 2,R 3和R 4彼此独立地为:氢或氟原子; NC或F3C组; 烷基,烷氧基或酰氧基,每种情况具有1至18个碳原子; 或C 6 -C 18芳氧基,芳基或杂芳基,其中以O,N和/或S为基的1至3个原子作为杂原子存在;或其中至少两个基团R 1,R 2,R 3和 R4彼此连接并形成至少一个具有5至18个碳原子的脂族或芳族环,并且在式(III)中,基团R 5,R 6和R 7相同或不同,为C 1 -C 18烷基,HOC (= O) - ,H 3 C(= O)CH 2 - 或(C 6 -C 18 - 芳基)-CH 2 - 基或基团R 5,R 6和R 7中的至少两个彼此连接并形成至少一个脂族或芳族 具有5至18个碳原子的环。
    • 10. 发明授权
    • Method for producing chiral dihydrotagetone, and its conversion to chiral 5-isobutyl-3-methyl-4,5-dihydro-2(3H)-furanone
    • 制备手性二氢吉他酮的方法及其转化为手性5-异丁基-3-甲基-4,5-二氢-2(3H) - 呋喃酮
    • US06579992B2
    • 2003-06-17
    • US09815335
    • 2001-03-23
    • Arun Kumar SinhaBhupendra Prasad JoshiRuchi Dogra
    • Arun Kumar SinhaBhupendra Prasad JoshiRuchi Dogra
    • C07D40700
    • C07C51/29C07C59/347
    • A natural inexpensive acyclic monoterpene ketone (dihydrotagetone) of formula (4), isolated from the oil of Tagetes sp., was smoothly oxidized with meta-periodate/potassium permanganate into 2,6-dimethyl-4-oxo-heptanoic acid of formula (3), the reduction of 3 with metal hydride such as sodium borohydride or lithium aluminium hydride provided 4-hydroxyacid of formula (2) which on without isolation undergone lactonization in acidic medium furnished two chiral centered 5-isobutyl-3-methyl-4,5-dihydro-2(3H)-furanone of formula (1) as an analogue of whisky lactone 5-butyl-4-methyl-4,5-dihydro-2(3H)-furanone of formula (1a) responsible for high quality of alcoholic beverage (whisky, wine, brandy and scotch), in addition, coconut flavored 5-butyl-4-methyl-4,5-dihydro-2(3H)-furanone of formula (1) is also as an analogue of coconut aldehyde (&ggr;-nonalactone, F.E.M.A. No. 2751) of formula (1b) which is responsible for flavoring a wide range of food stuffs including baked goods and confectionery.
    • 从Tagetes sp。油中分离得到的式(4)的天然廉价的无环单萜酮(二氢t酮)用高碘酸钾/高锰酸钾被平滑地氧化成式(4)的2,6-二甲基-4-氧代 - 庚酸 3)中,用金属氢化物如硼氢化钠或氢化铝锂还原3,得到式(2)的4-羟基酸,其在酸性介质中经过内酯化而没有分离,提供了两个手性中心的5-异丁基-3-甲基-4- (1)的5-二氢-2(3H) - 呋喃酮作为负责高品质的式(1a)的威士忌内酯5-丁基-4-甲基-4,5-二氢-2(3H) - 呋喃酮的类似物 的酒精饮料(威士忌,葡萄酒,白兰地和苏格兰威士忌),此外,式(1)的椰子风味的5-丁基-4-甲基-4,5-二氢-2(3H) - 呋喃酮也是椰子的类似物 式(1b)的醛(γ-非内酯,FEMA No.2751),其负责调味各种食品,包括烘焙食品和糖果 y。