公开(公告)号：DE69017170D1

公开(公告)日：1995-03-30

申请号：DE69017170

申请日：1990-12-24

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  NAKAYAMA HITOSHI ,  WADA MASARU ,  NAGATA TERUYUKI ,  YAMAGUCHI AKIHIRO

IPC: C07C201/12 ,  C07C205/38 ,  C07C315/04 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: A preparation process of a bis(3-nitrophenoxy) compound represented by the formula: wherein X is a direct bond, divalent hydrocarbon having from 1 to 10 carbon atoms or a divalent group selected from -C(CF3 )2-, -CO-, -S-, -SO-, SO2- or -O-, which comprises reacting 4,4'-bisphenol with m-dinitrobenzene in the presence of an alkali metal carbonate or alkali metal hydrogen carbonate having a particle size of 250 mu m or less while removing generated water from the reaction system during the reaction. In one embodiment of the process, the reaction is carried out while simultaneously adding 4,4'-bisphenol and m-dinitrobenzene to a reaction vessel which was previously charged with the base and an aprotic polar solvent.

公开(公告)号：DE69017170T2

公开(公告)日：1995-07-27

申请号：DE69017170

申请日：1990-12-24

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  NAKAYAMA HITOSHI ,  WADA MASARU ,  NAGATA TERUYUKI ,  YAMAGUCHI AKIHIRO

IPC: C07C201/12 ,  C07C205/38 ,  C07C315/04 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: A preparation process of a bis(3-nitrophenoxy) compound represented by the formula: wherein X is a direct bond, divalent hydrocarbon having from 1 to 10 carbon atoms or a divalent group selected from -C(CF3 )2-, -CO-, -S-, -SO-, SO2- or -O-, which comprises reacting 4,4'-bisphenol with m-dinitrobenzene in the presence of an alkali metal carbonate or alkali metal hydrogen carbonate having a particle size of 250 mu m or less while removing generated water from the reaction system during the reaction. In one embodiment of the process, the reaction is carried out while simultaneously adding 4,4'-bisphenol and m-dinitrobenzene to a reaction vessel which was previously charged with the base and an aprotic polar solvent.

公开(公告)号：JPH04202175A

公开(公告)日：1992-07-22

申请号：JP33002090

申请日：1990-11-30

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  OE TADAYUKI ,  KASE MOTOHIRO ,  YAMAGUCHI TERUHIRO

IPC: C07C319/20 ,  C07C319/14 ,  C07C321/14 ,  C07C321/18 ,  C08K5/36 ,  C08K5/37

Abstract: NEW MATERIAL:The compound of formula I (R is 8-30C aliphatic hydrocarbon group). USE:A resin modifier, a stabilizer, a mold-releasing agent for thermosetting resins such as unsaturated polyester and epoxy resin, etc. PREPARATION:The objective compound of formula I can be produced by reacting a mercapto compound of formula II with a halogenated compound of formula III (X is halogen) in the presence of a base (e.g. NaOH, KOH, NaHCO3 and Na2CO3). The amount of the base is >=3 mol, preferably 3-4mol based on 1mol of the compound of formula II. The compound of formula I is easily soluble in organic solvent and is excellent e.g. as a mold-releasing agent for the molding of a resin.

公开(公告)号：JPH04202162A

公开(公告)日：1992-07-22

申请号：JP32997590

申请日：1990-11-30

Applicant: MITSUI TOATSU CHEMICALS

Inventor： OE TADAYUKI ,  MATSUO MITSUKI ,  YAMAGUCHI TERUHIRO ,  KASE MOTOHIRO

IPC: C07C209/08 ,  C07C211/14 ,  C08K5/17

Abstract: NEW MATERIAL:A compound shown by formula I (R is 8-24C aliphatic saturated or unsaturated hydrocarbon group; R is 1-5C alkyl; (n) is 1-10; (m) is 0-5). EXAMPLE:N,N'-Dimethyl-N,N'-distearylethylenediamine. USE:The compound shown by formula I shows ready solubility in resin raw materials and organic solvents, useful as a mold release material, especially as an internal mold release agent. PREPARATION:A secondary amine shown by formula II is allowed to react with an alkyl halide shown by the formula R-X (X is halogen) in the presence of a dehydrohalogenating agent to give the objective compound shown by formula I.

