EP0000815B1 - Verfahren zur Herstellung von N-Aryl- oder N-Aralkyl-Urethanen - Google Patents

Verfahren zur Herstellung von N-Aryl- oder N-Aralkyl-Urethanen Download PDF

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Publication number
EP0000815B1
EP0000815B1 EP78300188A EP78300188A EP0000815B1 EP 0000815 B1 EP0000815 B1 EP 0000815B1 EP 78300188 A EP78300188 A EP 78300188A EP 78300188 A EP78300188 A EP 78300188A EP 0000815 B1 EP0000815 B1 EP 0000815B1
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EP
European Patent Office
Prior art keywords
compound
amino
process according
aryl
component
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Expired
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EP78300188A
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English (en)
French (fr)
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EP0000815A1 (de
Inventor
Katsuharu Miyata
Makoto Aiga
Seiji Hasegawa
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Mitsui Toatsu Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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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 urethanation reaction is conducted with rhodium chlorocarbonyl as the catalyst 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 group 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 substituted urethanes in which the urethanes are produced from specified aromatic aryl and aralkyl primary amine compounds, carbon monoxide and hydroxyl group-containing compounds.
  • a process for producing 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, characterised in that component (i) is an aryl or aralkyl primary amino compound having a nitro group, a nitroso group or a carbamate group, that 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 a promoter a Lewis acid and/or a compound thereof, and that the reaction is conducted at elevated temperature and under a carbon monoxide partial pressure of 10-1000kg/cm 2.
  • component (i) is an aryl primary amino compound and preferably component (i) has a nitro group.
  • 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, aniline m- and p-carbamate, 2-amino-4-nitrotoluene, 2-amino-4-nitrosotoluene, 2-aminotoluene-4-carbamate, 2-nitro-4-aminotoluene, 2-nitroso-4-aminotoluene, 4-aminotoluene-2-carbamate, 2-amino-6-nitrotoluene, 2-amino-6-nitrosotoluene, 2-aminotoluene-6-carbamate, 4-amino-4'-nitrobiphenyl, 4-amino-4'-nitrobiphen
  • 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 aminotoluenecarbamates are most preferable because these compounds are more reactive than others.
  • hydroxyl group-containing compounds useful in the process of the invention include primary, secondary and tertiary monohydric alcohols and polyhydric alcohols and polyhydric alcohols, and monohydric phenols and polyhydric phenols.
  • Typical of 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 such 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, methoxybenzyl 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 such 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'-isopropylidenediphenyl, 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 are used as the promoter.
  • the term "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 Bronsted acids.
  • Such acids include halides, sulphates, acetates, phosphates, and nitrates such as tin, titanium, germanium, aluminium, iron, nickel, zinc, cobalt, manganese, thallium, zirconium, copper, lead, vanadium, niobium, tantalum, mercury, etc. More particularly, suitable Lewis acids include ferric chloride, ferrous chloride, stannic chloride and copper acetate. Of these, ferrous chloride and ferric chloride are the most preferable. Further, 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-diethylcyclohexylamine, 1,4-diazabicyclo-[2,2,2]octane, and nitrogen-containing heterocyclic compounds wherein nitrogen forms part of the ring system such as pyridine, quinoline and isoquinoline.
  • nitrogen-containing heterocyclic compounds wherein nitrogen forms part of the ring system 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 Jess 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 compound having a carbamate group and to 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 vary widely 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/cm 2 gauge, preferably 30-500 kg/cm 2 gauge as expressed in terms of the partial pressure of carbon monoxide. Addition of a 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 per 100 moles, preferably 10-50 moles per 100 moles of the starting primary amine. An amount less than 1 mole of water per 100 moles 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Position Input By Displaying (AREA)
  • Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

