公开(公告)号：US4510331A

公开(公告)日：1985-04-09

申请号：US390984

申请日：1982-06-22

Applicant: Noriaki Yoshimura ,  Masuhiko Tamura

Inventor： Noriaki Yoshimura ,  Masuhiko Tamura

IPC: C07C29/141 ,  C07C29/17 ,  C07C31/125 ,  C07C33/025 ,  C07C45/51 ,  C07C45/62 ,  C07C47/21 ,  C07C51/235 ,  C07C51/363 ,  C07C209/26 ,  C07C227/08 ,  C07C45/67

CPC classification number: C07C255/00 ,  C07C209/26 ,  C07C227/08 ,  C07C29/141 ,  C07C29/175 ,  C07C31/125 ,  C07C33/025 ,  C07C45/512 ,  C07C45/62 ,  C07C51/235 ,  C07C51/363

Abstract: There are disclosed a process for producing 7-octen-1-al which comprises isomerizing 2,7-octadien-1-ol in the presence of a catalyst comprising oxides of at least two metals selected from the group consisting of copper, chromium and zinc and processes for producing derivatives of 7-octen-1-al.

Abstract translation: 公开了一种生产7-辛烯-1-al的方法，该方法包括在包含选自铜，铬和锌的至少两种金属的氧化物的催化剂存在下异构化2,7-辛二烯-1-醇 以及制备7-辛烯-1-基的衍生物的方法。

公开(公告)号：US4306087A

公开(公告)日：1981-12-15

申请号：US175842

申请日：1980-08-06

Applicant: Mitsuo Matsumoto ,  Masuhiko Tamura

Inventor： Mitsuo Matsumoto ,  Masuhiko Tamura

IPC: B01J31/00 ,  B01J31/24 ,  B01J31/28 ,  C07B61/00 ,  C07C45/00 ,  C07C45/49 ,  C07C45/50 ,  C07C67/00 ,  C07C47/02

CPC classification number: B01J31/2404 ,  B01J31/185 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/2457 ,  C07C45/49 ,  C07C45/50 ,  B01J2231/321 ,  B01J2531/822 ,  B01J31/20

Abstract: In hydroformylating an olefinic compound in an organic solvent and in the presence of a rhodium complex and a trisubstituted phosphine to give the corresponding aldehyde, at least one diphosphino compound of the following general formula (I) is added to the reaction system in a proportion of 0.20 to 5.0 equivalents per rhodium atom in the rhodium complex ##STR1## wherein A.sup.1 and A.sup.2, respectively, are aryl groups; R.sup.1 and R.sup.2, respectively, are an aryl group or a saturated hydrocarbon residue containing 1 or more carbon atoms; and ##STR2## represents a substituted or unsubstituted alicyclic hydrocarbon group containing 3 to 6 carbon atoms in the main ring.The addition of diphosphino compound (I) has a remarkable life-prolonging effect on the rhodium catalyst.

Abstract translation: 在有机溶剂中，在铑络合物和三取代膦的存在下，将烯属化合物加氢甲酰化，得到相应的醛，将至少一种下列通式（I）的二膦化合物以一定比例的 铑络合物中的铑原子为0.20〜5.0当量（I）其中A1和A2分别为芳基; R1和R2分别是含有1个或更多个碳原子的芳基或饱和烃基; 在该主环中，“IMAGE”表示含有3〜6个碳原子的取代或未取代的脂环族烃基。 二膦化合物（I）的添加对铑催化剂具有显着的延长寿命。

公开(公告)号：US4052442A

公开(公告)日：1977-10-04

申请号：US608756

申请日：1967-01-12

Applicant: Masuhiko Tamura ,  Teruo Yasui

Inventor： Masuhiko Tamura ,  Teruo Yasui

IPC: C07C69/16 ,  C07C69/28 ,  C07C67/05

CPC classification number: C07C67/055

Abstract: A process for preparing glycol esters such as ethylene glycol diacetate which comprises contacting a monoolefin such as ethylene with an organic monocarboxylic acid such as acetic acid containing a palladous salt and either a nitrate or a nitrite.

