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    • 1. 发明授权
    • Method for producing phosphabenzene compounds
    • 膦酸化合物的制备方法
    • US06255532B1
    • 2001-07-03
    • US09509672
    • 2000-03-30
    • Rocco PacielloEdgar ZellerBernhard BreitMichael Röper
    • Rocco PacielloEdgar ZellerBernhard BreitMichael Röper
    • C07F950
    • C07F9/6568B01J31/2419B01J31/2461B01J2231/321B01J2531/822B01J2531/845
    • A process for the preparation of phosphabenzene compounds of the formulae I and II where R1 to R6, independently of one another, are hydrogen, COOM SO3M, NR3X, NR2, OR, COOR or SR, where M is hydrogen, NH4 or an alkali metal, X is an anion, R is hydrogen, C1-6-alkyl, or C1-12-alkyl, C6-12-aryl, C7-12-aralkyl or C3-6-heterocycloalkyl having 1 to 3 heteroatoms which may be substituted by the above radicals or linked to form fused rings, and —W— is a bridge comprising a covalent bond, an oxo group, a sulfur group, an amino group, a di-C1-6-alkylsilicon group or a C1-16-radial, which may be part of one or more linked cyclic or aromatic rings and may be interrupted by 1 to 3 heteroatoms, where the phosphabenzene ring o- or m-position not bonded to the bridge may carry one of the radicals R1 to R6, with the exception of bis-3,3′-(2,4,6-triphenyl-3-phosphabenzene)-1,1-biphenyl, by reacting corresponding pyrilium salts with PH3 in the presence of a catalytic amount of acid and in the presence or absence of a solvent or diluent, where the pyrilium salts are mixed with PH3 at above 0° C. and reacted at from 0° C. to 200° C. and at a pressure greater than 1 bar.
    • 制备式I和II的膦酸化合物的方法,其中R 1至R 6彼此独立地为氢,COOM SO 3 M,NR 3 X,NR 2,OR,COOR或SR,其中M为氢,NH 4或碱金属, X是阴离子,R是氢,C 1-6 - 烷基或C 1-12 - 烷基,C 6-12 - 芳基,C 7-12 - 芳烷基或具有1至3个杂原子的C 3-6 - 杂环烷基,其可以被 并且-W-是包含共价键,氧代基团,硫基团,氨基基团,二-C1-6烷基硅基团或C1-16-放射状核团的桥, 其可以是一个或多个连接的环状或芳香环的一部分,并且可以被1至3个杂原子中断,其中未键合到桥的膦酰基环或 - 位置可以携带基团R1至R6中的一个,其中 通过使相应的吡啶鎓盐与PH 3在催化量的酸的存在下反应,并在存在或不存在下,将双-3'' - (2,4,6-三苯基-3-苯基苯基) 没有溶剂或稀释剂,其中吡啶鎓盐在0℃下与PH3混合,并在0℃至200℃和大于1巴的压力下反应。
    • 4. 发明授权
    • Method for the production of aldehydes
    • 醛的生产方法
    • US06310261B1
    • 2001-10-30
    • US09582780
    • 2000-07-03
    • Bernhard GeisslerMichael RöperEdgar ZellerRocco PacielloJürgen DeckerHartwig VossNorbert Mahr
    • Bernhard GeisslerMichael RöperEdgar ZellerRocco PacielloJürgen DeckerHartwig VossNorbert Mahr
    • C07C4550
    • C08G73/0206B01J31/1658B01J31/1805B01J2231/321B01J2531/80B01J2531/822C07C45/50Y02P20/584C07C47/02
    • The invention relates to a method for the production of aldehydes or aldehydes and alcohols by hydroformylation of olefins in the presence of a complexing catalyst homogeneously dissolved in a reaction mixture, containing a metal of Group VIIIa of the periodic table of the elements and a phosphorus-free, polydentate nitrogen compound suitable for complex formation as ligand at temperatures ranging from 50 to 100° C. and pressures from 20 to 1,000 bar and recirculating the catalyst complex in the hydroformylation reaction, wherein a) derivatized polyamines are used that are substantially non-water soluble and suitable for complex formation and have a mean molecular weight of more than 1,000 Dalton and at least 10 nitrogen atoms; b) the catalyst complex remaining in the bottom of the distillation column and the excess ligands obtained from the reaction mixture are recirculated totally or partially in the hydroformylation once the hydroformylation reaction and the separation or partial separation by distillation of the aldehydes and the alcohols has been completed; c) continues or at least batchwise evacuation of at least part of the high boiler from the bottom of the distillation of the reaction mixture is then carried out.
