公开(公告)号：JPH01102051A

公开(公告)日：1989-04-19

申请号：JP25828987

申请日：1987-10-15

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU

IPC: C07C229/08 ,  C07C67/00 ,  C07C227/00

Abstract: PURPOSE:To obtain the title compound in high purity and yield at a low cost, taking advantage of the solubility difference of alanine and ammonium chloride to hydrated alcohol, by adding a specific amount of an alcohol to an aqueous solution of alanine containing ammonium chloride. CONSTITUTION:L-2-chloropropionic acid, D-2-chloropropionic acid or DL-2- chloropropionic acid is aminated with ammonia and the obtained aqueous solution of L-alanine, D-alanine or DL-alanine containing ammonium chloride is added with 5-20pts.wt. of an alcohol based on 1pt.wt. of water in the aqueous solution to obtain the objective compound. The alcohol used in the present process is preferably an alcohol having low boiling point, e.g. methanol or ethanol. In the case of requiring higher purity, the product is dissolved again in water and subjected to desalting treatment, etc., with an ion exchange resin.

公开(公告)号：JPH01102050A

公开(公告)日：1989-04-19

申请号：JP25828887

申请日：1987-10-15

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU

IPC: C07C229/08 ,  C07C67/00 ,  C07C227/00

Abstract: PURPOSE:To easily improve purity of alanine without necessitating a large-sized apparatus, by washing alanine with a hydrated alcohol in the removal of ammonium chloride from alanine crystal containing ammonium chloride. CONSTITUTION:L-2-chloropropionic acid, D-2-chloropropionic acid or DL-2- chloropropionic acid is aminated with ammonia and the obtained L-alanine, D-alanine or DL-alanine crystal containing ammonium chloride is washed with a hydrated alcohol to obtain the objective compound in purified state. The alcohol used in the present process is preferably an alcohol having low boiling point, e.g. methanol or ethanol. The water content of the hydrated alcohol is usually 2-40wt.%, especially preferably 5-15wt.%. In the case of requiring higher purity, the process is combined with a desalting treatment with an ion exchange resin.

公开(公告)号：JPS6425742A

公开(公告)日：1989-01-27

申请号：JP17922287

申请日：1987-07-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  KIYONO SHINJI

IPC: B01J31/04 ,  B01J27/053 ,  C07C51/00 ,  C07C51/235 ,  C07C53/19 ,  C07C67/00

Abstract: PURPOSE:To obtain the titled compound useful as an intermediate for producing industrial chemicals, in high conversion ratio without requiring a specific device in oxidizing 2-chloropropionaldehyde, by using a zinc- or cadmium-containing compound as a catalyst. CONSTITUTION:A zinc- or cadmium-containing compound is used as a catalyst and 2-chloropropionaldehyde is oxidized with oxygen or an oxygen-containing gas in a liquid phase at 20-120 deg.C, preferably 40-90 deg.C to give the aimed compound. The reaction is preferably carried out in the presence of a solvent, to be concrete, dimethyl sulfoxide may be cited as the solvent. The concentration of the raw material in the solvent is preferably 5-15wt.%. Zinc oxide is cited as the zinc-containing compound of the catalyst, cadmium oxide as the cadmium-containing compound and the amount of the catalyst used is preferably 0.01-5wt.% in the liquid phase.

公开(公告)号：JPS6419036A

公开(公告)日：1989-01-23

申请号：JP17388687

申请日：1987-07-14

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  KIYONO SHINJI

IPC: B01J27/08 ,  B01J23/18 ,  B01J27/232 ,  C07C51/00 ,  C07C51/235 ,  C07C53/19 ,  C07C67/00

Abstract: PURPOSE:To obtain 2-chloropropionic acid which is useful as an industrial chemical under reduced corrosive conditions, practically in high selectivity, by using a bismuth-containing compound as a catalyst to effect liquid-phase oxidation of 2-chloropropionaldehyde with O2. CONSTITUTION:The liquid phase oxidation of 2-chloropropionaldehyde of formula I carried out, preferably in a solvent such as 2-chloropropionic acid, preferably in a concentration of 5-15wt.%, in the presence of a catalyst of a bismuth- containing compound such as bismuth basic carbonate hemihydrate, using O2 or O2-containing gas, preferably at 40-90 deg.C, preferably at a partial O2 pressure of 5-100kg/cm to give 2-chloropropionic acid of formula II, which is useful as a synthetic intermediate of agrochemicals. The bismuch-containing compound is, e.g., bismuth basic carbonate, bismuth oxide,bismuth hydroxide, bismuth tribromide, or bismuth phosphate. The amount of the catalyst used is preferably 0.01-5wt.% in the liquid phase.

