Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
  • H01J29/86—Vessels; Containers; Vacuum locks
  • H01J29/89—Optical or photographic arrangements structurally combined or co-operating with the vessel
  • H01J29/898—Spectral filters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids

Definitions

• This invention relates to a process for preparing N-aryl or N-aralkyl substituted urethanes. More particularly, it relates to a process for preparing N-aryl or N-aralkyl substituted urethanes by reacting (i) an aryl or aralkyl nitrogen-containing compound, (ii) an organic compound containing at least one hydroxyl group, and (iii) carbon monoxide in the presence of a catalyst.
• U.S. Patent Specification No. 3,338,956 describes a process using rhodium chlorocarbonyl as a catalyst for the urethanation reaction.
• British Patent Specification No. 1,543,051 discloses a process in which the uretbanation reaction is conducted with rhodium chlorocarbonyl as the catalpst and a multi-valent metal halide as the promoter.
• aryl or aralkyl nitro compounds are essentially used as the aryl or aralkyl nitrogen-containing compounds to permit the nitro groug or groups to take part in the urethanation reaction.
• N-aryl and N-aralkyl urethanes As a result of an extensive study of a process of producing N-aryl and N-aralkyl urethanes, we have found an improved process for producing N-aryl and N-aralkyl substitded urethanes in which the urethanes are produced from specified aromatic aryl and aralkyl primary amine compounds, carbon monoxide and hydroxyl group-containing compounds.
• N-aryl or N-aralkyl substituted urethanes by reacting (i) an aryl or aralkyl nitrogen-containing compound, (ii) an organic compound having at least one hydroxyl group, and (iii) carbon monoxide in the presence of a catalyst, .
• component (i) is an aryl or aralkyl primary amino compound having a nitro group, a nitroso group or a carbamate group
• the catalyst consists of a catalytic system comprising a metal and/or a compound thereof chosen from palladium, rhodium and ruthenium and compounds thereof and as promoter a Lewis acid and/or a compound thereof, and that the reaction is conducted at elevated temperature and under high pressure conditions.
• the aryl and aralkyl amino compounds which are employed as the chief starting material are aryl and aralkyl primary amino compounds having a nitro group, a nitroso group or a carbamate group.
• aryl and aralkyl compounds include m- and p-nitroaniline, m- and p-nitrosoaniline, m- and p-carbamatesniline, 2-amino-4-nitrotoluene, 2-amino-4-nitrosotoluene, 2-amino-4-carbamatetoluene, 2-nitro-4-aainotoluene, 2-nitroso-4-aminotoluene, 2-carbamate-4-aminotoluene, 2-amino-6-nitrotoluene, 2-amino-6-nitrosotoluene, 2-amino-6-carbamatetoluene, 4-amino-4'-nitrobiphenyl
• aryl and aralkyl amino compounds are also usable. These aryl and aralkyl amino compounds may be used singly or in combination. It will be noted that the nitro group of aryl or aralkyl nitro compounds are also converted into a corresponding urethane under reaction conditions used in the practice of the invention. Of the above-mentioned amino compounds, nitroaminotoluenes and aminocarbamatetoluenes are most preferable because these compounds are more reactive than others.
• the hydroxyl group-containing compounds useful in the process of the invention include primary, secondary and tertiary monohydric alcohols and polyhydri:c alcohols and polyhydric alcohols, and monohydric phenols and polyhydric phenols. Typical or such compounds are ethanol and phenol.
• Suitable alcohols may be expressed by a general formula R(OH) n in which R represents a linear or branched alkyl, a cycloalkyl, an alkylene, a cycloalkylene or an aralkyl group, and n is 1 or 2 or a higher integer.
• These alcohols may further include a substituent containing an oxygen, nitrogen, halogen or sulphur atom such as, for example, halogen, sulphoxide, sulpho, amide, carbonyl or a carboxylic acid ester group.
• a substituent containing an oxygen, nitrogen, halogen or sulphur atom such as, for example, halogen, sulphoxide, sulpho, amide, carbonyl or a carboxylic acid ester group.
• Examples of the alcohols expressed by the general formula R(OH) n include monohydric alcohols much as methyl alcohol, ethyl alcohol, n- and iso-propyl alcohol, n-, iso- and t-butyl alcohol, linear or branched amyl alcohol, hexyl alcohol, cyclohexyl alcohol, lauryl alcohol, cetyl alcohol, benzyl alcohol, chlorobenzyl alcohol, methoxylbenzyl alcohol, etc., dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc., trihydric alcohols such as glycerol, hexanetriol, etc., and more polyfunctional polyols.
• monohydric alcohols much as methyl alcohol, ethyl alcohol, n- and iso-propyl alcohol, n-, iso- and t-butyl alcohol, linear or branched amyl alcohol, hexyl alcohol,
• Suitable examples of phenols include phenol itself, chlorophenol, cresol, ethylphenol, linear or branched propylphenol, butyl- and higher alkylphenols, catechol, resorcin, 4,4'-dihydroxydiphenylmethane, 2.2'-isopropyl idenediphenyl, anthranol, phenanthrol, pyrogallol, phloroglucinol, etc.
• methanol, ethanol and isobutanol are preferred since the use of these alcohols results in higher velocity of reaction and higher yield of a final product.
• the platinum group metals and/or compounds thereof which are used as an integer of the catalytic system in the process of the invention are palladium, rhodium and ruthenium elements or compounds thereof, or a mixture thereof.