    • 本发明涉及通过在均匀溶解在含有元素周期表第Ⅷa族金属的反应混合物的络合催化剂存在下烯烃的加氢甲酰化生产醛或醛和醇的方法, 在50至100℃的温度和20至1,000巴的压力下适合于络合物形成配位体的多余的多齿氮化合物,并且在加氢甲酰基化反应中再循环催化剂配合物,其中a)使用基本上不相容的衍生的多胺, 水溶性且适合于络合物形成,并且具有大于1,000道尔顿和至少10个氮原子的平均分子量; b)一旦加氢甲酰化反应和通过蒸馏醛和醇的分离或部分分离已经被残留在蒸馏塔底部的催化剂络合物和从反应混合物中得到的过量配体在加氢甲酰化反应中被全部或部分再循环 完成 c)然后执行从反应混合物的蒸馏底部继续或至少间歇抽出高锅炉的至少一部分。
    • 9. 发明申请
    • METHOD FOR HYDROFORMYLATION
    • 氢化方法
    • US20100240896A1
    • 2010-09-23
    • US12741296
    • 2008-11-04
    • Jens RudolphJoachim Schmidt-LeithoffRocco PacielloBernhard BreitTomas Smejkal
    • Jens RudolphJoachim Schmidt-LeithoffRocco PacielloBernhard BreitTomas Smejkal
    • C07C51/373C07F9/28C07D213/04C07F15/00C07F15/06
    • C07F15/008C07F9/5022C07F9/58
    • The present invention relates to a process for the hydroformylation of compounds of the formula (I), where X is C, P(Rx), P(O—Rx) S or S(═O), where Rx is H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; A is a divalent bridging group having from 1 to 4 bridging atoms; and R1 is H, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; or salts thereof; in which the compound of the formula (I) is reacted with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal of transition group VIII with a compound of the formula (II), where Pn is a pnicogen atom; W is a divalent bridging group having from 1 to 8 bridging atoms; R2 is a functional group capable of forming an intermolecular, noncovalent bond with the group —X(═O)OH; R3, R4 are each alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; a, b, c are each 0 or 1; and Y1, Y2 and Y3 are each O, S, NRa or SiRbRc; and also compounds of the formula (II.a), where W′ is a divalent bridging group having from 1 to 5 bridging atoms between the flanking bonds, Z is O, S, S(═O), S(═O)2, N(RIX) or C(RIX)(RX); and RI to RX are each, independently of one another, H, halogen, nitro, cyano, amino, alkyl, etc.; or two radicals RI, RII, RIV, RVI, RVIII and RIX together represent the second part of a double bond.
    • 本发明涉及式(I)化合物加氢甲酰化的方法,其中X为C,P(Rx),P(O-Rx)S或S(= O)),其中Rx为H,烷基, 环烷基,杂环烷基,芳基或杂芳基; A是具有1至4个桥连原子的二价桥连基团; R 1为H,烷基,烯基,炔基,环烷基,杂环烷基,芳基或杂芳基; 或其盐; 其中式(I)的化合物与一氧化碳和氢气在包含过渡族VIII的金属与式(II)的化合物的络合物的存在下反应,其中Pn是酚醛原子; W是具有1至8个桥连原子的二价桥连基团; R2是能够与基团-X(= O)OH形成分子间,非共价键的官能团; R 3,R 4各自为烷基,环烷基,杂环烷基,芳基或杂芳基; a,b,c各自为0或1; Y1,Y2和Y3分别为O,S,NRa或SiRbRc; 以及式(II.a)化合物,其中W'是在侧翼键之间具有1至5个桥连原子的二价桥连基团,Z是O,S,S(= O),S(= O)2 ,N(RIX)或C(RIX)(RX); R 1和R 2各自独立地为H,卤素,硝基,氰基,氨基,烷基等; 或两个基团RI,RII,RIV,RVI,RVIII和RIX一起表示双键的第二部分。