公开(公告)号：JPS6416744A

公开(公告)日：1989-01-20

申请号：JP17286487

申请日：1987-07-13

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  KIYONO SHINJI

IPC: C07C53/19 ,  B01J23/14 ,  C07C51/00 ,  C07C51/235 ,  C07C67/00

Abstract: PURPOSE:To obtain the titled compound useful as an intermediate for producing industrial chemicals in high yield at a readily controllable oxidation rate without causing corrosion problems and peracid as by-product in oxidizing 2- chloropropionaldehyde, by using a germanium compound as a catalyst. CONSTITUTION:2-Chloropropionaldehyde is oxidized with oxygen or an oxygen- containing gas in a liquid phase by using a germanium compound as a catalyst at 20-120 deg.C, preferably 40-80 deg.C in a solvent, preferably acetic acid or dimethyl sulfoxide to give the aimed compound. The concentration of the raw material in the solvent is usually 1-50wt.%, especially 5-15wt.%. Complete removal of water in the reaction system is not required, and the amount of the water in the liquid phase is preferably -10wt.%, especially partial pressure of oxygen. The amount of the catalyst used is properly 0.01-5wt.% in the liquid phase.

公开(公告)号：JPS6416736A

公开(公告)日：1989-01-20

申请号：JP16981187

申请日：1987-07-09

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  FUJITA YOSHIHIRO

IPC: C07C45/50 ,  B01J31/24 ,  C07C45/00 ,  C07C47/14 ,  C07C67/00

Abstract: PURPOSE:To obtain the titled compound advantageously in reacting vinyl chloride with carbon monoxide and hydrogen in the presence of a rhodium compound, a base and water, by using a trivalent organic phosphorus compound or an oxide thereof as the base and a specific amine as the base. CONSTITUTION:In reacting vinyl chloride with carbon monoxide and hydrogen in the presence of a rhodium compound, a base and water to produce the titled compound useful as an intermediate for chemicals, agricultural chemicals and drugs, at least one of a trivalent organic phosphorus compound and an oxide thereof and at least one of amines having 10-11.5 pKa and >=130 deg.C boiling point, preferably mono- - trialkylamine containing >=4C alkyl group are used as the base to give the aimed compound at low temperature, under low pressure and in high selectivity. The reaction can be progressed stably for a long time by using a simple device.

公开(公告)号：JPS63310845A

公开(公告)日：1988-12-19

申请号：JP14399387

申请日：1987-06-11

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  KIYONO SHINJI

IPC: C07C53/19 ,  B01J23/14 ,  B01J27/053 ,  B01J27/135 ,  B01J27/25 ,  C07B61/00 ,  C07C51/00 ,  C07C51/235 ,  C07C67/00

Abstract: PURPOSE:To obtain 2-chloropropionic acid of high purity in high selectivity, by conducting liquid-phase oxidation of 2-chloropropionaldehyde in the presence of a specific catalyst using an oxygen-containing gas, thus facilitating the control of the oxidation reaction rate under reduced corrosive environments in an industrial scale. CONSTITUTION:2-Chloropropionaldehyde is oxidized in a solvent such as acetic acid in the presence of at least one metal compound selected from SnSO4, Sn(OH)2, SnCl2, and other Sn compounds, or PbBr2, Pb(NO3)2, and other Pb compounds in liquid phase using O2 or an O2-containing gas, preferably at 20-120 deg.C, particularly preferably at 40-80 deg.C, usually at an oxygen partial pressure below 100kg/cm to give the subject compound of formula II which is used as an intermediate of industrial chemicals and medicines. The use of a batchwise reactor facilitates the production of the subject compound of high purity, free from impurities such as monochloracetic acid.

