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    Process for manufacturing carbonyl compounds by oxidation with molecular oxygen of olefinic compounds in liquid phase in the presence of soluble bimetallic catalysts
    6.
    发明授权
    Process for manufacturing carbonyl compounds by oxidation with molecular oxygen of olefinic compounds in liquid phase in the presence of soluble bimetallic catalysts 失效
    在可溶性双金属催化剂存在下，通过在液相中用烯属化合物的分子氧氧化制备羰基化合物的方法

    公开(公告)号：US4085145A

    公开(公告)日：1978-04-18

    申请号：US686245

    申请日：1976-05-13

    申请人： Hubert Mimoun ,  Do Thao ,  Irenee Seree de Rochi

    发明人： Hubert Mimoun ,  Do Thao ,  Irenee Seree de Rochi

    IPC分类号： B01J31/00 ,  C07B61/00 ,  C07C45/00 ,  C07C45/34 ,  C07C45/35 ,  C07C45/36 ,  C07C67/00 ,  C07C45/10

    CPC分类号： C07C45/35 ,  C07C45/34 ,  C07C45/36

    摘要： Carbonyl compounds are manufactured by oxidation of olefines with molecular oxygen in the presence of a catalytic system comprising both a specific rhodium compound and a specific compound of a metal selected from iron, cobalt, nickel and copper. The reaction is conducted in a substantially anhydrous organic solvent selected from alcohols, polyols and glycol monoethers.The present invention concerns a process for manufacturing carbonyl compounds, particularly methyl ketones, in the liquid phase, by the catalytic oxidation of olefins with molecular oxygen, in a substantially anhydrous medium and in the presence of soluble bimetallic catalysts.In the processes of the Wacker type for converting olefins to ketones (U.S. Pat. No. 3,080,425), the catalysts are, for example, palladium chloride or rhodium oxyhydrate associated with copper chloride or iron sulfate; these processes are operated in the aqueous phase and water is the oxidizing agent for the reaction.According to the French Pat. No. 1,210,009, rhodium, iridium or palladium chloride associated with copper chloride is also used as catalyst for oxidizing olefins in the aqueous phase, and water is the oxidizing agent.According to the two above patents, it is essential to operate in a strongly acidic medium (concentrated acids are employed).Other patents also utilize the presence of water to carry out reactions of the same kind in an organic solvent with palladium catalysts of the same type: French Pat. Nos. 1,564,635 and 1,395,129; U.S. Pat. No. 3,370,073.The process according to the invention is performed essentially in the liquid phase, in a water-free solvent, in the presence of a rhodium catalyst, the other noble metals of the VIIIth group being excluded. Thus, by using rhodium instead of palladium, a metal commonly used in liquid phase, processes far higher selectivities are obtained, particularly when converting terminal olefins to methylketones, as well as far higher reaction rates.According to the process of the invention, the catalyst comprises both at least one organometallic salt or complex [A] and at least one organometallic salt or compound [B], of the general formulas:[A] : M.sub.1 X.sub.n L.sub.m[B] : M.sub.2 Z.sub.p L.sub.qIn the salt of complex [A], M.sub.1 is rhodium.X is an anionic group, preferably halogen (usually chlorine of fluorine), a carboxylate, a sulfate, a nitrate, a perchlorate, a thiocyanate, a tetrafluoroborate, an acetyl acetonate or a cyclopentadienyl.n is a integer selected from 1, 2 and 3.L is a coordinate, preferably a water molecule or an organic compound selected preferably from the olefins, diolefins, phosphines, dimethylsulfoxide and an acetylacetonate group.m is an integer from 1 to 3.Non-limitative examples of rhodium complexes are:Rhodium fluoride, RhF.sub.3, 3H.sub.2 Orhodium chloride, RhCl.sub.3, 3H.sub.2 Orhodium bromide, RhBr.sub.3, 2H.sub.2 0[rh X (olefin).sub.2 ].sub.2where X is chlorine or bromine and olefin is ethylene, propylene, tetrafluorethylene or cyclooctene; for example [RhCl (C.sub.2 H.sub.4).sub.2 ].sub.2 where C.sub.2 H.sub.4 is ethylene.