EP0212512A1 - Procédé de production d'esters de l'acide carbamique - Google Patents

Procédé de production d'esters de l'acide carbamique Download PDF

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Publication number
EP0212512A1
EP0212512A1 EP86111022A EP86111022A EP0212512A1 EP 0212512 A1 EP0212512 A1 EP 0212512A1 EP 86111022 A EP86111022 A EP 86111022A EP 86111022 A EP86111022 A EP 86111022A EP 0212512 A1 EP0212512 A1 EP 0212512A1
Authority
EP
European Patent Office
Prior art keywords
acid esters
electrolysis
carbamic
alkyl
manufacturing
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.)
Granted
Application number
EP86111022A
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German (de)
English (en)
Other versions
EP0212512B1 (fr
Inventor
Dieter Dr. Degner
Heinz Hannebaum
Michael Dr. Steiniger
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.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0212512A1 publication Critical patent/EP0212512A1/fr
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Publication of EP0212512B1 publication Critical patent/EP0212512B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the present invention relates to a new process for the preparation of carbamic acid esters.
  • Carbamic acid esters as is generally known, have been prepared from phosgene by reaction with alcohols to form chloroformic acid esters and subsequent aminolysis. Dealing with the highly toxic and corrosive preliminary and intermediate products requires considerable technical effort. HCl or halogen-containing waste salts are also obtained in these processes, the separation of which is often technically very complex (cf. Ullmann, Enzyklopadie der techn. Chemie, Vol. 9, p. 118 ff.).
  • the invention was based on the object of finding a process for the preparation of carbamic esters which is technically simple and economical and is distinguished by particular environmental friendliness.
  • carbamic acid esters of the general formula (I) R1NHCOOR2 (I), in which R1 is hydrogen or an alkyl, cycloalkyl or alkaryl radical and R2 is a low molecular weight alkyl radical, can be prepared particularly advantageously if formamides of the general formula (II) R1NHCHO (II) electrochemically oxidized in the presence of alcohols of the formula R2OH and in the presence of an ionogenic halide.
  • Suitable cycloalkyl radicals are those having 3 to 8, in particular 5 and 6, carbon atoms.
  • R1 can be alkylaryl radicals having 7 to 12, in particular 7 to 8, carbon atoms, e.g. represent benzyl or phenylethyl radicals.
  • radicals mentioned can still carry substituents which are inert under the reaction conditions, e.g. C1-C4 alkyl or alkoxy groups, halogen or nitrile groups.
  • the following formamides can be implemented: methylformamide, ethylformamide, n- and iso-propylformamide, n-butylformamide, n-octylformamide, cyclohexyl- or cyclopentylformamide, benzylformamide and the unsubstituted formamide.
  • R2 represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
  • R2 represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
  • n- or iso-propanol, n-butanol, n-propanol and in particular methanol, ethanol can be used.
  • Suitable ionogenic halides are salts of hydrogen iodide, hydrobromic acid and hydrochloric acid. Salts of hydrobromic acid, such as alkali, alkaline earth bromides and quaternary ammonium, especially tetraalkylammonium bromides are particularly preferred.
  • the cation does not play an essential role in the invention, therefore other ionic metal halides can also be used, but one becomes advantageous choose cheap halides. Examples include sodium, potassium, calcium and ammonium bromide, and di-, tri- and tetramethyl- or tetraethylammonium bromide.