公开(公告)号：US4301083A

公开(公告)日：1981-11-17

申请号：US109065

申请日：1980-01-02

Applicant: Noriaki Yoshimura ,  Masuhiko Tamura

Inventor： Noriaki Yoshimura ,  Masuhiko Tamura

IPC: C07C41/16 ,  C07C43/11 ,  C07C43/184 ,  C07C43/235 ,  C07C41/00 ,  C09F5/00

CPC classification number: C07C41/16 ,  C07C213/06 ,  C07C231/12 ,  C07C43/11 ,  C08G65/337

Abstract: Polyoxyalkylene compounds having at least four oxyalkylene units and one or two terminal hydroxyl groups are etherified by reacting same with organic primary chlorides or bromides in the presence of an aqueous, at least 30% by weight solution of sodium or potassium hydroxide to produce the corresponding etherified polyoxyalkylene derivatives. The molar ratio of the organohalide to the hydroxyl group(s) of the polyoxyalkylene compound is at least 1.2, and the molar ratio of the alkali metal hydroxide to such hydroxyl group(s) is at least 1.

Abstract translation: 具有至少四个氧化烯单元和一个或两个末端羟基的聚氧化烯化合物在含水，至少30重量％的氢氧化钠或氢氧化钾溶液的存在下，与有机一级氯化物或溴化物反应而醚化，产生相应的醚化 聚氧化烯衍生物。 有机卤化物与聚氧化烯化合物的羟基的摩尔比为1.2以上，碱金属氢氧化物与该羟基的摩尔比为1以上。

公开(公告)号：US4271320A

公开(公告)日：1981-06-02

申请号：US71670

申请日：1979-08-31

Applicant: Yasuo Tokitoh ,  Noriaki Yoshimura ,  Masuhiko Tamura

Inventor： Yasuo Tokitoh ,  Noriaki Yoshimura ,  Masuhiko Tamura

IPC: C07C29/141 ,  C07C45/30 ,  C07C45/34 ,  C07C45/80 ,  C07C45/83 ,  C07C29/136 ,  C07C29/14 ,  C07C45/27 ,  C07C45/36

CPC classification number: C07C45/80 ,  C07C29/141 ,  C07C45/30 ,  C07C45/34 ,  C07C45/83 ,  Y02P20/584

Abstract: An industrially suitable process for producing a higher carbonyl compound by the oxidation of an olefinic compound having at least six carbon atoms is provided. Said improved process comprises oxidizing the olefinic compound in aqueous medium containing palladium or salt thereof and a copper salt in the presence of a specific water-soluble polyoxyalkylene compound in an amount of from about 1/4 to about 3 parts by weight per 1 part by weight of water contained in the reaction mixture. The improvement is demonstrated in terms of yield, selectivity, separation of the product, and recycle of the catalyst.

Abstract translation: 提供了通过氧化具有至少6个碳原子的烯属化合物来生产高级羰基化合物的工业上合适的方法。 所述改进的方法包括在特定水溶性聚氧化烯化合物存在下，将含有钯或其盐和铜盐的水性介质中的烯烃化合物氧化为约1/3〜3重量份/ 1份/ 包含在反应混合物中的水的重量。 在产率，选择性，产物分离和催化剂循环方面证明了改进。

公开(公告)号：US4215077A

公开(公告)日：1980-07-29

申请号：US7660

申请日：1979-01-29

Applicant: Mitsuo Matsumoto ,  Masuhiko Tamura

Inventor： Mitsuo Matsumoto ,  Masuhiko Tamura

IPC: C07C29/16 ,  C07C45/49 ,  C07C45/50 ,  C07C45/80 ,  C07F9/50 ,  C07C45/10

CPC classification number: C07F9/5027 ,  C07C29/16 ,  C07C45/49 ,  C07C45/50 ,  C07C45/80

Abstract: Hydroformylation of olefins is effected in an organic solvent in the presence of a rhodium complex and a trisubstituted phosphine to give the corresponding aldehydes. Addition of a diphosphinoalkane of the general formula ##STR1## wherein, in the formula, A.sup.1 and A.sup.2 are each aryl, R.sup.1 and R.sup.2 are each aryl or saturated hydrocarbon residues containing one or more carbon atoms, and Z is an alkylene radical whose principal chain contains 2 to 5 carbon atoms and optionally may have one or more lower alkyl substituents, to the hydroformylation reaction system in an amount of 0.20 to 2.5 equivalents per gram atom of the rhodium contained in the rhodium complex markedly prolongs the life of the rhodium catalyst.

