公开(公告)号：DE1259339B

公开(公告)日：1968-01-25

申请号：DES0092247

申请日：1964-07-24

Applicant: EDISON SOC

Inventor： RIBALDONE GIUSEPPE ,  VARESE GALLARATE ,  SMAI FRANCO ,  MILANESE NOVATE ,  BORTESI GIAMPIERO

IPC: C07D201/10

公开(公告)号：CH447178A

公开(公告)日：1967-11-30

申请号：CH1035864

申请日：1964-08-07

Applicant: EDISON SOC

Inventor： GIUSEPPE RIBALDONE ,  FRANCO SMAI ,  GIAMPIERO BORSOTTI

IPC: C07D201/10 ,  C07D41/00 ,  C07D29/22

公开(公告)号：GB1041433A

公开(公告)日：1966-09-07

申请号：GB265464

申请日：1964-01-21

Applicant: TOYO RAYON CO LTD

IPC: C01B7/00 ,  C01B7/01 ,  C07D201/10

Abstract: Sulphur dioxide is removed from hydrogen chloride and sulphurous acid from hydrochloric acid by contacting the impure material with nitrosyl chloride in the presence of water or dilute HCl. Thus cycloalkane is photo-reacted with a gas mixture of NOCl and HCl to give cycloalkyloxime hydrochloride which is subjected to Beckmann's re-arrangement in the presence of H2SO4 catalyst to give the lactam, the by-product HCl containing SO2 is contacted with NOCl in the presence of water or dilute HCl. The NOCl source may be the effluent gases from the cycloalkyloxime hydrochloride reaction or is part of the NOCl/HCl mixture used in the manufacture of the lactam.ALSO:In a process for the preparation of lactams, a cycloalkane is photo-reacted with a gas mixture of nitrosyl chloride and HCl to give a cycloalkyloxime hydrochloride which is subjected to Beckmann's rearrangement in the presence of H2SO4 to give the lactam, the by-product HCl containing SO2 being contacted with NOCl in the presence of water or dilute HCl to remove the SO2 content. The NOCl source may be effluent gases from the cycloalkyloxime hydrochloride reaction or is part of the NOCl/HCl mixture used in the manufacture of the lactam.

公开(公告)号：GB1031907A

公开(公告)日：1966-06-02

申请号：GB2613563

申请日：1963-07-02

Applicant: MITSUBISHI CHEM IND

IPC: C07D201/10

Abstract: Caprolactam is prepared by reacting hexahydrobenzoic acid with nitrosyl-chloroanhydrosulphate at a temperature of - 20 DEG to 200 DEG C. The molar ratio of nitrosyl-chloroanhydro-sulphate to hexahydrobenzoic acid may be 1: 0.5-8, preferably 1: 0.6-1.5. The reaction may be carried out in the presence of a small quantity, usually 0.05 to 5.0 mols. per mole of nitrosyl-chloroanhydrosulphate, of an inorganic acid or anhydride thereof or a sulphonic acid.

公开(公告)号：FR1438705A

公开(公告)日：1966-05-13

申请号：FR20419

申请日：1965-06-11

Applicant: STAMICARBON

IPC: C07D201/10

Abstract: o -Lactams are prepared by reacting cycloalkyl ketones of formula R-CO-R1 where R and R1 are hydrocarbon groups at least one being a cycloalkyl group, with a nitrosating agent in the presence of boron trifluoride. As by-products carboxylic acid derivatives are formed which may be hydrolysed to the acids. A list of suitable nitrosating reagents is given and nitrosyl chloride is exemplified. It is also possible to use a complex of the nitrosating agent and boron trifluoride. When dicycloalkyl ketones are used caprolactam is formed together with a cycloalkyl carboxylic acid which may then react further with the nitrosating reagent to give more caprolactam. The reaction may be carried out in solution, suitably in a saturated hydrocarbon, and is preferably carried out in the presence of water. The examples describe the preparation of capryl lactam from cyclooctyl methyl ketone, and caprolactam from cyclohexyl methyl ketone, using nitrosylchloride.