1. Verfahren zur Herstellung N-Aryl- oder N-Aralkyl-substituierter Urethane durch Umsetzen (i) einer Aryl- oder Aralkylstickstoff-haltigen Verbindung, (ii) einer organischen Verbindung mit wenigstens einer Hydroxyl-Gruppe und (iii) Kohlenmonoxid in Gegenwart eines Katalysators, dadurch gekennzeichnet, daß die Komponente (i) eine Aryl- oder Aralkyl-prim.-Amino-Verbindung mit einer NitroGruppe, einer Nitroso-Gruppe oder einer Carbamat-Gruppe ist, daß der Katalysator aus einem katalytischen System mit einem Metall und/oder einer Verbindung von diesem, ausgewählt unter Palladium, Rhodium und Ruthenium und deren Verbindungen, und als Promoter einer Lewis-Säure und/oder einer Verbindung hiervon besteht, und daß die Umsetzung bei erhöhter Temperatur und unter einem , Kohlenmonoxid-Partialdruck von 10-1000 kg/cm2 erfolgt.
2. Verfahren nach Anspruch 1, bei dem die Komponente (i) ein Nitroaminotoluol ist.
3. Verfahren nach Anspruch 1, bei dem die Komponente (i) ein Aminotoluol-alkylcarbamat ist.
4. Verfahren nach einem vorhergehenden Anspruch, bei dem das Metall und/oder eine Verbindung hiervon Palladium und/oder Palladiumhalogenid ist.
5. Verfahren nach einem vorhergehenden Anspruch, bei dem der Promoter Eisen(11)chlorid und/ oder eine Verbindung hiervon oder Eisen(III)chlorid und/oder eine Verbindung hiervon ist.
6. Verfahren nach einem der Ansprüche 1 bis 4, bei dem der Promoter ein Komplex aus Eisen(11)chlorid und einer stickstoffhaltigen heterocyclischen Verbindung ist, wobei der Stickstoff einen Teil des Ringsystems bildet.
7. Verfahren nach Anspruch 6, bei dem Wasser dem Reaktionssystem in einer Menge von 1-70 Mol pro 100 Mol der Komponente (i) zugesetzt wird.
8. Verfahren nach einem vorhergehenden Anspruch, bei dem die Komponente (ii) eine Verbindung der allgemeinen Formel R(OH)n ist, wobei R eine lineare oder verzweigte Alkyl-, eine Cycloalkyl-, eine Alkylen-, eine Cycloalkylen- oder eine Aralkyl-Gruppe bedeutet und n 1 oder 2 oder eine höhere ganze Zahl ist, wobei die Verbindung gegebenenfalls mit einem ein Sauerstoff-, Stickstoff-, Halogen- oder Schwefelatom enthaltenden Substituenten substituiert ist.
9. Verfahren nach einem vorhergehenden Anspruch, bei dem die Komponente (i) ein Aminotoluolcarbamat ist.
10. Verfahren nach einem vorhergehenden Anspruch, bei dem die Komponente (i) unter 2-Amino-4-nitrotoluol, 2-Aminotoluol-4-äthylcarbamat, m-Nitroanilin, p-Nitroanilin, Anilin-m-äthylcarbamat, 4-Amino-2-nitrotoluol, 4-Aminotoluol-2-äthylcarbamat und 2-Aminotoluol-4-isobutylcarbamat ausgewählt ist.
EP78300188A 1977-07-25 1978-07-24 Verfahren zur Herstellung von N-Aryl- oder N-Aralkyl-Urethanen Expired EP0000815B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP88400/77 1977-07-25
JP8840077A JPS5423432A (en) 1977-07-25 1977-07-25 Cathode-ray tube display unit

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EP0000815A1 EP0000815A1 (de) 1979-02-21
EP0000815B1 true EP0000815B1 (de) 1982-01-27

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DE (1) DE2861574D1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2903950A1 (de) * 1979-02-02 1980-08-07 Bayer Ag Verfahren zur herstellung von urethanen
DE2908250A1 (de) * 1979-03-02 1980-09-11 Bayer Ag Verfahren zur herstellung von urethanen
EP0036895A1 (de) * 1980-03-20 1981-10-07 BASF Aktiengesellschaft Verfahren zur Herstellung von aromatischen Urethanen
JPH0734522U (ja) * 1993-12-01 1995-06-23 古河電気工業株式会社 プレハブ架線用電線
KR20100138970A (ko) 2008-03-18 2010-12-31 바스프 에스이 톨릴렌디아민으로부터 형성된 금속 카르바메이트

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JPS5423432A (en) 1979-02-22
DE2861574D1 (en) 1982-03-11
JPS615257B2 (de) 1986-02-17
EP0000815A1 (de) 1979-02-21

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