Process for transition metal-catalyzed asymmetric hydrogenation of acrylic acid derivatives, and a novel catalyst system for asymmetric transition metal catalysis
    1.
    发明授权
    Process for transition metal-catalyzed asymmetric hydrogenation of acrylic acid derivatives, and a novel catalyst system for asymmetric transition metal catalysis 有权
    用于过渡金属催化的丙烯酸衍生物的不对称氢化方法,以及用于不对称过渡金属催化的新型催化剂体系

    公开(公告)号:US07473792B2

    公开(公告)日:2009-01-06

    申请号:US11666922

    申请日:2005-12-05

    IPC分类号: C07F15/00 B01J31/00 C07C57/02

    摘要: A process for transition metal-catalyzed, asymmetric hydrogenation of acrylic acid derivatives of the formula (I) in which R1 is H or an optionally substituted alkyl, aryl or heteroaryl radical, R2 is an optionally substituted alkyl, aryl or heteroaryl radical, and R3 is H or a C1-C6-alkyl radical, which comprises hydrogenating compounds of the formula (I), optionally in a solvent, in the presence of one or more hydrogen donors, using a catalyst system which comprises a transition metal from the group of ruthenium, rhodium and iridium and a combination of a chiral phosphorus ligand of the formula (II) in which Cn, together with the two oxygen atoms and the phosphorus atom, forms an optionally substituted ring having from 2 to 6 carbon atoms and R4 is an optionally substituted alkyl, aryl, alkoxy or aryloxy radical or NR5R6 where R5 and R6 may each independently be H or an optionally substituted alkyl, aryl, aralkyl or alkaryl radical, or, together with the nitrogen atom, may form a ring, and an achiral phosphine ligand of the formula (III) in which R is an optionally substituted alkyl or aryl radical, to the corresponding compounds of the formula (IV) in which R1, R2 and R3 are each as defined above, and also a novel catalyst system for asymmetric transition metal catalysis.

    摘要翻译: R 1为H或任选取代的烷基,芳基或杂芳基的式(I)的丙烯酸衍生物的过渡金属催化不对称氢化的方法,R 2为任选取代的烷基,芳基或杂芳基,R 3为 是H或C 1 -C 6烷基,其包括在一个或多个氢供体存在下,任选地在溶剂中使式(I)化合物氢化,使用包含过渡金属 钌,铑和铱以及式(II)的手性磷配体的组合,其中Cn与两个氧原子和磷原子一起形成任选取代的具有2至6个碳原子的环,R 4是 任选取代的烷基,芳基,烷氧基或芳氧基或NR5R6,其中R5和R6各自独立地为H或任选取代的烷基,芳基,芳烷基或烷芳基,或与氮原子一起形成 g和其中R是任选取代的烷基或芳基的式(III)的非手性膦配体与相应的式(IV)化合物反应,其中R 1,R 2和R 3各自如上所定义,以及 一种用于不对称过渡金属催化的新型催化剂体系。

    Process for the preparation of a linear aldehyde organic compound
    4.
    发明授权
    Process for the preparation of a linear aldehyde organic compound 失效
    制备线性醛有机化合物的方法

    公开(公告)号:US5811589A

    公开(公告)日:1998-09-22

    申请号:US552851

    申请日:1995-11-03

    CPC分类号: C07C45/50 C07C67/347

    摘要: Process for the preparation of a linear aldehyde organic compound by hydroformylation (b) starting from an internally unsaturated functionalised organic compound whereby first (a) a portion of the internally unsaturated functionalized organic compound is isomerized to a terminally unsaturated functionalised organic compound in the presence of a suitable isomerization catalyst, wherein following the isomerization step (a), the hydroformylation (b) is effected in the presence of carbon monoxide, hydrogen and a catalyst which preferentially catalyzes the hydroformylation reaction of the terminally unsaturated functionalised organic compound to the linear aldehyde organic compound, the internally unsaturated functionalised organic compound remaining practically unhydroformylated, whereupon (c) the linear aldhyde organic compound is separated out of the mixture and (d) the remainder of the unsaturated functionalised organic compound-containing mixture is recirculated to the isomerization step (a).