Abstract translation: 烯烃的加氢甲酰化在有机溶剂中，在铑络合物和三取代膦存在下进行，得到相应的醛。 加入通式为“IMAGE”的二膦酰基烷烃，式中，A1和A2各自为芳基，R1和R2分别为含有一个或多个碳原子的芳基或饱和烃基，Z为主链 含有2-5个碳原子，并且任选地可以具有一个或多个低级烷基取代基，其加氢甲酰化反应体系的含量为0.20-2.5当量/克原子的铑络合物中所含的铑显着地延长了铑催化剂的寿命。

公开(公告)号：US4723036A

公开(公告)日：1988-02-02

申请号：US430694

申请日：1982-09-30

Applicant: Takanori Kitamura ,  Masuhiko Tamura

Inventor： Takanori Kitamura ,  Masuhiko Tamura

IPC: C07C69/16 ,  C07C67/44

CPC classification number: C07C69/16 ,  Y02P20/584

Abstract: There is provided a process for producing propylene glycol monoacetate which comprises the steps of(I) hydroformylating vinyl acetate with a gaseous mixture of hydrogen and carbon monoxide in an organic solvent in the presence of a substantially water-insoluble rhodium complex and a tri-substituted phosphine to form .alpha.-acetoxypropionaldehyde,(II) subjecting at least part of the reaction mixture obtained in step (I) to extraction with an aqueous medium to obtain an aqueous layer containing .alpha.-acetoxypropionaldehyde and an extraction residue containing the catalyst components, and recycling the extraction residue to the hydroformylation step (I),(III) contacting the aqueous layer containing .alpha.-acetoxypropionaldehyde obtained in step (II) with a carboxylic acid ester of general formula (A)C.sub.l H.sub.2l+1 COOC.sub.m H.sub.2m+1 (A) wherein l is an integer of 0 to 4; m is an integer of 1 to 5; and the sum of l and m is 3 to 5, or a dicarboxylic acid ester of general formula (B)ROOC(CH.sub.2).sub.n COOR' (B) wherein R and R' each is an alkyl group of 2 to 3 carbon atoms; and n is an integer of 0 to 2 to thereby separate .alpha.-acetoxypropionaldehyde extractively from the aqueous layer, and(IV) hydrogenating the .alpha.-acetoxypropionaldehyde contained in the extract layer as obtained in step (III) in liquid phase in the presence of a Raney nickel or modified Raney nickel catalyst under conditions such that the concentration of .alpha.-acetoxypropionaldehyde in the reaction mixture does not exceed 0.1 mole per liter.Further provided is an improved process for hydrogenating .alpha.-acetoxypropionaldehyde which is advantageously employable in the above step (IV).

Abstract translation: 提供了一种生产丙二醇单乙酸酯的方法，其包括以下步骤：（I）在基本上不溶于水的铑络合物和三取代的存在下，在有机溶剂中，用氢气和一氧化碳的气体混合物将乙酸乙烯酯加氢甲酰化 膦以形成α-乙酰氧基丙醛，（II）使步骤（I）中获得的至少一部分反应混合物用水性介质萃取以获得含有α-乙酰氧基丙醛的水层和含有催化剂组分的萃取残余物，以及再循环 将步骤（II）中获得的含有α-乙酰氧基丙醛的水层与通式（A）ClHI1 + 1COOCmH2m + 1（A）的羧酸酯接触的加氢甲酰化步骤（I），（III）的提取残余物与（III） 0〜4的整数; m为1〜5的整数。 1和m的总和为3〜5，或通式（B）的ROOC（CH 2）n COOR'（B）的二羧酸酯，其中R和R'各自为2〜3个碳原子的烷基; n为0〜2的整数，由此从水层中提取出α-乙酰氧基丙醛，（IV）在步骤（III）中得到的步骤（III）中得到的α-乙酰氧基丙醛氢化， 阮内镍或改性阮内镍催化剂，使得反应混合物中α-乙酰氧基丙醛的浓度不超过0.1摩尔/升。 进一步提供一种用于氢化α-乙酰氧基丙醛的改进方法，其有利于在上述步骤（IV）中使用。

