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WO1998055451A1 - Procede de preparation de carbamates - Google Patents

Procede de preparation de carbamates Download PDF

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Publication number
WO1998055451A1
WO1998055451A1 PCT/EP1998/002889 EP9802889W WO9855451A1 WO 1998055451 A1 WO1998055451 A1 WO 1998055451A1 EP 9802889 W EP9802889 W EP 9802889W WO 9855451 A1 WO9855451 A1 WO 9855451A1
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WO
WIPO (PCT)
Prior art keywords
reaction
metal
catalyst
carbonate
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1998/002889
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English (en)
Inventor
Richard Colin Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Huntsman International LLC
Original Assignee
Imperial Chemical Industries Ltd
Huntsman International LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd, Huntsman International LLC filed Critical Imperial Chemical Industries Ltd
Priority to AU77660/98A priority Critical patent/AU7766098A/en
Publication of WO1998055451A1 publication Critical patent/WO1998055451A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups

Definitions

  • the present invention relates to a method for the preparation of carbamates by reaction of amines with organic carbonates. It is known to react amines with organic carbonates in order to obtain carbamates.
  • US-A 5.347.034 discloses a process for producing poly(O-alkylurethanes) of the diphenylmethane series by reacting the corresponding amines with dialkyl carbonates in the presence of a catalyst, such that the formed poly(O-alkylurethanes) crystallize out in a highly pure form upon cooling.
  • EP-A 391.473 describes a process for producing carbamates using reduced amounts of catalyst by first reacting an amine with a (cyclo)alkyl carbonate in the presence of a carbamation catalyst to produce a mixture of a carbamate and an urea, further reacting the urea with carbonate to produce the corresponding carbamate, and finally recovering the carbamate from the reaction mixture.
  • DE-A 3.202.690 a method for preparing aromatic urethanes is described by reacting aromatic amines and alkylcarbonates in the presence of an alcoholate of an alkali metal or an alkaline earth metal.
  • US-A 4.268.684 discloses a method for the preparation of carbamates by reacting an organic carbonate with an aromatic amine in the presence of certain zinc, tin or cobalt salts which are only active at temperatures of at least 200° C whereas in US-A 4.268.683 zinc or tin salts are used which are soluble in the reaction mixture at the reaction conditions.
  • EP-A 48.371 describes the preparation of N,O-disubstituted urethanes by reacting primary amines with dialkylcarbonates in the presence of neutral or basic inorganic or organic lead, titanium, zinc or zirconium compounds.
  • the invention thus concerns a method for the preparation of carbamates by reaction of amines with organic carbonates in the presence of a metal based catalyst wherein the reaction is carried out under such conditions that a precipitate containing said metal is formed during or after the reaction.
  • the method allows easy recovery of the spent catalyst, i.e. the metal containing compound, thus improving the economics and environmental impact of the process.
  • the precipitation can be brought about in any suitable manner.
  • the catalyst is converted into an insoluble metal carbonate by reaction with the organic carbonate present in the reaction mixture.
  • a suitable Bronstedt acid or a salt thereof will then be added in order to form a precipitate containing the metal.
  • a suitable Bronstedt acid or metal salt thereof may be any inorganic or organic acid or salt which reacts with the catalyst to form a precipitate containing the metal of the catalyst (for example HCI). Its choice thus largely depends on the type of catalyst used. In a preferred method at least 90% by weight of the catalyst is eventually converted into a metal containing precipitate.
  • the invention concerns the above method in which the precipitate containing the metal is subsequently separated from the reaction mixture.
  • the precipitate may be removed continuously during or after the termination of the reaction by any suitable method.
  • a preferred separation method is filtration.
  • Amine compounds which can be used in the present method include aliphatic, cycloaliphatic or aromatic mono-, di- or polyamines.
  • Suitable amines according to the process of the invention include, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclopropylamine, cyclobutylamine, cyclohexylamine, laurylamine, stearylamine, phenylamine, 4-chlorophenylamine, 2-fluorophenyl amine, 3,4-dichlorophenylamine, aniline, benzylamine, tolylamine, diisopropyl phenylamine, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
  • 2,2'-diaminodiphenylmethane and higher homologs polyaminopolyphenylmethanes
  • 2,4-toluenediamine 2,6-toluenediamine
  • m-phenylenediamine 1 ,4-butylenediamine
  • 1 ,6-hexylenediamine 1 ,5-naphthylenediamine
  • 1 ,4-cyclohexylenediamine isophoronediamine, 2,2,4-trimethylhexamethylenediamine and mixtures thereof.
  • aromatic di- or polyamines like toluenediamines, diaminodiphenylmethanes or polyaminopolyphenylmethanes or any mixtures thereof
  • Suitable organic carbonates include cyclic or alicyclic carbonates such as, for example, ethylene carbonate, propylene carbonate, styrene carbonate, diphenyl carbonate, methyl phenyl carbonate.dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dihexyl carbonate, methyl ethyl carbonate, methyl butyl carbonate and the like.
