EP1100784A1 - Procede pour la preparation de n,n'-carbonyldiazoles - Google Patents

Procede pour la preparation de n,n'-carbonyldiazoles

Info

Publication number
EP1100784A1
EP1100784A1 EP99936551A EP99936551A EP1100784A1 EP 1100784 A1 EP1100784 A1 EP 1100784A1 EP 99936551 A EP99936551 A EP 99936551A EP 99936551 A EP99936551 A EP 99936551A EP 1100784 A1 EP1100784 A1 EP 1100784A1
Authority
EP
European Patent Office
Prior art keywords
azole
formula
phosgene
process according
solvent
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
EP99936551A
Other languages
German (de)
English (en)
Inventor
Johannes Scherer
Alexander Klausener
Robert Söllner
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1100784A1 publication Critical patent/EP1100784A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to an improved process for the preparation of N, N'-carbonyldiazoles by reacting azoles with phosgene.
  • N, N'-carbonyldiazoles can be obtained if azoles are reacted with phosgene (see DE-AS 10 33 210).
  • Tetrahydrofuran, other ethers and hydrocarbons are proposed as solvents, in particular anhydrous tetrahydrofuran and mixtures of
  • the azole hydrochloride precipitate formed during the reaction accumulates as a viscous, sticky mass which adheres firmly to the vessel wall and stirrer, making it very difficult to stir.
  • the stiffness of stirring then limits the maximum possible space yield to relatively low values.
  • the precipitate solidifies towards the end of the phosgene addition, hard balls are formed which can cause damage to the reaction vessel and its internals (e.g. stirrers, immersion tubes, etc.).
  • X 1 , X 2 and X 3 each independently represent CR 1 or nitrogen, where R 1 is hydrogen or Ci- -alkyl and
  • R 2 represents hydrogen
  • X 2 represents CR 1 or nitrogen, where R 1 is hydrogen or C 6 -C 6 -alkyl,
  • a solvent which is characterized in that the azole of the formula (II) is metered in with phosgene into an aromatic solvent dehydrated by distillation in such a way that, in the time in which 1 mol of azole of the formula is metered in, 0 17 to 0.34 mol of phosgene are metered in.
  • the azole hydrochloride for example imidazole hydrochloride
  • the stirring resistance is significantly lower than when the method is not according to the invention. It is therefore possible, according to the invention, to use significantly higher reactant concentrations than previously, which results in a significantly improved space yield compared to the prior art.
  • the azole hydrochloride is also crystalline towards the end of the metering in of azoles of the formula (II) and phosgene
  • Precipitation before It can be easily and completely flushed out of the reactor into a filtering device with the reaction mixture.
  • the filtration times are short due to the crystallinity of the precipitate.
  • azole of the formula (II) is used in the process according to the invention, and an N, N'-carbonyldiazole of the formula (I) is obtained in which the two azole rings are identical.
  • Imidazole is very particularly preferred here.
  • Phosgene can be used in the usual technical quality. It is advantageous to use 0.2 to 0.3 mol, in particular 0.22 to 0.27 mol, of phosgene per mole of azole of the formula (II). It is particularly preferred to use 0.25 mol of phosgene per mole of azole of the formula (II).
  • aromatic solvents there are e.g. Benzene, toluene, xylenes, monochlorobenzene, dichlorobenzenes, trichlorobenzenes and mixtures of these solvents are suitable.
  • aromatic solvents there are e.g. Benzene, toluene, xylenes, monochlorobenzene, dichlorobenzenes, trichlorobenzenes and mixtures of these solvents are suitable.