  • the method according to the invention does not require a special electrolysis cell. It can advantageously be carried out in an undivided flow cell.
  • All anode materials which are customary per se and are stable under the electrolysis conditions, such as noble metal, for example gold or platinum or metal oxides such as NiO x, can be used as anodes.
  • the preferred anode material is graphite.
  • the cathode material consists, for example, of metals such as lead, iron, steel, nickel or precious metals such as platinum.
  • the preferred cathode material is also graphite.
  • the composition of the electrolyte can be chosen within wide limits.
  • the electrolyte consists of 10-80 wt% R1NHCHO 10 - 80% by weight. R2OH 0.1 - 10% by weight halide.
  • a solvent can be added to the electrolyte, for example to improve the solubility of the formamide or the halide.
  • examples include nitriles such as acetonitrile, carbonates such as dimethyl carbonates and ethers such as tetrahydrofuran.
  • the current density is not a limiting factor for the method according to the invention, it is e.g. 1 to 25 A / dm2, preferably 3 to 12 A / dm2.
  • the temperature is expediently chosen so that it is at least 5 to 10 ° C. below the boiling point of the electrolyte.
  • electrolysis is preferably carried out at temperatures of 20 to 30 ° C.
  • the process according to the invention offers the possibility of largely converting the formamides without there being any deterioration in yield.
  • the current yields are also unusually high in the process according to the invention.
  • the formamide is already fully converted in electrolysis with 2 to 2.5 F / mol formamide.
  • the electrolysis discharges can be worked up by methods known per se.
  • the electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off, the halides are separated in a known manner, for example by filtration or extraction, and the carbamic acid esters are distilled or recrystallized. Alkanol, possibly unreacted formamide and cosolvent as well as halides can advantageously be returned to electrolysis.
  • the process according to the invention can be carried out batchwise or continuously.
  • the carbamic acid esters produced by the process according to the invention are versatile intermediates for the synthesis of isocyanates, crop protection agents and auxiliaries, e.g. for finishing textiles.
  • the electrooxidation was carried out in an undivided electrolysis cell with graphite anodes and cathodes at temperatures of 20 to 25 ° C.
  • the electrolyte which contains sodium bromide as the conductive salt, was pumped through the cell at 200 l / h via a heat exchanger.
  • the composition of the electrolyte is shown in Table 1.
  • the work-up was carried out in such a way that the alcohol was distilled off at atmospheric pressure up to a bottom temperature of 120 to 130 ° C. and the remaining residue was distilled in at 5 to 40 mbar.
  • the purification was carried out by recrystallization from ethyl acetate.
  • the residue was filtered hot after separating the alcohol at 80-100 ° C. (separation of NaBr); the urethanes then crystallized from the filtrate at 20-30 ° C. in spectroscopic (1 H-NMR) pure form.
  • the carbamic acid esters were obtained at a conversion of 100% in yields of 57 to 88%, based on the starting material (II).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP86111022A 1985-08-17 1986-08-09 Procédé de production d'esters de l'acide carbamique Expired EP0212512B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853529531 DE3529531A1 (de) 1985-08-17 1985-08-17 Verfahren zur herstellung von carbamidsaeureestern
DE3529531 1985-08-17