公开(公告)号：FR1436220A

公开(公告)日：1966-04-22

申请号：FR13656

申请日：1965-04-16

Applicant: SNIA VISCOSA

IPC: B01J19/18 ,  B01J19/24 ,  C07D201/10

公开(公告)号：GB1019544A

公开(公告)日：1966-02-09

申请号：GB3128064

申请日：1964-08-04

Applicant: ORGANICO

IPC: C07D201/10

Abstract: A process for the preparation of a cycloalkanone oxime and/or the corresponding lactam, by chemical nitrosation of a cycloalkane consists in subjecting a cycloalkane to the action of nitrosyl chloride in the presence of gaseous hydrochloric acid and a strong acid, insoluble in the reaction medium, comprising sulphuric acid or one of the phosphoric acids, and either isolating the oxime obtained or transforming the oxime obtained into a lactam by means of heating in the presence of a strong acid comprising sulphuric acid or one of the phosphoric acids, wherein the strong acid is recovered in dilute form after separation from the oxime or lactam reaction product and is concentrated, decolorized, and freed from its chlorinated and nitrogenous organic impurities by heating with nitric acid containing 50 to 100% of HNO3, and is then finally re-used in the process. Preferably the strong acid is pretreated with chlorine prior to its concentration after which the chlorinated oils formed are decanted and the acid concentrated. The nitric acid used may be introduced at once or gradually into the acid to be recovered at a temperature of 100-200 DEG C. and any excess of nitric acid being eliminated and being recovered by distillation. In an example a solution of cyclododecane and phosphoric acid is saturated with hydrochloric acid gas and nitrosyl chloride added whilst the solution is subjected to radiation from a mercury vapour lamp and a stream of hydrochloride gas still passed in. The resulting phosphoric layer containing cyclododecanone oxime is decanted and the cyclododecanone oxime is precipitated and purified. Into the dilute phosphoric acid recovered from the drying of the first portion of oxime a slow current of chlorine is passed. The oily products formed are separated by filtration and concentrated. The coloration of the phosphoric acid is 8 on the Gardner scale. 5 grams of 95% nitric acid is added, heating is gradually effected to 200 DEG C. under reflux. The excess nitric acid is eliminated at 200 DEG C. under a vacuum of 2 mm. of mercury. The coloration of the phosphoric acid thus obtained is 2 on the Gardner scale. In another example the phosphoric solution of cyclododecanone oxime prepared as above is heated for an hour and the reaction mixture diluted when the dodecanolactam is precipitated and the precipitate extracted with chloroform and the aqueous phosphoric layer decanted from the chloroform layer of the lactam is concentrated at 200 DEG C. under vacuum until a concentration of 103% of H3PO4 is obtained, this acid being black in colour. 95% nitric acid is added, the mixture is gradually heated under reflux to a temperature of 200 DEG C. and maintained for 6 hours when the excess of nitric acid is distilled under a vacuum of 2 mm. of mercury. The phosphoric acid thus obtained is practically colourless.

公开(公告)号：BE665338A

公开(公告)日：1965-12-13

申请号：BE665338D

申请日：1965-06-11

IPC: C07D201/10

Abstract: o -Lactams are prepared by reacting cycloalkyl ketones of formula R-CO-R1 where R and R1 are hydrocarbon groups at least one being a cycloalkyl group, with a nitrosating agent in the presence of boron trifluoride. As by-products carboxylic acid derivatives are formed which may be hydrolysed to the acids. A list of suitable nitrosating reagents is given and nitrosyl chloride is exemplified. It is also possible to use a complex of the nitrosating agent and boron trifluoride. When dicycloalkyl ketones are used caprolactam is formed together with a cycloalkyl carboxylic acid which may then react further with the nitrosating reagent to give more caprolactam. The reaction may be carried out in solution, suitably in a saturated hydrocarbon, and is preferably carried out in the presence of water. The examples describe the preparation of capryl lactam from cyclooctyl methyl ketone, and caprolactam from cyclohexyl methyl ketone, using nitrosylchloride.

公开(公告)号：GB1010152A

公开(公告)日：1965-11-17

申请号：GB1604063

申请日：1963-04-23

Applicant: TOYO RAYON CO LTD

IPC: C07D201/04 ,  C07D201/10

Abstract: Cyclododecanoneoxime is prepared by irradiatcyclododecane in presence of a chlorine-containing nitrosation agent and a cycloalkane (up to C8), separating the resulting oil containing oxime hydrochlorides and diluting with water to precipitate cyclododecanoneoxime. The remaining solution may be neutralized to a pH at least 6.0 with aqueous alkali to precipitate the other oxime. By effecting the Beckmann rearrangement on the said oil a mixture of lactams is obtained which on dilution with water affords o -lauric lactam. In an example, e -caprolactam is recovered from the filtrate. Specification 1,010,151 is referred to.

公开(公告)号：FR1406506A

公开(公告)日：1965-07-23

申请号：FR90002500

申请日：1964-04-20

Applicant: ALSTHOM CGEE

Inventor： CARRASSE JEAN

IPC: B01J19/00 ,  B01J19/18 ,  B01J19/24 ,  C07D201/10 ,  C10J3/46