公开(公告)号：US4334117A

公开(公告)日：1982-06-08

申请号：US183500

申请日：1980-09-04

Applicant: Noriaki Yoshimura ,  Masuhiko Tamura

Inventor： Noriaki Yoshimura ,  Masuhiko Tamura

IPC: B01J31/00 ,  B01J31/24 ,  C07B61/00 ,  C07C1/00 ,  C07C2/74 ,  C07C11/12 ,  C07C67/00

CPC classification number: B01J31/0237 ,  B01J31/189 ,  B01J31/2404 ,  C07C2/74 ,  B01J2231/323 ,  B01J2531/824 ,  B01J2531/828 ,  B01J2531/90 ,  B01J2540/32 ,  C07C2523/42 ,  C07C2523/44 ,  C07C2531/24 ,  Y02P20/584

Abstract: This invention provides an improved process for producing alkadienes which comprises (1) contacting butadiene or isoprene with a catalyst such as platinum or palladium or a compound of one of said metals in a sulfolane solution, in the presence of a tertiary lower alkylamine formate and at least one phosphine compound of the formula: ##STR1## wherein R.sup.1 is a substituted or unsubstituted C.sub.1-10 hydrocarbon group; R.sup.2 is H, a saturated aliphatic C.sub.1-5 hydrocarbon group, nitro or halogen; m is 1, 2 or 3; n is 0 or 1; x is 0, 1 or 2; y and z each is 0, 1, 2 or 3 (provided that y and z are not zero concurrently and x+y+z=3); A is --SO.sub.3 M wherein M is a cation selected from among H, alkali metals, alkaline earth metals and NH.sub.4 or the formate or an inorganic acid salt of ##STR2## wherein R.sup.3 and R.sup.4 each means a saturated aliphatic C.sub.1-4 hydrocarbon group in an amount of 4 to 200 moles per gram atom of the metal constituting the catalyst to form dimeric alkadienes; (2) separating the reaction mixture into an alkadiene-containing layer and a catalyst-containing layer; and (3) recycling the catalyst-containing layer to the alkadiene production process. The improved process makes it possible to maintain the catalytic activity over a prolonged period of time and to facilitate separation and reuse of the catalyst.

Abstract translation: 本发明提供了一种生产链烷二烯的改进方法，其包括（1）在叔低级烷基胺甲酸盐存在下，将丁二烯或异戊二烯与催化剂如铂或钯或其中一种金属的化合物在环丁砜溶液中接触，并在 至少一种下式的膦化合物：其中R 1是取代或未取代的C 1-10烃基; R2是H，饱和脂族C 1-5烃基，硝基或卤素; m为1,2或3; n为0或1; x是0,1或2; y和z各自为0,1,2或3（假设y和z不同时为零，x + y + z = 3）; A是-SO 3 M，其中M是选自H，碱金属，碱土金属和NH 4的阳离子，或者其中R 3和R 4各自表示饱和脂族C 1-4烃基， 量为4〜200摩尔/克原子构成催化剂的金属，形成二聚二链烷二烯; （2）将反应混合物分离成含链二烯的层和含催化剂的层; 和（3）将含催化剂的层再循环到二烯烃生产过程中。 改进的方法使得可以在更长的时间内保持催化活性，并促进催化剂的分离和再利用。