  • Distillation to drain the solvents can e.g. so happen that the respective solvent is heated to boiling temperature before use at normal or reduced pressure until no more discharge of water is observed.
  • the respective solvent is heated to boiling temperature before use at normal or reduced pressure until no more discharge of water is observed.
  • between 0.1 and 5, preferably between 0.5 and 2% by weight of the solvent is distilled off.
  • the azole used can be in the form of a solution or suspension at a temperature of e.g. 20 to 120 ° C, preferably 60 to 100 ° C, can be metered into the abovementioned solvents or as a melt. This type of dosing makes it easier to control the dosing speed.
  • the method according to the invention can e.g. be carried out at temperatures of 50 to 120 ° C. Preferably one works at 70 to 100 ° C.
  • reaction mixture for some time after e.g. Stir for 30 minutes to 5 hours at elevated temperature.
  • the reaction mixture can e.g. Work up so that the azole hydrochloride precipitate formed is separated at 50 to 120 ° C, preferably at 70 to 100 ° C, by filtration.
  • the filtration works well due to the consistency of the precipitation.
  • N, N'-carbonyldiazole can be isolated from the mother liquor obtained in the hydrochloride separation if the mother liquor is cooled to +40 to -70 ° C, preferably to +25 to -20 ° C, and the product which crystallizes out is filtered off.
  • the product is obtained in a well crystallized form in purities of over 95%.
  • azole hydrochloride which according to the prior art appears to have to be disposed of or otherwise used. It has also been found that an azole which has been wholly or partly obtained from azole hydrochloride, in particular from, can be used in the process according to the invention
  • Azole hydrochloride which is obtained as a by-product in the synthesis of N, N'-carbonyldiazole.
  • the recovery of azoles from azole hydrochlorides can e.g. be carried out in such a way that azole hydrochlorides, in particular in the synthesis of N, N'-
  • Azole hydrochlorides formed in carbonyldiazoles, in a solvent mixture comprising, on the one hand, an aromatic solvent such as benzene, toluene, a xylene, monochlorobenzene, a dichlorobenzene, a trichlorobenzene or mixtures thereof, preferably in the solvent in which the synthesis of N, N'-carbonyldiazole was carried out, and on the other hand a solvent of the formula
  • R 4 represents hydrogen or C j -C 4 alkyl
  • n corresponds to the valence of M
  • M represents an alkali or alkaline earth metal
  • R 4 has the meaning given for formula (III),
  • R 4 preferably represents hydrogen or methyl
  • M preferably represents lithium, sodium or potassium.
  • the imidazole hydrochloride precipitate was filtered off and washed with 200 g of chlorobenzene at 80 ° C. The combined filtrates were cooled to 20 ° C. The precipitated carbonyldiimidazole precipitate was filtered off, washed with 200 g of dried chlorobenzene and opened at 60 ° C. at 50 mbar.
  • the imidazole hydrochloride precipitate was filtered off and washed with 200 g of chlorobenzene at 80 ° C. The combined filtrates were cooled to 20 ° C. The precipitated carbonyldiimidazole precipitate was filtered off with 200 g of dried Washed chlorobenzene and dried at 60 ° C at 50 mbar. 265.0 g of colorless crystals (98.0% carbonyldiimidazole, 89.0% of theory) were obtained.
  • the imidazole hydrochloride precipitate was filtered off and washed with 200 g of chlorobenzene at 80 ° C. The combined filtrates were cooled to 20 ° C. The precipitated carbonyldiimidazole precipitate was filtered off, washed with 200.0 g of dried chlorobenzene and dried at 60 ° C. and 50 mbar. 255.0 g of colorless crystals (97.5% carbonyldiimidazole, 83.3% of theory) were obtained.

