公开(公告)号：JPS577456A

公开(公告)日：1982-01-14

申请号：JP8018080

申请日：1980-06-16

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  TAKAGI USAJI ,  KASUGA TAKAHARU ,  IKEDA KEIICHI

IPC: B01J31/22 ,  B01J31/28

Abstract: PURPOSE:The reaction between an aromatic nitro compound and carbon monoxide is conducted in the presence of a maine catalyst of a noble metal and a cocatalyst of a compound of a metal of VA group at high temperature under high pressure to produce the titled compound used as a raw material of polyurethane directly in high yield. CONSTITUTION:At least one selected from a mixture of a compound of noble metal such as Ru and a heteroaromatic nitrogen compound such a pyrrole, a complex of noble metal coordinated by the above nitrogen compound such as bis(pyridine) dichloropalladium (II) and a mixture of the complex and the nitrogen compound is used as a main catalyst and at least one of cyclopentadienyl halide of transition metal of group VA in the periodic table is used as a cocatalyst to effect the reaction between an aromatic nitro compound such as nitrobenzene and carbon monoxide at high temperature under high pressure, thus producing the titled compound. The addition of the cocatalyst permits the reduction in the main catalyst required to about 1/10 of the amount used in the conventional process and facilitates are recovery.

公开(公告)号：JPS54125604A

公开(公告)日：1979-09-29

申请号：JP3240478

申请日：1978-03-23

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TAKAGI USAJI ,  TSUMURA RIYUUICHIROU ,  MAZAKI TAKAHARU

IPC: C07C205/02 ,  C07C67/00 ,  C07C201/00

Abstract: PURPOSE:To prepare lower nitroparaffins useful as solvents, etc., in high yield without formation of by-products, by reacting easily available, low cost lower alkyl chlorides with an alkali metal nitrite. CONSTITUTION:1-3C Lower alkyl chloride, e.g. methyl chloride or ethyl chloride, and an alkali metal nitrite are reacted in an aprotic organic solvent, to prepare the corresponding lower nitroparaffin. NaNO2 is especially preferable as the alkali metal nitrite, and DMSO or DMF is preferable as the aprotic organic solvent. The molar ratio of alkyl chloride to nitrite is 1 to 1-10. The reaction is usually carried out below 50 deg.C under ordinary pressure.

公开(公告)号：JPS56169649A

公开(公告)日：1981-12-26

申请号：JP7374080

申请日：1980-06-03

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TAKAGI USAJI ,  KASUGA TAKAHARU ,  TSUMURA RIYUUICHIROU

IPC: C07C201/10 ,  B01J31/00 ,  B01J31/02 ,  C07C67/00 ,  C07C201/00 ,  C07C205/02

Abstract: PURPOSE:To obtain the titled compound in high selectivity and in high yield, by reacting an inexpensive lower alkyl chloride as a raw material which exists in an organic phase with an alkali metal salt of nitric acid in a solid phase using a catalyst transferring between phases under mild conditions. CONSTITUTION:A 1-3C lower alkyl chloride is present directly in the absence of a solvent, or is dissolved in a hydrophobic organic solvent so that it exists in the organic phase, while an alkali metal salt of nitric acid is made to exist in solid state directly in a solid phase. The both compounds are reacted using a catalyst transferring between the organic and solid phases, to give a corresponding lower nitroparaffin. A large cyclic polyether, e,g., dibenz-18-crown-6, etc. or a crypstand shown by the formula (l, m, and n are 0-2) may be used as the catalyst transferring between the phases. The reaction temperature is preferably 5-90 deg.C, the pressure is normal pressure to 5kg/cm G, and, if necessary, it may be reduced pressure.

