公开(公告)号：US06515165B1

公开(公告)日：2003-02-04

申请号：US09889882

申请日：2001-07-24

Applicant: Keizo Inoue ,  Shinya Nagano ,  Tomohide Ina

Inventor： Keizo Inoue ,  Shinya Nagano ,  Tomohide Ina

IPC: C07C6974

CPC classification number: G03F7/0045 ,  C07C67/14 ,  C07C67/48 ,  C07C69/753 ,  C07C2602/42 ,  C07C2603/74

Abstract: In a process of the present invention for producing a bridged cyclic polycarboxylic acid t-butyl ester, a bridged cyclic polycarboxylic halide of following Formula (1): (wherein ring Z is a bridged cyclic carbon ring; X is a halogen atom; and m denotes an integer of 2 or more, where ring Z may have a substituent) is allowed to react with t-butyl alcohol or its alkali metal salt to thereby yield an ester of following Formula (2): (wherein tBu is a t-butyl group; and ring Z and m have the same meanings as defined above.) This process can commercially efficiently produce a bridged cyclic polycarboxylic acid t-butyl ester. The compound of Formula (1) can be prepared by allowing a bridged cyclic polycarboxylic acid of following Formula (3): (wherein ring Z is a bridged cyclic carbon ring; and m denotes an integer of 2 or more, where ring Z may have a substituent) to react with a halogenating agent.

Abstract translation: 在本发明的制备桥联环状多元羧酸叔丁酯的方法中，具有下式（1）的桥连环状多羧酸卤化物（其中环Z是桥连环碳环; X是卤素原子; m 表示2以上的整数，其中环Z可以具有取代基）与叔丁醇或其碱金属盐反应，从而得到下式（2）的酯:(其中tBu是叔丁基 基团;且环Z和m具有与上述相同的含义。）该方法可商业上有效地制备桥连环状多元羧酸叔丁酯。 式（1）的化合物可以通过使下述式（3）的桥连环状多元羧酸（其中环Z为桥连环状碳环; m表示2以上的整数，其中环Z可以具有 取代基）与卤化剂反应。

公开(公告)号：US06346651B1

公开(公告)日：2002-02-12

申请号：US09482923

申请日：2000-01-14

Applicant: Tomohide Ina ,  Noboru Kamei ,  Hiroyuki Miura

Inventor： Tomohide Ina ,  Noboru Kamei ,  Hiroyuki Miura

IPC: C07C4528

CPC classification number: C07C45/67 ,  B01J8/20 ,  B01J19/002 ,  B01J19/18 ,  B01J31/0235 ,  B01J31/1805 ,  B01J2208/00283 ,  B01J2208/00707 ,  B01J2208/00867 ,  C07C45/34 ,  C07C45/82 ,  C07C49/603

Abstract: &bgr;-isophorone is formed by isomerizing &agr;-isophorone in the presence of an isomerizing catalyst (an aliphatic C5-20 polycarboxylic acid) in an isomerizing-reaction unit 1. The &bgr;-isophorone thus formed is oxidized with oxygen in an inert solvent in the presence of an oxidizing catalyst (a complex salt of a transition metal and an N,N′-disalicylidenediamine) in an oxidizing-reaction unit 2, thereby forming ketoisophorone. After removing a low-boiling point component, which is an impurity (non-conjugated cyclic ketone), from the reaction mixture using a distilling unit 3, a high-boiling component (oxidizing catalyst) is separated in a distilling unit 4, and then ketoisophorone is separated from the solvent in the separation unit 5. Thereafter, the solvent containing 0 to 5,000 ppm (weight basis) of the impurities and substantially free from ketoisophorone is recycled to the oxidizing reaction through a recycling line 6. According to the present invention, the combination of the isomerizing reaction and the oxidizing reaction makes it possible to produce ketoisophorone from &agr;-isophorone while maintaining the activity of the oxydizing catalyst.