公开(公告)号：US4214111A

公开(公告)日：1980-07-22

申请号：US958144

申请日：1978-11-06

Applicant: Takanori Kitamura ,  Masuhiko Tamura

Inventor： Takanori Kitamura ,  Masuhiko Tamura

IPC: C07C2/22 ,  C07C3/18 ,  C07C5/04

CPC classification number: C07C2/22

Abstract: A method of producing liquid hydrocarbons useful e.g. as lubricants or base oils for cosmetics is disclosed. The method comprises copolymerizing in the presence of an aluminum halide catalyst (i) at least one alpha-olefin having a terminal vinyl group and containing 6 to 14 carbon atoms, (ii) isobutylene and/or diisobutylene, and optionally (iii) 1-butene, coexisting in a specified ratio, and optionally hydrogenating the resulting polymer.

Abstract translation: 一种生产液体烃的方法，例如有用的。 公开了用于化妆品的润滑剂或基础油。 该方法包括在卤化铝催化剂（i）至少一种具有末端乙烯基并含有6至14个碳原子的α-烯烃的存在下共聚合，（ii）异丁烯和/或二异丁烯，以及任选的（iii）1- 丁烯，以规定的比例共存，并任选地氢化所得聚合物。

公开(公告)号：US4500727A

公开(公告)日：1985-02-19

申请号：US359414

申请日：1982-03-18

Applicant: Takanori Kitamura ,  Mitsuo Matsumoto ,  Masuhiko Tamura

Inventor： Takanori Kitamura ,  Mitsuo Matsumoto ,  Masuhiko Tamura

IPC: C07C67/03 ,  C07C69/14 ,  C07C69/24 ,  C07C69/68

CPC classification number: C07C67/293 ,  C07C67/03 ,  C07C67/29 ,  C07C67/30 ,  Y02P20/584

Abstract: A process for producing methyl lactate by (I) hydroformylating vinyl acetate or vinyl propionate with a gaseous mixture of hydrogen and carbon monoxide in an organic solvent in the presence of a substantially water-insoluble rhodium complex and a tri-substituted phosphine to form .alpha.-acetoxy- or propionyloxy-propionaldehyde, (II) subjecting at least part of the reaction mixture obtained in step (I) to extraction with an aqueous medium to obtain an aqueous layer containing .alpha.-acetoxy- or propionyloxy-propionaldehyde and an extraction residue containing the catalyst components, and recycling the extraction residue to the hydroformylation step (I), (III) separating .alpha.-acetoxy- or propionyloxy-propionaldehyde from the aqueous layer containing the same as obtained in step (II), (IV) oxidizing .alpha.-acetoxy- or propionyloxy-propionaldehyde obtained in step (III) in the liquid phase with oxygen gas or an oxygen-containing gas in the presence of an oxidation catalyst to form .alpha.-acetoxy- or propionyloxy-propionic acid, and (V) reacting .alpha.-acetoxy- or propionyloxy-propionic acid obtained in step (IV) with methanol in the presence of an acid catalyst, and recovering the resultant methyl lactate by distillation.

Abstract translation: （I）在有机溶剂中，在基本上不溶于水的铑络合物和三取代的膦存在下，通过（I）在氢气和一氧化碳的气体混合物中将乙酸乙烯酯或丙酸乙烯酯加氢甲酰化以生产甲酸乳酸的方法， 乙酰氧基 - 或丙酰氧基 - 丙醛，（II）使步骤（I）中获得的反应混合物的至少一部分用水性介质萃取，得到含有α-乙酰氧基或丙酰氧基丙醛的水层和含有 催化剂组分，并将提取残余物循环到加氢甲酰化步骤（I）中，（III）从含有与步骤（II）中获得的相同的水层分离α-乙酰氧基或丙酰氧基丙醛，（IV）氧化α-乙酰氧基 - 或步骤（III）中获得的丙酰氧基 - 丙醛在氧气或含氧气体的液相中，在氧化催化剂存在下形成α - 乙酰氧基 - 或丙酰氧基 - 丙酸，和（V）使在步骤（IV）中获得的α-乙酰氧基 - 或丙酰氧基 - 丙酸与甲醇在酸催化剂存在下反应，并通过蒸馏回收得到的乳酸甲酯。