  • Any metal based catalyst capable of forming a metal compound which is present as a precipitate during or after completion of the reaction may be used.
  • Organic or inorganic salts which may be used include, for example, acetates, chlorides, nitrates, sulfonates, propionates, isopropanoates, butanoates, 2-ethylhexanoates, n-octoates, isononanoates, benzoates, chlorobenzoates, naphthenates, stearates, itaconates, pivalates, phenolates, acetylacetonates, alkoxides, C 16 /C 18 -alkenylsuccinoates (ASA), C 12 -alkenylsuccinoates (DSA) and the like.
  • ASA alkoxides
  • alkanoates having from 1 to 15 carbons atoms.
  • Suitable catalysts include, for example, zinc catalysts such as zinc chloride, zinc acetate, zinc propionate, zinc octoate, zinc benzoate, zinc p-chlorobenzoate, zinc naphthenate, zinc stearate, zinc itaconate, zinc pivalate, zinc phenolate, zinc acetylacetonate, zinc methoxide, lead catalysts like lead acetate and lead octoate, and tin catalysts like stannous chloride, stannous octoate, and mixtures thereof.
  • the metal in the catalyst is selected from the group consisting of Ti, Zr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, Bi and Cd.
  • a method wherein the precipitate containing the metal is a metal carbonate is preferred.
  • the catalyst is generally used in amounts between 10 3 and 20 mole% based on the amount of amines used.
  • the polyamines and the organic carbonates may be reacted in stoichiometric quantities.
  • reaction conditions and reagents are chosen so that as much of the catalyst as possible is converted into a metal compound which is present as a precipitate at the end of the reaction.
  • the method may be carried out at atmospheric or superatmospheric pressures.
  • a pressure of not more than 20 bar is preferred.
  • reaction time is dependent on the temperature and on the type and quantity of the carbamate compound, but will normally be between 0.5 and 6 hours. Reaction times of less than 3 hours are common, and reaction times of less than 2.5 hours have been achieved without any problem.
  • the reaction temperature will be between 50 and 300°C.
  • the method of the invention is carried out at temperatures between 100 and 250°C.
  • the presence of a solvent is not required, but it may be added without adversely affecting the reaction.
  • Any solvent or mixture of solvents which is inert to the reactants under the reaction conditions may be employed.
  • Suitable solvents which may be employed include, for example, aromatic hydrocarbons such as benzene, halogenated aromatic hydrocarbons such as monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene or 1-chloronaphthalene, alkylated aromatic hydrocarbons like toluene, xylene, ethylbenzene, cumene or tetrahydronaphthalene, other functionalised aromatic hydrocarbons such as anisole, diphenylether, ethoxybenzene, benzonitrile, 2-fluoroanisole, 2,3-dimethylanisole or trifluorotoiuene, alkanes such as n-pentane, n-hexane, n-heptane or higher or branched alkanes, cyclic alkanes like cyclopentane, cyclohexane or derivatives thereof, halogenated alkanes like chloroform, dichlor
  • the method can be conducted in any apparatus which can be equipped, if required, with agitation means and heating and/or cooling means to keep the temperature within the desired range.
  • the method of the present invention may be conducted batchwise or as a semi-continuous or continuous process.
  • reaction alcohols are formed as by-product. These can be removed from the reaction mixture either continuously during or after completion of the reaction by e.g. distillation.
  • the present invention is illustrated by, but not limited to, the following examples.
  • a mixture of 2.0g (8 mmol) polymeric diamino diphenyl methane, 42.8g (0.475 mol) dimethyl carbonate and 0.23g (0.18 mmol active catalyst) of a lead octoate (lead salt of 2-ethyl hexanoic acid) solution in mineral terpentine oil (MTO) (18 wt% Pb) was charged into a 100 ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.
  • MTO mineral terpentine oil
  • a mixture of 1.2g (9.83 mmol) 2,4-diaminotoluene , 42.8g (0.475 mol) dimethyl carbonate and 0.098g (0.082 mmol active catalyst) of a lead octoate (mainly lead salt of 2-ethyl hexanoic acid) solution in MTO (18 wt% Pb) was charged into a 100 ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.
  • a lead octoate mainly lead salt of 2-ethyl hexanoic acid
  • a mixture of 2.0g (8 mmol) polymeric diamino diphenyl methane, 42.7g (0.47 mol) dimethyl carbonate and 0.12g (0.1 mmol active catalyst) of a lead isononanoate (lead salt of 3,5,5-trimethyl hexanoic acid) solution in MTO was charged into a 100 ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.
  • a mixture of 2.0g (8 mmol) polymeric diamino diphenyl methane, 42.7g (0.47 mol) dimethyl carbonate and 0.218g (0.2 mmol active catalyst) of a zinc isononanoate (zinc salt of 3,5,5-trimethyl hexanoic acid) solution in MTO (6 wt% Zn) was charged into a 100 ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de carbamates. Ce procédé consiste à faire réagir des amines avec des carbonates organiques en présence d'un catalyseur à base de métal. La réaction est mise en oeuvre dans des conditions telles qu'un précipitat contenant ce métal se forme au cours de la réaction ou après cette dernière.
PCT/EP1998/002889 1997-06-05 1998-05-15 Procede de preparation de carbamates Ceased WO1998055451A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU77660/98A AU7766098A (en) 1997-06-05 1998-05-15 Method for the preparation of carbamates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97109080 1997-06-05
EP97109080.8 1997-06-05