Abstract translation: 在异构化反应单元1中异构化催化剂（脂族C 5-20多元羧酸）存在下，通过异构化α-异佛尔酮形成β-异佛尔酮。由此形成的β-异佛尔酮在惰性溶剂中用氧气 在氧化反应单元2中存在氧化催化剂（过渡金属和N，N'-二水杨酸二胺的配盐），从而形成酮异佛尔酮。 使用蒸馏单元3从反应混合物中除去作为杂质（非共轭环酮）的低沸点成分后，在蒸馏单元4中分离高沸点成分（氧化催化剂），然后 在分离单元5中将酮异二酮与溶剂分离。此后，含有0〜5,000ppm（重量）的杂质且基本上不含酮异二酮的溶剂通过再循环管线6再循环至氧化反应。根据本发明 异构化反应和氧化反应的组合使得可以在保持氧化催化剂的活性的同时，从α-异佛尔酮生产酮异二酮。

公开(公告)号：US06528658B1

公开(公告)日：2003-03-04

申请号：US09673568

申请日：2000-10-18

Applicant: Hiroyuki Miura ,  Hitoshi Watanabe ,  Tomohide Ina ,  Hidehiko Nakajima

Inventor： Hiroyuki Miura ,  Hitoshi Watanabe ,  Tomohide Ina ,  Hidehiko Nakajima

IPC: C07D20902

CPC classification number: B01J31/40 ,  B01J31/006 ,  B01J31/0247 ,  B01J2231/70 ,  C07C29/50 ,  C07C45/33 ,  C07C45/82 ,  C07C2601/14 ,  Y02P20/584 ,  C07C35/08 ,  C07C49/403

Abstract: A series of steps of (A) a step for bringing a cycloalkane into contact with molecular oxygen (oxidizing reactor 2) in the presence of an oxidizing catalyst having an imide unit of the following formula (I): wherein X represents oxygen atom or hydroxyl group; (B) a step for separating the catalyst, and by-produced acid component or a derivative thereof from the reaction mixture (filter 3, extracting column 4, hydrolyzing unit 7, saponifying unit 8); and (C) steps for separating the cycloalkane, a cycloalkanol, and a cycloalkanone from the reaction mixture individually (distilling columns 5, 6, 9, and 10) makes it possible to produce cycloalkanones efficiently. A first component (lower-boiling point component) containing the cycloalkane and a second component (higher-boiling point component) containing the cycloalkanone and cycloalkanol may be separated from the reaction mixture, and the cycloalkanone and the cycloalkanol may be separated from the higher-boiling point component. Such production process is capable of providing cycloalkanones with high efficiency.

Abstract translation: （A）在具有下式（I）的酰亚胺单元的氧化催化剂存在下使环烷烃与分子氧（氧化反应器2）接触的步骤的一系列步骤：其中X表示氧原子或羟基 （B）从反应混合物（过滤器3，萃取塔4，水解单元7，皂化单元8）分离催化剂和副产物酸成分或其衍生物的步骤; 和（C）从反应混合物中单独分离环烷烃，环烷醇和环烷酮的步骤（蒸馏塔5,6,9和10）可以有效地制备环烷酮。 含有环烷烃的第一组分（低沸点组分）和含有环烷酮和环烷醇的第二组分（高沸点组分）可以从反应混合物中分离出来，而环烷酮和环烷醇可以从较高级分离出来， 沸点成分。 这种生产方法能够高效地提供环烷酮。

公开(公告)号：US06410797B1

公开(公告)日：2002-06-25

申请号：US09623081

申请日：2000-08-28

Applicant: Tomohide Ina ,  Hiroyuki Miura ,  Ikuo Takahashi

Inventor： Tomohide Ina ,  Hiroyuki Miura ,  Ikuo Takahashi

IPC: C07C4561

CPC classification number: B01J31/2243 ,  B01J2531/0252 ,  B01J2531/72 ,  C07C45/34 ,  C07C45/67 ,  C07C45/82 ,  C07C49/603

Abstract: In the presence of an oxidizing catalyst, a &bgr;-isophorone derivative of the following formula (1) is oxidized in a solvent substantially from acid components (organic carboxylic acids) to form a ketoisophorone derivative of the following formula (2). The amount of the acid component in the solvent is 0 to 4,000 ppm (weight basis). The oxidizing catalyst is a complex salt of a transition metal and an N,N′-disalicylidenediamine. In the reaction, a cyclic base may further be employed as a co-catalyst. The solvent separated from the reaction mixture may be recycled to the oxidation reaction after removal of the acid component contained therein.