公开(公告)号：JPS5668653A

公开(公告)日：1981-06-09

申请号：JP14448479

申请日：1979-11-09

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  TAKAGI USAJI ,  KASUGA TAKAHARU ,  IKEDA KEIICHI

IPC: C07B61/00 ,  B01J31/00 ,  B01J31/02 ,  B01J31/18 ,  C07C67/00 ,  C07C241/00 ,  C07C265/00

Abstract: PURPOSE:To prepare the titled compound useful as a raw material of polyurethane, easily in high yield, by reacting an aromatic nitro compound with CO in the presence of a main catalyst composed of a platinum-group metal compound and a cocatalyst composed of a specific composite metal oxide under high temperature and pressure. CONSTITUTION:An aromatic isocyanate is prepared by reacting (A) a 6-32C aromatic mono- or poly-nitro compound (e.g. nitrobenzene) with (B) 3mol, based on 1mol of the nitro group, of CO, in the presence of (C) at least one catalyst selected from (a) a mixture of a compound of a platinum group metal (e.g. Ru, Rh, Pd, etc.) and a heteroaromatic-ring nitrogen compound, (b) a complex of a platinum group metal compound and a heteroaromatic-ring nitrogen compound, and (c) a mixture of the above complex and a heteroaromatic-ring nitrogen compound, using (D) a cocatalyst comprising a composite metal oxide composed of Zn and Mo (the atomic ratio of Zn to Mo is 0.01-100), at 100-250 deg.C under a pressure of 50-500kg/cm .

公开(公告)号：JPS56169648A

公开(公告)日：1981-12-26

申请号：JP7373980

申请日：1980-06-03

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TAKAGI USAJI ,  KASUGA TAKAHARU ,  TSUMURA RIYUUICHIROU

IPC: B01J31/00 ,  B01J31/02 ,  C07C67/00 ,  C07C201/00 ,  C07C201/10 ,  C07C205/02

Abstract: PURPOSE:To obtain the titled substance in high selectivity and in high yield, by reacting an inexpensive lower alkyl chloride as a raw material which is made to exist in an organic phase with an aqueous solution of an alkali metal salt of nitrous acid using a catalyst transferring between phases under mild conditions. CONSTITUTION:A 1-3C lower alkyl chloride, e.g., methyl chloride, is present directly in the absence of a solvent, or dissolved in a widely used solvent immiscible with water, e.g., petroleum ether, benzene, etc. so that it exists in the organic phase, while an alkali metal salt of nitrous acid is made into an aqueous solution and the salt is made to exist in the water phase. The both compounds are reacted using a catalyst transferring between the organic and the water phases, to give a corresponding lower nitroparaffin. Various kinds of quaternary ammonium salts, quaternary pyridinium salts, quaternary salts of pyridine homologues, quaternary phosphonium salts, etc. are used as the catalyst transferring between the phases. The reaction temperature is 5-90 deg.C, preferably 15-40 deg.C, and the reaction pressure is properly normal pressure to 5kg/cm G.

公开(公告)号：JPS56138159A

公开(公告)日：1981-10-28

申请号：JP4019080

申请日：1980-03-31

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  TAKAGI USAJI ,  KASUGA TAKAHARU ,  IKEDA KEIICHI

IPC: B01J23/00 ,  B01J23/28 ,  B01J31/00 ,  B01J31/22 ,  C07C67/00 ,  C07C241/00 ,  C07C265/00

Abstract: PURPOSE:To obtain the titled compound useful as a raw material for polyurethane, by reacting an aromatic nitro compound with CO in the presence of a mixture of a platinum group metallic compound with a heterocyclic aromatic nitrogen compound as a catalyst and Mo as a cocatalyst. CONSTITUTION:An aromatic nitro compound, e.g. nitrobenzene, is reacted with CO in the presence of at least one of catalyst selected from (A) a mixture of a platinum group metallic compound with a heterocyclic aromatic nitrogen compound, (B) a complex of the platinum group metallic compound with the heterocyclic aromatic nitrogen compound and (C) a mixture of the complex with the heterocyclic aromatic nitrogen compound and a heteropoly-acid of Mo, e.g. H4(SiMo12O40), as a cocatalyst to give an aromatic isocyanate in high yield industrially and advantageously. EFFECT:The heteropoly-acid of Mo shows improved effect on the activation and stabilization of the catalyst.