Publications (2)

Publication Number Publication Date
EP0212512A1 true EP0212512A1 (fr) 1987-03-04
EP0212512B1 EP0212512B1 (fr) 1988-11-17

Family

ID=6278769

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86111022A Expired EP0212512B1 (fr) 1985-08-17 1986-08-09 Procédé de production d'esters de l'acide carbamique

Country Status (13)

Country Link
US (1) US4661217A (fr)
EP (1) EP0212512B1 (fr)
JP (1) JPH076075B2 (fr)
CN (1) CN1013887B (fr)
AU (1) AU587849B2 (fr)
CA (1) CA1275066A (fr)
DE (2) DE3529531A1 (fr)
DK (1) DK388786A (fr)
FI (1) FI86715C (fr)
HU (1) HU199109B (fr)
IL (1) IL79645A (fr)
NO (1) NO163965C (fr)
ZA (1) ZA866150B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0308744A1 (fr) * 1987-09-12 1989-03-29 BASF Aktiengesellschaft Procédé de préparation d'imidazolidinones et oxazolidinones

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3606478A1 (de) * 1986-02-28 1987-09-03 Basf Ag Verfahren zur herstellung von biscarbamaten und neue biscarbamate
US5214169A (en) * 1988-04-25 1993-05-25 Merrell Dow Pharmaceuticals Inc. N-(2,3-epoxycyclopentyl) carbamate derivatives
JP3168031B2 (ja) * 1990-11-16 2001-05-21 トヨタ自動車株式会社 耐熱性ヘラパタイト及びその製造方法
CN107964668B (zh) * 2016-10-19 2019-08-16 中国科学院上海有机化学研究所 化合物中C(sp3)-H键转化为C(sp3)-O键方法及制备得到的化合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE676746A (fr) * 1965-02-19 1966-08-18
FR2298614A1 (fr) * 1975-01-25 1976-08-20 Hoechst Ag Procede de preparation de n-(a-alcoxyethyl)-carboxamides
EP0067463A1 (fr) * 1981-06-05 1982-12-22 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'isocyanates et/ou de ses dérivés

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459643A (en) * 1967-02-03 1969-08-05 Sprague Electric Co Alkoxylation of n-methyl-n-hydrocarbylamides
US3464960A (en) * 1967-12-15 1969-09-02 Us Army Mixture for rapid polymerization
DE2336976A1 (de) * 1973-07-20 1975-02-13 Hoechst Ag Verfahren zur herstellung von n-(alphaalkoxyaethyl)-carbonsaeureamiden
US4138408A (en) * 1975-12-20 1979-02-06 Hoechst Aktiengesellschaft ω-Alkoxy derivatives of lactams and process for their manufacture
DE2655741A1 (de) * 1976-12-09 1978-06-15 Hoechst Ag Verfahren zur herstellung von carbamidsaeureestern hoehersiedender alkohole
DE2919756A1 (de) * 1979-05-16 1980-11-27 Hoechst Ag Verfahren zur herstellung von n- alpha -alkoxyethyl-carbonsaeureamiden
DE3233309A1 (de) * 1982-09-08 1984-03-08 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von n-substituierten carbamaten
EP0106352B1 (fr) * 1982-10-19 1989-06-14 Mitsubishi Rayon Co., Ltd. Composition de polymère
US4457813A (en) * 1983-03-04 1984-07-03 Monsanto Company Electrolysis cells and electrolytic processes
DE3435388A1 (de) * 1984-09-27 1986-04-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von aromatischen carbonsaeureestern
US4588482A (en) * 1985-06-10 1986-05-13 Basf Aktiengesellschaft Preparation of phthalaldehyde acetals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE676746A (fr) * 1965-02-19 1966-08-18
FR2298614A1 (fr) * 1975-01-25 1976-08-20 Hoechst Ag Procede de preparation de n-(a-alcoxyethyl)-carboxamides
EP0067463A1 (fr) * 1981-06-05 1982-12-22 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'isocyanates et/ou de ses dérivés

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0308744A1 (fr) * 1987-09-12 1989-03-29 BASF Aktiengesellschaft Procédé de préparation d'imidazolidinones et oxazolidinones

Also Published As

Publication number Publication date
DK388786A (da) 1987-02-18
FI863246A (fi) 1987-02-18
JPS6240389A (ja) 1987-02-21
JPH076075B2 (ja) 1995-01-25
US4661217A (en) 1987-04-28
DE3529531A1 (de) 1987-02-26
NO863297L (no) 1987-02-18
DE3661202D1 (en) 1988-12-22
AU6150786A (en) 1987-02-19
IL79645A (en) 1990-07-12
CN1013887B (zh) 1991-09-11
NO163965B (no) 1990-05-07
FI863246A0 (fi) 1986-08-08
IL79645A0 (en) 1986-11-30
CA1275066A (fr) 1990-10-09
NO863297D0 (no) 1986-08-15
NO163965C (no) 1990-08-15
AU587849B2 (en) 1989-08-31
ZA866150B (en) 1987-04-29
DK388786D0 (da) 1986-08-15
HUT43032A (en) 1987-09-28
FI86715B (fi) 1992-06-30
HU199109B (en) 1990-01-29
EP0212512B1 (fr) 1988-11-17
FI86715C (fi) 1992-10-12
CN86105208A (zh) 1987-02-18

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