Abstract translation: 在氧化催化剂的存在下，下式（1）的β-异佛尔酮衍生物在溶剂中基本上由酸组分（有机羧酸）氧化形成下式（2）的酮 - 异佛尔酮衍生物。 溶剂中的酸成分的量为0〜4,000ppm（以重量计）。 氧化催化剂是过渡金属和N，N'-二脒基二胺的复合盐。 在该反应中，还可以使用环状碱作为助催化剂。 从反应混合物中分离的溶剂可以在除去其中所含的酸成分后再循环到氧化反应中。

公开(公告)号：US5731255A

公开(公告)日：1998-03-24

申请号：US504547

申请日：1995-07-20

Applicant: Li Rui Pan ,  Tomohide Ina ,  Kazuyuki Matsuoka

Inventor： Li Rui Pan ,  Tomohide Ina ,  Kazuyuki Matsuoka

IPC: B01J31/16 ,  B01J31/18 ,  B01J31/24 ,  C07C67/38 ,  C07C37/36 ,  B01J31/00

CPC classification number: B01J31/1616 ,  B01J31/24 ,  B01J31/2404 ,  C07C67/38 ,  B01J2231/321 ,  B01J2531/80 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/828 ,  B01J2531/842 ,  B01J2531/845 ,  B01J2531/847 ,  B01J31/1895

Abstract: A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkyl-sulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.

Abstract translation: 羰基化催化体系包括（A）负载在载体上的（A1）元素周期表第Ⅷ族金属源（例如钯，氯化钯），（A2）配体如三苯基膦和（A3） 一种酸如烷基磺酸，或（B）除了钯（例如铂化合物）之外的（B1）第Ⅷ族金属源，（B2）配体如三苯基膦和（B3）电子的组合 具有不小于2的电子偶联性DELTA nu D的助孕化合物（例如，胺如杂环叔胺）。 催化体系（B）还可以包含（B4）酸，例如甲磺酸。 在催化体系（A）或（B）的存在下，允许炔属或烯属不饱和化合物与一氧化碳和具有活性氢的亲核化合物如水，醇和羧酸在液相中反应 得到具有高转化率和选择性的不饱和或饱和羧酸或其酯。

公开(公告)号：US20060011462A1

公开(公告)日：2006-01-19

申请号：US10528689

申请日：2003-10-03

Applicant: Akira Horiguchi ,  Tomohide Ina ,  Hiroyuki Miura

Inventor： Akira Horiguchi ,  Tomohide Ina ,  Hiroyuki Miura

IPC: B01D3/34 ,  C07C409/24

CPC classification number: C07C51/12 ,  C07C51/44 ,  C07C53/08 ,  C07C53/122

Abstract: In the presence of a catalytic system, an alcohol having “n” carbon atom(s) or a derivative thereof is allowed to react with carbon monoxide in a reactor 3 continuously, a higher bp catalyst component is separated from the resultant reaction mixture by a catalyst-separating column 5 to give a crude mixture, the crude mixture is fed to a higher bp component-separation column 8 to separate an overhead fraction from a bottom fraction containing at least a carboxylic acid having “n+2” carbon atoms, the overhead fraction is fed to a carboxylic acid-separating column 11, and are distilled in the presence of at least water and an ester of the carboxylic acid with the alcohol to separate a overhead fraction containing at least the ester and water from a bottom fraction containing the carboxylic acid having “n+1” carbon atoms. The overhead fraction from the carboxylic acid-separating column is fed to an aldehyde-separating column 14 to remove an overhead fraction containing an aldehyde. Such a process insures that impurities are efficiently separated from a reaction mixture by carbonylation of an alcohol, and that a carboxylic acid is purified easily at a lower cost.

Abstract translation: 在催化体系的存在下，使具有“n”个碳原子的醇或其衍生物的醇在反应器3中连续与一氧化碳反应，将高沸点催化剂组分与所得反应混合物分离， 催化剂分离塔5以得到粗混合物，将粗混合物加入到较高沸点成分分离塔8中，以分离塔塔馏分与至少含有“n + 2”碳原子的羧酸的塔底馏分， 将塔顶馏分进料到羧酸分离塔11中，并在至少水和羧酸的​​酯存在下与醇蒸馏，以从含有至少含有酯和水的塔底馏分分离含有 具有“n + 1”个碳原子的羧酸。 将来自羧酸分离塔的塔顶馏分进料到醛分离塔14以除去含有醛的塔顶馏分。 这样的方法确保通过醇的羰基化有效地将杂质与反应混合物分离，并且以较低的成本容易地提纯羧酸。

公开(公告)号：US5869738A

公开(公告)日：1999-02-09

申请号：US965487

申请日：1997-11-06

Applicant: Li Rui Pan ,  Tomohide Ina ,  Kazuyuki Matsuoka

Inventor： Li Rui Pan ,  Tomohide Ina ,  Kazuyuki Matsuoka

IPC: B01J31/16 ,  B01J31/18 ,  B01J31/24 ,  C07C67/38 ,  C07C67/36

CPC classification number: B01J31/1616 ,  B01J31/24 ,  B01J31/2404 ,  C07C67/38 ,  B01J2231/321 ,  B01J2531/80 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/828 ,  B01J2531/842 ,  B01J2531/845 ,  B01J2531/847 ,  B01J31/1895

Abstract: A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkylsulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.