公开(公告)号：JPS63270637A

公开(公告)日：1988-11-08

申请号：JP10328787

申请日：1987-04-28

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU ,  HEN PARAA ,  KIYONO SHINJI

IPC: C07C59/08 ,  C07C51/00 ,  C07C51/44 ,  C07C51/48 ,  C07C67/00

Abstract: PURPOSE:To efficiently obtain the titled compound useful as a food additive, etc., in high purity by simple operation, by using isopropyl acetate as an extracting solvent in separating lactic acid from a solution containing the lactic acid by extraction. CONSTITUTION:Isopropyl acetate is used as an extracting solvent to separate and obtain lactic acid from a lactic acid-containing aqueous solution. The extracting operation is carried out normally at 10-80 deg.C, preferably at 15-45 deg.C. The amount of the isopropyl acetate used varies with the concentration of the lactic acid or extraction ratio in the extracting operation; however, a volume of 1-50 times based on water in the lactic acid-containing aqueous solution is normally preferred. Operation temperature in separating and recovering the lactic acid from the lactic acid-containing isopropyl acetate after the extraction is normally 10-80 deg.C, especially preferably 15-45 deg.C.

公开(公告)号：JPS62270541A

公开(公告)日：1987-11-24

申请号：JP11354486

申请日：1986-05-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU

IPC: C07B61/00 ,  B01J31/00 ,  B01J31/18 ,  B01J31/20 ,  B01J31/24 ,  C07C45/00 ,  C07C45/50 ,  C07C47/14 ,  C07C67/00

Abstract: PURPOSE:To obtain the titled compound which is an intermediate for chemicals, etc., in high selectivity with high catalyst activity under low temperature and pressure condition, by carrying out reaction in the presence of a rhodium compound, base and carboxylic acid in reacting vinyl chloride with carbon monoxide and hydrogen. CONSTITUTION:Vinyl chloride, carbon monoxide and hydrogen are used as raw materials and reacted in the presence of a rhodium compound, base and carboxylic acid at a temperature within the range of 20-150 deg.C, preferably 20-100 deg.C under a reaction pressure within the range of 10-200kg/cm gauge, preferably within the range of 30-150kg/cm gauge to afford the aimed compound. The above-mentioned base is preferably in combination with at least one or more trivalent organic phosphorus compounds or oxides thereof and at least one or more nitrogen-containing compounds having a pKa within the range of 3-11. A carboxylic acid having particularly 1.5-5.0pKa in an aqueous solution, e.g. acetic acid, etc., is preferred for the carboxylic acid.

公开(公告)号：JPS62270540A

公开(公告)日：1987-11-24

申请号：JP11354386

申请日：1986-05-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： ONO HIROSHI ,  KASUGA TAKAHARU

IPC: C07B61/00 ,  B01J31/00 ,  B01J31/18 ,  B01J31/20 ,  B01J31/24 ,  C07C45/00 ,  C07C45/50 ,  C07C47/14 ,  C07C67/00

Abstract: PURPOSE:To obtain the titled compound useful as a useful intermediate for chemicals and agricultural chemicals, medicines, etc., in high yield with high catalyst activity under low temperature and pressure condition, by using a specific base in reacting vinyl chloride with carbon monoxide and hydrogen in the presence of a catalyst. CONSTITUTION:Vinyl chloride, carbon monoxide and hydrogen are used as raw materials and reacted in the presence of a rhodium compound as a catalyst and further at least one oxide of a trivalent organic phosphorus compound at a temperature within the range of 20-150 deg.C under a reaction pressure within the range of 10-200kg/cm gauge, preferably within the range of 30-150kg/cm gauge to afford the aimed compound. The above-mentioned base is particularly preferably in combination with at least one nitrogen-containing compound having a pKa within the range of 3-11 and pyridine compounds, quinoline compounds, etc., may be specifically cited. The coexistence of water in the reaction system is further preferred.