• examples of such compounds are halides, cyanides, thiocyanides, isocyanides, oxides, sulphates, nitrates, carbonyl compounds of palladium, rhodium or ruthenium, their addition compounds or complexes with tertiary amines such as triethylamine, pyridine, isoquinoline, etc., and their complexes with organic phosphorous compounds such as triphenylphosphine.
• These catalysts may be used for the reaction as such or may be supported on carriers such as alumina, silica, carbon, barium sulphate, calcium carbonate, asbestos, bentonite, diatomaceous earth, fuller's earth, organic ion-exchange resins, inorganic ion-exchange resins, magnesium silicate, aluminium silicate, molecular sieves and the like.
• carriers such as alumina, silica, carbon, barium sulphate, calcium carbonate, asbestos, bentonite, diatomaceous earth, fuller's earth, organic ion-exchange resins, inorganic ion-exchange resins, magnesium silicate, aluminium silicate, molecular sieves and the like.
• carriers may be charged into a reactor separately from palladium, rhodium, ruthenium or their compounds. In view of a great catalytic activity, palladium and/or its compounds are preferable to other platinum group metals or compounds thereof.
• Lewis acids and/or compounds thereof are used as the promoter.
• * Lewis acids herein used is intended to imply those as described, for example, in Physical Organic Chemistry by Jack Hine, 1962 (McGraw Hill Book Co., New York), including Br8nsted acids.
• Such acids include halides, sulphates, acetates, phosphates, nitrates such as a tin, titanium, germanium, aluminium, iron,nickel, zinc, cobalt, manganese, thallium, zirconium, copper, lead, vanadium, niobium, tantalum, mercury, etc.
• suitable Lewis acids include ferric chloride, ferrous chloride, stannic chloride and copper acetate. Of these, ferrous chloride and ferric chloride are the most preferable.
• the compounds of the Lewis acids may be, for example, complexes with tertiary amines or organic phosphorous compounds.
• tertiary amines capable of producing complexes include triethylamine, N,N-diethylaniline, N,N-diethylcyclohexyl- amine, 1,4-diazabicyclo-[2,2,2]octane, and nitrogen-containing heterocyclic compounds such as pyridine, quinoline and isoquinoline.
• phosphorous compounds or phosphines include triphenylphosphine, dimethylphenylphosphine, bisdiphenylphosphinoethane and the like.
• complexes of ferrous chloride and nitrogen-containing heteroaromatic compounds are preferred since they are less corrosive towards the inside surface of a reactor, can improve the yield of a final product, and permit easier recovery of the catalyst as compared with other promoters.
• the reaction is conducted using the hydroxyl group-containing organic compound and carbon monoxide in such amounts that the hydroxyl group and carbon monoxide are in at least equimolar or greater ratios to the amino group in the case of an amino to compound having a carbamate group and/a total of the amino group and the nitro or nitroso group in the case of an amino compound having a nitro or nitroso group.
• the amount of the platinum group metal may widely vary depending on the kind of the amino compound and other reaction conditions but is generally in a range of 1 - 1 x 10 -5 , preferably 5 x 10 -1 - 1 x 10 -4 , as metal element, by weight ratio to the amino compound.
• the Lewis acid used as the promoter may be used in a range of 2 - 2 x 10 -3 , preferably 1 - 5 x 10 -2 , by weight ratio to the amino compound.
• the reaction temperature is generally maintained in a range of 80° - 230°C, preferably 140 - 200°C.
• the reaction pressure is in the range of 10 - 1000 kg/cm2 gauge, preferably 30 - 500 kg/cm 2 gauge as expressed in terms of the partial pressure of carbon monoxide. Addition of small amount of water will shorten the reaction time. In this case, the amount of water added is in a range.of 1 - 70 moles, preferably 10 - 50 moles per mole of the starting primary amine. An amount less than 1 mole of water per mole of the amino compound does not have an appreciable effect on the reaction time, whereas a larger amount lowers the yield of a final product.
• the reaction time depends on the property or kind of the amino compound, reaction temperature, reaction pressure, the kind and amount of the catalyst, amount of water and the type of reactor but is generally in a range of 5 minutes to 6 hours.
• reaction mixture After the completion of the reaction, the reaction mixture may be cooled. After discharging the gas from the reaction system, the reaction product may be subjected to a treatment by an ordinary separation technique such as filtration, distillation or other suitable means thereby separating the resulting urethane from unreacted materials, by-products, the solvent and catalyst.
• an ordinary separation technique such as filtration, distillation or other suitable means thereby separating the resulting urethane from unreacted materials, by-products, the solvent and catalyst.
• the diurethane produced has the formula

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• Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1977
  • 1977-07-25 JP JP8840077A patent/JPS5423432A/ja active Granted
• 1978
  • 1978-07-24 EP EP78300188A patent/EP0000815B1/fr not_active Expired
  • 1978-07-24 DE DE7878300188T patent/DE2861574D1/de not_active Expired

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