Abstract

L'invention concerne un procédé pour la préparation de N,N'-carbonyldiazoles par réaction d'azoles avec du phosgène dans un solvant, selon lequel on introduit, dans un solvant aromatique déshydraté par distillation, une dose de 1 mole d'azole et en même temps une dose de 0,17 à 0,34 mole de phosgène. On décrit également des possibilités particulièrement avantageuses pour le retraitement du mélange de réaction.
EP99936551A 1998-07-28 1999-07-16 Procede pour la preparation de n,n'-carbonyldiazoles Ceased EP1100784A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19833913 1998-07-28
DE19833913A DE19833913A1 (de) 1998-07-28 1998-07-28 Verfahren zur Herstellung von N,N'-Carbonyldiazolen
PCT/EP1999/005072 WO2000006551A1 (fr) 1998-07-28 1999-07-16 Procede pour la preparation de n,n'-carbonyldiazoles

Publications (1)

Publication Number Publication Date
EP1100784A1 true EP1100784A1 (fr) 2001-05-23

Family

ID=7875557

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99936551A Ceased EP1100784A1 (fr) 1998-07-28 1999-07-16 Procede pour la preparation de n,n'-carbonyldiazoles

Country Status (13)

Country Link
US (1) US6392057B1 (fr)
EP (1) EP1100784A1 (fr)
JP (1) JP2002521474A (fr)
KR (1) KR20010072086A (fr)
CN (1) CN1311781A (fr)
AU (1) AU5160599A (fr)
CA (1) CA2338631A1 (fr)
DE (1) DE19833913A1 (fr)
HK (1) HK1040079A1 (fr)
HU (1) HUP0103373A3 (fr)
IL (1) IL140529A0 (fr)
PL (1) PL345697A1 (fr)
WO (1) WO2000006551A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19830556A1 (de) * 1998-07-08 2000-01-13 Basf Ag Verfahren zur Herstellung von Carbonyldiimidazolen
DE10035011A1 (de) 2000-07-19 2002-01-31 Bayer Ag Verfahren zur Herstellung von N,N`-Carbonyldiazolen und Azolidsalzen
JP3867046B2 (ja) * 2001-02-23 2007-01-10 株式会社日立製作所 分析システム
US6455702B1 (en) * 2001-05-16 2002-09-24 Aims Fine Chemicals, Inc. Process for the production of N,N-carbonyl diimidazole
DE10359797A1 (de) * 2003-12-19 2005-07-21 Bayer Chemicals Ag Verfahren zur Herstellung von N,N'-Carbonyldiazolen
WO2005095355A1 (fr) * 2004-03-30 2005-10-13 Hodogaya Chemical Co., Ltd. Procédé servant à produire du n,n'-carbonyldiimidazole
DE102004023606A1 (de) * 2004-05-13 2005-12-01 Bayer Chemicals Ag Verfahren zur Herstellung von N,N'-Carbonyldiazolen
US10522251B2 (en) 2016-07-08 2019-12-31 International Business Machines Corporation Infrared detectors and thermal tags for real-time activity monitoring
US10311273B2 (en) 2016-10-18 2019-06-04 International Business Machines Corporation Thermal tags for real-time activity monitoring and methods for detecting the same
US10906469B2 (en) * 2019-01-31 2021-02-02 Nissan North America, Inc. Vehicle console assembly

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1033210B (de) 1956-12-06 1958-07-03 Basf Ag Verfahren zur Herstellung von Kohlensaeureamiden von Imidazolen, Triazolen und Tetrazolen
DE4424400A1 (de) 1994-07-11 1996-01-18 Bayer Ag Verbessertes Verfahren zur Herstellung von N,N'-Carbonyldiazolen, insbesondere N,N'-Carbonyldiimidazol
WO1998031672A1 (fr) * 1997-01-17 1998-07-23 Ppg Industries Ohio, Inc. Procede d'elaboration de composes n, n'-diazole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0006551A1 *

Also Published As

Publication number Publication date
AU5160599A (en) 2000-02-21
IL140529A0 (en) 2002-02-10
WO2000006551A1 (fr) 2000-02-10
US6392057B1 (en) 2002-05-21
DE19833913A1 (de) 2000-02-03
HUP0103373A2 (hu) 2001-12-28
CN1311781A (zh) 2001-09-05
CA2338631A1 (fr) 2000-02-10
JP2002521474A (ja) 2002-07-16
HUP0103373A3 (en) 2003-01-28
HK1040079A1 (zh) 2002-05-24
KR20010072086A (ko) 2001-07-31
PL345697A1 (en) 2002-01-02

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