Abstract translation: 羰基化催化体系包括（A）负载在载体上的（A1）元素周期表第Ⅷ族金属源（例如钯，氯化钯），（A2）配体如三苯基膦和（A3） 一种酸如烷基磺酸，或（B）除了钯（例如铂化合物）之外的（B1）第Ⅷ族金属源，（B2）三苯基膦等配体和（B3）给电子化合物 具有不小于2的电子供体DELTA nu D（例如胺如杂环叔胺）。 催化体系（B）还可以包含（B4）酸，例如甲磺酸。 在催化体系（A）或（B）的存在下，允许炔属或烯属不饱和化合物与一氧化碳和具有活性氢的亲核化合物如水，醇和羧酸在液相中反应 得到具有高转化率和选择性的不饱和或饱和羧酸或其酯。

公开(公告)号：US06642419B1

公开(公告)日：2003-11-04

申请号：US09673564

申请日：2000-10-18

Applicant: Hiroyuki Miura ,  Hitoshi Watanabe ,  Tomohide Ina ,  Hidehiko Nakajima

Inventor： Hiroyuki Miura ,  Hitoshi Watanabe ,  Tomohide Ina ,  Hidehiko Nakajima

IPC: C07C4500

CPC classification number: B01J31/0247 ,  B01J31/006 ,  B01J31/2208 ,  B01J2231/70 ,  B01J2531/845 ,  C07C45/33 ,  C07C49/403

Abstract: In the presence of (1) an oxidizing catalyst comprising an imide compound such as N-hydroxyphthalimide, or (2) an oxidizing catalyst comprising such imide compound and a transition metal element-containing compound as a co-oxidizing agent (e. g., oxides, halides, complexes, hetero polyacid salts) a hydrocaron, an alcohol, an aldehyde, or a ketone as a substrate is brought into contact with molecular oxygen for oxidation. In the above-described oxidation process, the water content of the oxidizing reaction system is 200 mol or lower relative to 1 mol of the imide compound. According to the present invention, a substrate is efficiently oxidized with molecular oxygen under mild conditions, and there can be obtained the object compound(s) of high quality.

Abstract translation: 在（1）包含酰亚胺化合物如N-羟基邻苯二甲酰亚胺的氧化催化剂的存在下，或（2）包含这种酰亚胺化合物的氧化催化剂和作为助氧化剂的过渡金属元素化合物（例如氧化物， 卤化物，络合物，杂多酸盐）作为底物的烃类，醇，醛或酮与分子氧接触以进行氧化。 在上述氧化方法中，氧化反应体系的水分相对于1摩尔酰亚胺化合物为200摩尔或更低。 根据本发明，在温和条件下，用分子氧有效地氧化底物，可以得到高质量的目标化合物。

公开(公告)号：US06369263B1

公开(公告)日：2002-04-09

申请号：US09623135

申请日：2000-08-28

Applicant: Tomohide Ina

Inventor： Tomohide Ina

IPC: C07C6748

CPC classification number: C07C67/52 ,  C07C67/00 ,  C07C69/017 ,  C07C69/16

Abstract: A hydroquinone diester derivative represented by the formula (1): wherein R1 and R2 are the same or different, each representing an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group is crystallized from a reaction mixture containing the hydroquinone diester derivative, and the resulting product in crystallized form is washed. A solvent for the crystallization is composed of an organic carboxylic acid and water, and the crystallized product is washed with warm or hot water of 40° C. or above. In the formula (1), R1 and R2 are C1-4alkyl groups.

Abstract translation: 由式（1）表示的氢醌二酯衍生物：其中R 1和R 2相同或不同，各自代表烷基，环烷基，芳基或杂环基，从含有氢醌二酯衍生物的反应混合物中结晶 洗涤结晶形式的产物。 用于结晶的溶剂由有机羧酸和水组成，结晶产物用40℃或更高的温水或热水洗涤。 在式（1）中，R 1和R 2是C 1-4烷基。