公开(公告)号：JPS54160341A

公开(公告)日：1979-12-19

申请号：JP6762978

申请日：1978-06-07

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  TAKAGI USAJI ,  MAZAKI TAKAHARU ,  IKEDA KEIICHI

IPC: B01J31/00 ,  B01J31/02 ,  B01J31/22 ,  C07C67/00 ,  C07C241/00 ,  C07C265/00

Abstract: PURPOSE:To obtain the title compound useful as a raw material for polyurethane in high yield, by reacting an aormatic nitro compound with CO in the presence of a catalyst consisting of a halide of a platinum group metal and a cocatalyst of a specific compound oxide at high temperature and pressure. CONSTITUTION:An aromatic nitro compound, e.g. nitrobenzene, is reacted with CO in the presence of a catalyst consisting of a halide of a platinum group metal, e.g. palladium chloride, and a aromatic heterocyclic nitrogen compound, e.g. pyrrole, and/or their complex, e.g. bis (pyridine)-dichloropalladium (X), and a cocatalyst of a compound oxide, e.g. prepared by calcining a mixture of molybdenum trioxide and copper oxide, of the formula CuO.m Mo On (m is 0.1-100; n is 0-3) at 300-1,000 deg.C, at high temperature and presure to give an isocyanate. EFFECT:Prolonged catalyst life, easy catalyst recovery and economical.

公开(公告)号：JPS5225725A

公开(公告)日：1977-02-25

申请号：JP9976975

申请日：1975-08-19

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  ABE TAKESHI

IPC: C09K19/22 ,  B01J27/00 ,  B01J27/02 ,  B01J31/00 ,  B01J31/02 ,  C07B61/00 ,  C07C67/00 ,  C07C241/00 ,  C07C251/02 ,  C07C251/24

Abstract: PURPOSE:Schiff's bases are easily prepared in high yield by the reaction of aromatic nitro compounds with CO in the presence of selenium compounds as catalysts.

公开(公告)号：JPS5219624A

公开(公告)日：1977-02-15

申请号：JP9605675

申请日：1975-08-07

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  TAKAGI USAJI ,  ABE TAKESHI

IPC: C07B61/00 ,  B01J31/00 ,  B01J31/02 ,  B01J31/16 ,  C07C20060101 ,  C07C67/00 ,  C07C241/00 ,  C07C263/04 ,  C07C265/00 ,  C07C265/12 ,  C07C265/14 ,  C08G18/76

Abstract: PURPOSE:High purity isocyanates are prepared in high yield by the liquid-phase decomposition of carbamic acid esters in teh presence of the metal compound selected from Gp. IB, IIB, etc., dissolved in an inert solvent as a catalyst.

公开(公告)号：JPS5810548A

公开(公告)日：1983-01-21

申请号：JP10628481

申请日：1981-07-09

Applicant: MITSUI TOATSU CHEMICALS

Inventor： TSUMURA RIYUUICHIROU ,  MIYATA KATSUJI ,  TAKAGI USAJI

IPC: C07B61/00 ,  B01J23/00 ,  B01J23/40 ,  B01J27/00 ,  B01J27/10 ,  B01J31/00 ,  B01J31/16 ,  B01J31/18 ,  C07C67/00 ,  C07C241/00 ,  C07C265/00

Abstract: PURPOSE:To prepare the titled compound usefual as a raw material of polyurethane, economically, with easy recovery and reuse of expensive catalyst, by reacting an aromatic nitro compound with CO in the presence of a catalyst composed of a noble metal and a nitrogen compound and a cocatalyst consisting of chlorine. CONSTITUTION:The titled compound is prepared by reacting an aromatic nitro compound with CO at high temperature and pressure, in the presence of a catalyst containing at least one material selected from the group of a mixture of a noble metal or its compound and a hetero-aromatic nitrogen compound, a complex of a noble metal coordinated to said nitrogen compound, and a mixture of said complex and said nitrogen compound, and a cocatalyst consisting of chlorine. The cocatalyst increases the activity and selectivity of the catalyst, and reduces the necessary amount of the expensive noble metal catalyst. since the catalyst can be recovered easily and has low corrosivity, the use of a particular reaction apparatus is not necessary, and the process is extremely economical.