Publications (1)

Publication Number Publication Date
WO1998055451A1 true WO1998055451A1 (fr) 1998-12-10

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ID=8226878

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/002889 Ceased WO1998055451A1 (fr) 1997-06-05 1998-05-15 Procede de preparation de carbamates

Country Status (3)

Country Link
AU (1) AU7766098A (fr)
WO (1) WO1998055451A1 (fr)
ZA (1) ZA984534B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009115539A1 (fr) 2008-03-18 2009-09-24 Basf Se Carbamates métalliques à base de tolylène-diamines
WO2009115538A1 (fr) 2008-03-18 2009-09-24 Basf Se Procédé de fabrication d'uréthanes à partir d'amines aromatiques monofonctionnelles et difonctionnelles
WO2011048124A1 (fr) 2009-10-21 2011-04-28 Basf Se Procédé de production d'uréthannes
WO2013060950A1 (fr) * 2011-10-28 2013-05-02 Societe D'exploitation Generale De Produits Industriels - S.E.G. (Sas) PROCEDE DE PREPARATION D'UN COMPOSE COMPRENANT AU MOINS UN MOTIF β-HYDROXY-URETHANE ET/OU AU MOINS UN MOTIF ϒ-HYDROXY-URETHANE.
US8519174B2 (en) 2008-03-18 2013-08-27 Basf Se Metal carbamates formed from diaminophenylmethane
US8729291B2 (en) 2008-08-22 2014-05-20 Basf Se Method for producing urethanes composed of di-functional aromatic amines and dialkyl carbonates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268683A (en) * 1980-02-21 1981-05-19 The Dow Chemical Company Preparation of carbamates from aromatic amines and organic carbonates
EP0510459A2 (fr) * 1991-04-23 1992-10-28 Bayer Ag Procédé de préparation de poly(o-alkyluréthanes) de la série des diphénylméthanes
EP0520273A2 (fr) * 1991-06-27 1992-12-30 Bayer Ag Procédé pour la préparation de bis(éthoxy carbonylamino) toluols et leur utilisation dans la préparation de diisocyanatotoluols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268683A (en) * 1980-02-21 1981-05-19 The Dow Chemical Company Preparation of carbamates from aromatic amines and organic carbonates
EP0510459A2 (fr) * 1991-04-23 1992-10-28 Bayer Ag Procédé de préparation de poly(o-alkyluréthanes) de la série des diphénylméthanes
EP0520273A2 (fr) * 1991-06-27 1992-12-30 Bayer Ag Procédé pour la préparation de bis(éthoxy carbonylamino) toluols et leur utilisation dans la préparation de diisocyanatotoluols

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009115539A1 (fr) 2008-03-18 2009-09-24 Basf Se Carbamates métalliques à base de tolylène-diamines
WO2009115538A1 (fr) 2008-03-18 2009-09-24 Basf Se Procédé de fabrication d'uréthanes à partir d'amines aromatiques monofonctionnelles et difonctionnelles
US8481777B2 (en) 2008-03-18 2013-07-09 Basf Se Metal carbamates formed from tolylenediamines
US8519174B2 (en) 2008-03-18 2013-08-27 Basf Se Metal carbamates formed from diaminophenylmethane
US8846970B2 (en) 2008-03-18 2014-09-30 Basf Se Metal carbamates formed from tolylenediamines
US8846971B2 (en) 2008-03-18 2014-09-30 Basf Se Metal carbamates formed from diaminophenylmethane
US8921598B2 (en) 2008-03-18 2014-12-30 Basf Se Method for producing urethanes composed of mono and di-functional aromatic amines
US8729291B2 (en) 2008-08-22 2014-05-20 Basf Se Method for producing urethanes composed of di-functional aromatic amines and dialkyl carbonates
WO2011048124A1 (fr) 2009-10-21 2011-04-28 Basf Se Procédé de production d'uréthannes
US8871965B2 (en) 2009-10-21 2014-10-28 Basf Se Method for producing urethanes
WO2013060950A1 (fr) * 2011-10-28 2013-05-02 Societe D'exploitation Generale De Produits Industriels - S.E.G. (Sas) PROCEDE DE PREPARATION D'UN COMPOSE COMPRENANT AU MOINS UN MOTIF β-HYDROXY-URETHANE ET/OU AU MOINS UN MOTIF ϒ-HYDROXY-URETHANE.
FR2981931A1 (fr) * 2011-10-28 2013-05-03 Gen Produits Ind S E G Soc D Expl Procede de preparation d'un compose comprenant au moins un motif beta-hydroxy-urethane et/ou au moins un motif gamma-hydroxy-urethane.

Also Published As

Publication number Publication date
ZA984534B (en) 1998-12-07
AU7766098A (en) 1998-12-21

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