[Rh X (polyolefin)].sub.2where X is chlorine or bromine, and polyolefin is 1,5-cyclooctadiene, 1,5-hexadiene, butadiene or cyclododecatriene, for example [RhCl (C.sub.8 H.sub.12)].sub.2 where C.sub.8 H.sub.12 is 1,5-cyclooctadiene.Rh (acac) (olefin).sub.2where "acac" is an acetylacetonate group and olefin is ethylene or tetrafluorethylene.In the salt or complex [B] to be used with the complex A:M.sub.2 is a transition metal selected from iron, cobalt, nickel and copper,Z is an anionic group, preferably halogen, a carboxylate, a sulfate, a nitrate, a perchlorate or a tetrafluoroborate.p is an integer selected from 1, 2 and 3.L' is a coordinate, preferably a molecule of water or an organic molecule, for example dimethylformamide, hexamethylphosphoramide or dimethylsulfoxide.q is 0 or an integer from 1 to 6.Non-limitative examples are:iron, cobalt, nickel and copper perchlorates and nitrates of the general formulas M.sub.2 (ClO.sub.4).sub.2, 6H.sub.2 O and M.sub.2 (NO.sub.3).sub.2, 6H.sub.2 O.copper and iron halides of the formula M.sub.2 Z.sub.p, .sub.q H.sub.2 O with Z = fluorine, chlorine or bromine and M.sub.2 = iron or copper, p is 2 or 3 and q is 0 or an integer from 1 to 6.complexes such as: Cu (ClO.sub.4).sub.2, 4 L'; Fe (ClO.sub.4).sub.2, 4 L' or Cu (NO.sub.3).sub.2, 4 L', where L' is a coordinate such as dimethylformamide, hexamethylphosphoramide or dimethylsulfoxide; for example:Cu (ClO.sub.4).sub.2 (HMPT).sub.4 or Cu (NO.sub.3).sub.2 (HMPT).sub.4where HMPTis hexamethylphosphoramide.This invention applies to branched or unbranched olefinic compounds having from 2 to 16 carbon atoms per molecule and whose general formula is R.sub.1 -- CH .dbd. CH -- R.sub.2 where R.sub.1 and R.sub.2 are identical or not and represent either hydrogen atoms or alkyl, aryl, alkylaryl or aralkyl radicals having 1 - 14 carbon atoms per molecule.According to the invention, there are preferably used primary terminal olefins of the above general formula where R.sub.1 = H and R.sub.2 = alkyl, aryl, alkylaryl or aralkyl; they contain 3 - 16 carbon atoms and yield methylketones selectively. They are thus of the formula CH.sub.2 .dbd. CH -- R.sub.2. From ethylene, there is obtained ethanal.Non-limitative examples are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 5-methyl-1-hexene and styrene.The primary terminal olefins may be used in a pure state or diluted with other inert or olefinic hydrocarbons. Thus oxidizing partially hydrogenated steam cracking C.sub.4 cuts containing a mixture of olefins such as 1-butene and cis and trans 2-butenes and butane leads selectively to the formation of methylethyl ketone obtained by oxidation of 1-butene, the other olefins being only slightly oxidized.The oxidation reaction is conducted in liquid phase in an organic solvent; the catalyst in the form of its two constituents [A] and [B] being solubilized in the medium.The solvent is an alcohol or a polyalcohol. It comprises preferably from 1 to 20 carbon atoms per molecule. The alcohol may be a primary, secondary or tertiary alcohol; the polyalcohol (or polyol) comprises at least 2 alcohol groups.Examples of solvents are: methanol, ethanol, n-propanol, isopropanol, 2-butanol, 3,3-dimethyl-2-butanol, cyclohexanol, methyl phenyl carbinol, ethylene glycol, 1,2-propane diol and glycerol.Other useful solvents are the glycol monoethers (cellosolves) of the formula R -- O -- CH.sub.2 -- CH.sub.2 OH, particularly methylcellosolve of the formula CH.sub.3 -- O -- CH.sub.2 -- CH.sub.2 OH.The alcoholic or polyalcoholic solvents yield better results than those obtained with other conventional solvents such as ketones, ethers and esters.It is essential that the solvent be substantially anhydrous since, irrespective of the solvent, the reaction improves when the water concentration in the medium decreases. Water may be tolerated, however, at concentrations up to 1% b.w. in the solvent, and preferably not above 0.5%, whenever possible not above 0.2%. A dehydration agent may be added to the medium, if necessary, for example 2,2'-dimethoxypropane.The temperature at which the reaction takes place is from about 0.degree. C to about 150.degree. C, preferably from 30.degree. C to 130.degree. C.The oxidation gas may be pure oxygen or oxygen diluted with nitrogen or any inert gas.The oxygen partial pressure is from 0.1 to 25 bars.Conversely to the prior art processes, it is conducted in substantially neutral medium (pH usually between about 6 and 8).In the process according to the invention, the molar ratio [B]/[A] is usefully from 0.5 to 10 and preferably from 1 to 4.The molar ratio [A]/olefine, in mole per liter, is usefully from 10.sup.-3 to 5 .times. 10.sup.-1, preferably from 5 .times. 10.sup.-3 to 10.sup.-1.The present invention is illustrated by the following examples:

    摘要翻译： 羰基化合物通过在包含特定铑化合物和选自铁，钴，镍和铜的金属的特定化合物的催化体系存在下用分子氧氧化来制备。 该反应在基本无水的有机溶剂中进行，所述有机溶剂选自醇，多元醇和二醇单醚。

    Process for the preparation of lactones or epoxides
    7.
    发明申请
    Process for the preparation of lactones or epoxides 失效
    制备内酯或环氧化物的方法

    公开(公告)号：US20050283008A1

    公开(公告)日：2005-12-22

    申请号：US11210501

    申请日：2005-08-23

    申请人： Hubert Mimoun

    发明人： Hubert Mimoun

    IPC分类号： C07D301/12 ,  C07D315/00 ,  C07D307/02

    CPC分类号： C07D315/00 ,  C07D301/12

    摘要： The present invention relates to a process for the oxidation, in an inert solvent, of a non-aromatic or non-enonic ethylenic bond or of a non-conjugated cyclic ketones into the corresponding epoxides, respectively lactone, using H2O2 as oxidant, a content in water of the reaction medium below 15% w/w and, as sole catalyst, an alkaline or alkaline earth salt or complex.

    摘要翻译： 本发明涉及一种在惰性溶剂中将非芳族或非烯烃烯键或非共轭环酮氧化成相应的环氧化物，分别为内酯的H 2 O 2的方法， 作为氧化剂，反应介质的水中的含量低于15％w / w，作为唯一的催化剂，为碱金属或碱土金属盐或络合物。

    Fragrant macrocyclic lactones
    9.
    再颁专利
    Fragrant macrocyclic lactones 有权
    芬芳的大环内酯

    公开(公告)号：USRE36493E

    公开(公告)日：2000-01-11

    申请号：US282453

    申请日：1999-03-31

    申请人： Hubert Mimoun ,  Pierre-Alain Blanc

    发明人： Hubert Mimoun ,  Pierre-Alain Blanc

    IPC分类号： A61K8/35 ,  A61Q13/00 ,  C07D313/00 ,  C07D315/00 ,  C11B9/00 ,  A61K7/46 ,  C11D3/50 ,  A61K9/04

    CPC分类号： C07D313/00 ,  C07D315/00 ,  C11B9/0084

    摘要： Perfuming ingredients which include at least one macrolide of formula ##STR1## having a double bond in one of the positions indicated by the dotted lines and wherein the symbol R represents a hydrogen atom or a methyl radical, are described. They are useful for the preparation of perfumes and perfumed consumer products to which they impart musky odors with original nuances.

    摘要翻译： 描述了包含至少一种式中具有双键的大环内酯类，其中一个位置由虚线表示，其中符号R表示氢原子或甲基。 它们可用于制备香水和香水消费品，使麝香气味具有原始的细微差别。