公开(公告)号：JPH0477457A

公开(公告)日：1992-03-11

申请号：JP19072590

申请日：1990-07-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  WADA MASARU ,  NAGATA TERUYUKI ,  YAMAGUCHI TERUHIRO

IPC: C07C201/08 ,  C07C205/06

Abstract: PURPOSE:To industrially advantageously obtain the subject compound in high yield with suppressing side reaction without requiring an excessive cooling equipment by performing a nitration reaction by simultaneously adding an indane derivative and a mixed acid into a reactor previously charged with a reaction solvent. CONSTITUTION:A reaction solvent such as 1,2-dichloroethane inert to well-known nitration agents is previously charged to a reactor and a nitration reaction is performed by simultaneously adding an indane derivative expressed by formula I (R1 and R2 are H or 1-4C lower alkyl) obtained by a reaction of a benzene derivative and isoprene in the presence of an acid catalyst and a mixed acid of sulfuric acid and nitric acid containing >=74% sulfuric acid preferably keeping at -20 deg.C to 0 deg.C to afford the objective compound expressed by formula II, useful as a raw material for producing a diaminoindane derivative as a raw material of isocyanate, epoxy resin and bismaleimide, etc., or as a hardener of polyurethane. 2-2.2 times mol of said nitric acid is used to 1mol of the compound expressed by formula I.

公开(公告)号：JPH04108767A

公开(公告)日：1992-04-09

申请号：JP22258490

申请日：1990-08-27

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MINAZU HIROSHI ,  KASE MOTOHIRO ,  NAKAYAMA HITOSHI ,  WATANABE KATSUJI ,  WADA MASARU ,  NAGATA TERUYUKI

IPC: B01J23/40 ,  B01J27/053 ,  B01J27/232 ,  C07B61/00 ,  C07C213/00 ,  C07C217/90 ,  C07C315/04 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: PURPOSE:To obtain the title compound useful as a raw material component for heat-resistant high polymer in high purity and good yield by subjecting a bis(3-nitrophenoxy) compound to catalytic reduction while adding the above- mentioned compound to a reactor in which an aprotic polar solvent and carried platinum group catalyst are charged. CONSTITUTION:A compound expressed by formula I [X is 1-10C divalent hydrocarbon group, C(CF3)2, CO, S, SO, SO2 or single bond] is reacted, by adding thereof in a rate corresponding to the progress of reaction, to a reactor in which an aprotic solvent and a platinum group catalyst carried on a support (preferably alumina or magnesium oxide) consisting of a metal oxide, sulfate and carbonate are previously charged, at ordinary pressure to a slight pressurization of about 1000mmH2 at 50-100 deg.C to provide the objective compound. According to the above-mentioned method, nitroso and hydroxylamine concentration in the system is maintained in low state and the subsidiary production of an azo compound by condensation of these compounds can be suppressed and filtration leakage of the catalyst is prevented.

公开(公告)号：JPH04103564A

公开(公告)日：1992-04-06

申请号：JP22105490

申请日：1990-08-24

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MINAZU HIROSHI ,  KASE MOTOHIRO ,  NAKAYAMA HITOSHI ,  WATANABE KATSUJI ,  WADA MASARU ,  NAGATA TERUYUKI

IPC: B01J25/00 ,  C07B61/00 ,  C07C213/00 ,  C07C217/90 ,  C07C315/04 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: PURPOSE:To obtain the high-purity title compound in good yield and suppressed subsidiary production of an azo compound without filtration leak of a catalyst by subjecting a bis(3-nitrophenoxy) compound to catalytic reduction while adding the above- mentioned compound to a reactor in which a Raney nickel catalyst and reaction solvent are previously charged. CONSTITUTION:When a compound expressed by formula I [X is 1-10C bivalent hydrocarbon group, C(CF3)2, CO, S, SO, SO2, O or single bond] is subjected to catalytic reduction, the reaction is carried out by using a Raney nickel catalyst, while adding said compound I to a reactor in which the reaction solvent and the catalyst are previously charged. The temperature of the reaction is controlled at 50-100 deg.C and of the pressure at ordinary pressure to a slight pressurization of about 1000mmH2O by an addition rate of said compound I corresponding to the reaction rate to provide the compound expressed by formula II in suppressed subsidiary production of an azo compound which is difficult to remove. The addition of the compound expressed by formula I is preferably carried out for >=45hr in the case of reaction temperature at 50 deg.C and for >=2hr in the case of reaction temperature at 85 deg.C. The compound expressed by formula II is important as a monomer component for heat resistant high polymer.