    摘要翻译: 通过加氢甲酰化制备线性醛有机化合物的方法(b)从内部不饱和官能化的有机化合物开始,由此首先(a)一部分内部不饱和官能化的有机化合物在存在下被异构化为末端不饱和官能化的有机化合物 合适的异构化催化剂,其中在异构化步骤(a)之后,加氢甲酰基化(b)在一氧化碳,氢气和催化剂的存在下进行,其优先催化末端不饱和官能化有机化合物与直链醛有机物的加氢甲酰化反应 化合物,内部不饱和官能化的有机化合物几乎保持未形成甲酰化,因此(c)线性醛酸有机化合物从混合物中分离出来,(d)剩余的不饱和官能化的含有机化合物的混合物再循环到异构化st ep(a)。

    Process for the preparation of dicarboxylic acids
    5.
    发明授权
    Process for the preparation of dicarboxylic acids 失效
    二羧酸的制备方法

    公开(公告)号:US5917049A

    公开(公告)日:1999-06-29

    申请号:US989404

    申请日:1997-12-12

    摘要: Process for the preparation of a heterocyclic o-dicarboxylic acid containing at least one N atom, in which a corresponding benzo-fused heterocyclic compound containing at least one N atom is oxidised in the presence of hydrogen peroxide, a Bronsted acid and an iron compound.Preferably Fe(NO.sub.3).sub.3 is used as the iron compound and HNO.sub.3 as the Bronsted acid. The amount of iron compound to be used preferably lies between 0.1 and 2 mol. %, relative to the amount of employed benzo-fused heterocyclic compound containing at least one N atom. Even higher yields can be obtained if a copper compound or an organic electron-transferring compound is also used, in addition to the iron compound.In particular, the process according to the invention can be used to prepare 2,3-pyridine dicarboxylic acids from corresponding quinoline compounds.

    摘要翻译: 制备含有至少一个N原子的杂环二羧酸的方法,其中在过氧化氢存在下将含有至少一个N原子的相应的苯并稠合杂环化合物氧化,得到Br + E, 戊二酸和铁化合物。 优选使用Fe(NO 3)3作为铁化合物,将HNO 3用作Br + E,O + EE + nsted酸。 使用的铁化合物的量优选为0.1〜2mol。 %,相对于使用含有至少一个N原子的苯并稠合杂环化合物的量。 除了铁化合物之外,如果还使用铜化合物或有机电子传递化合物,则可以获得更高的收率。 特别地,根据本发明的方法可用于由相应的喹啉化合物制备2,3-吡啶二羧酸。

    Process for the preparation of 5-formylvaleric acid and 5-formylvalerate
ester
    6.
    发明授权
    Process for the preparation of 5-formylvaleric acid and 5-formylvalerate ester 失效
    5-甲酰戊酸和5-甲酰戊酸酯的制备方法

    公开(公告)号:US5719312A

    公开(公告)日:1998-02-17

    申请号:US671929

    申请日:1996-06-27

    CPC分类号: C07C51/373 C07C67/347

    摘要: The invention relates to a process for the preparation of 5-formylvaleric acid or the corresponding 5-formylvalerate by hydroformylation of 3-pentenoic acid or 3-pentenoate ester with carbon monoxide and hydrogen in the presence of a catalyst comprising of rhodium and a phosphite ligand, wherein the phosphite ligand is represented by the following general formula ##STR1## where R.sup.1 and R.sup.2 are the same or different aromatic organic groups and where A is an n-valent group or atom and where n is an integer chosen upwards of 2 and where the respective �--O--P(OR.sup.1)(OR.sup.2)! group may be the same group or different groups and where the phosphite forms a chelate-type complex with rhodium.

    摘要翻译: 本发明涉及通过在包含铑和亚磷酸酯配体的催化剂存在下,用一氧化碳和氢气将3-戊烯酸或3-戊烯酸酯加氢甲酰化制备5-甲酰戊酸或相应的5-甲酰基戊酸酯的方法 其中亚磷酸酯配体由以下通式表示:其中R1和R2是相同或不同的芳族有机基团,其中A是n价基团或原子,其中n是选自2以上的整数,其中 相应的[-OP(OR1)(OR2)]基团可以是相同的基团或不同的基团,并且其中亚磷酸酯与铑形成螯合型络合物。