公开(公告)号：JPH0469369A

公开(公告)日：1992-03-04

申请号：JP18153790

申请日：1990-07-11

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  MINAZU HIROSHI ,  NAKAYAMA HITOSHI ,  WATANABE KATSUJI ,  WADA MASARU ,  NAGATA TERUYUKI

IPC: B01J23/40 ,  B01J23/70 ,  C07B61/00 ,  C07C213/02 ,  C07C217/90 ,  C07C315/04 ,  C07C317/12 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: PURPOSE:To prepare the subject compound in high purity and yield while inhibiting the by-production of azo components by charging hydrogen gas and simultaneously adding a bis(3-nitrophenoxy)compound into a reactor into which a reaction solvent and a catalyst are preliminarily charged. CONSTITUTION:When a compound of formula I [X is 1-10C divalent hydrocarbon group, C(CF3)2, CO, S, SO, SO2, O, single bond] is catalytically reduced, a reaction solvent and a hydrogenation catalyst are preliminarily charged to a reactor and a raw material compound of formula I is added into the reactor as a rate corresponding to the reaction rate with stirring, while the concentrations of nitroso compounds and hydroxylamine are controlled in low states to inhibit the by-production of azo compounds, thereby providing compound of formula II in good purity and high yield. The compound of formula II is important as a monomer for heat-resistant polymers, especially as a raw material for polyamides, polyimides, polyamideimides, etc.

公开(公告)号：JPH0477458A

公开(公告)日：1992-03-11

申请号：JP19072690

申请日：1990-07-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  WADA MASARU ,  NAGATA TERUYUKI ,  YAMAGUCHI TERUHIRO

IPC: C07C201/08 ,  C07C205/06

Abstract: PURPOSE:To obtain the subject compound in high yield without requiring an excessive cooling equipment by charging a reaction solvent in a reactor in advance and simultaneously adding 1,3,5-triisopropylbenzene and a mixed acid thereto for nitration while inhibiting side reactions. CONSTITUTION:A reaction solvent inert to a known nitrating agent such as 1,2-dichloroethane is charged to a reactor in advance. Nitration is carried out by simultaneously adding 1,3,5--triisopropylbenzene and a mixed acid between nitric acid and >=74wt.% sulfuric acid thereto while keeping the reaction temper ature preferably at -20 to 0 deg.C to obtain the objective compound useful as the raw material for synthesis of 2,4-diamino-1,3,5-triisopropylbenzene which is a raw material for synthesis of azo dyes, epoxy resin curing agents and chain-lengthening agents for polyurethane. The amount of the above-mentioned nitric acid used is 2-2.2 time moles based on 1 mol of 1,3,5-triisopropylbenzene.

公开(公告)号：JPH03232842A

公开(公告)日：1991-10-16

申请号：JP30613890

申请日：1990-11-14

Applicant: MITSUI TOATSU CHEMICALS

Inventor： KASE MOTOHIRO ,  NAKAYAMA HITOSHI ,  WADA MASARU ,  NAGATA TERUYUKI ,  YAMAGUCHI TERUHIRO

IPC: C07C201/12 ,  C07C205/38 ,  C07C315/04 ,  C07C317/22 ,  C07C319/20 ,  C07C323/20

Abstract: PURPOSE:To obtain the subject compound on an industrial scale at a low cost by reacting a 4,4'-bisphenol compound with m-dinitrobenzene in a polar aprotic solvent in the presence of a base comprising particles of alkali metal carbonate and bicarbonate having diameter smaller than a specific level while removing water produced as a by-product. CONSTITUTION:A 4,4'-bisphenol compound of formula I [X is 1-20C bivalent hydrocarbon group, C(CF3)2, CO, S, SO, SO2, O or direct bond to bond the phenylene groups] is condensed with m-dinitrobenzene in the presence of a base to obtain bis(3-nitrophenoxy) compound of formula III. The condensation reaction is carried out by using a base comprising particles of an alkali metal carbonate and an alkali metal bicarbonate having particle diameter of