[go: up one dir, main page]

WO2002062765A1 - PROCEDE DE PRODUCTION DE N,N'-CARBONYLBIS-ε-CAPROLACTAME - Google Patents

PROCEDE DE PRODUCTION DE N,N'-CARBONYLBIS-ε-CAPROLACTAME Download PDF

Info

Publication number
WO2002062765A1
WO2002062765A1 PCT/EP2002/001137 EP0201137W WO02062765A1 WO 2002062765 A1 WO2002062765 A1 WO 2002062765A1 EP 0201137 W EP0201137 W EP 0201137W WO 02062765 A1 WO02062765 A1 WO 02062765A1
Authority
WO
WIPO (PCT)
Prior art keywords
caprolactam
carbonylbis
organic solvent
reaction
organic
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/EP2002/001137
Other languages
German (de)
English (en)
Inventor
Michael Kluge
Sören HILDEBRANDT
Norbert Wagner
Thomas Wehlage
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
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 BASF SE filed Critical BASF SE
Publication of WO2002062765A1 publication Critical patent/WO2002062765A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2

Definitions

  • the invention relates to a process for the preparation of N, N'-carbonylbis- ⁇ -caprolactam.
  • N, N'-carbonylbis- ⁇ -caprolactam by reacting ⁇ -caprolactam with phosgene in the presence of a tertiary aliphatic amine as hydrogen chloride-binding agent.
  • WO 00/02863 discloses the preparation of N, N'-carbonyldimidazoles by reacting imidazole with phosgene in the presence of a tertiary amine in an inert organic solvent.
  • Tertiary amines are aliphatic tertiary amines, namely trimethyl, triethyl, tripropyl and tributylamine.
  • WO 98/31672 likewise discloses the preparation of N, N'-carbonyldimidazoles by reacting imidazole with phosgene in the presence of a tertiary amine in an inert organic solvent and also names triphenylamine, tribenzylamine, 1-methylpyrrolidine, 1- as the tertiary amines Methylpyrrole and 1-methylpiperidine.
  • No. 3,862,262 discloses the production of N, N'-carbonylbis- ⁇ -caprolactam by reacting ⁇ -caprolactam with phosgene in the presence of triethylamine in benzene as solvent. The product is worked up by filtering, washing the product-containing filtrate with water, removing the solvent and recrystallizing from isopropanol.
  • JP 42/17 832 discloses the preparation of N, N'-carbonylbis- ⁇ -caprolactam by reaction of ⁇ -caprolactam with phosgene in the presence of trimethylamine, triethylamine, tripropylamine and tributylamine in solvents such as benzene, toluene and diethyl ether.
  • phosgene is reacted with phosgene in the presence of triethylamine in benzene as the solvent.
  • the product-containing solution is filtered, the filtrate is washed with water and the solvent is stripped off. The yield of the processes known from the prior art is not always satisfactory.
  • the object of the invention is to provide an improved process for the preparation of carbonylbis- ⁇ -caprolactam which gives high yields.
  • the object is achieved by a process for the preparation of N, N'-carbonylbis- ⁇ -caprolactam by one-stage reaction of ⁇ -caprolactam with phosgene, optionally in an inert organic solvent, in the presence of an organic nitrogen base without an acylatable nitrogen atom that the organic nitrogen base has a pK a value between 5 and 7.
  • the invention also relates to the use of these organic nitrogen bases as hydrogen chloride-binding agents in a one-step process for the preparation of N, N'-carbonylbis- ⁇ -caprolactam.
  • Suitable organic nitrogen bases with a pK a value between 5 and " 7 are N, N-dimethylaniline, N, N-diethylaniline, 1-methylimidazole, 1-methylbenzimidazole, alpha, beta and gamma picoline, pyridine, 2 -Ethylpyridine, 2,3-lutidine, 2,4-lutidine, 3,5-lutidine, 2-methylquinoline, 4-methylquinoline and 5-methylquinoline.
  • Preferred organic nitrogen bases have a pK a value between 6 and 7.
  • Examples are N, N-diethylaniline, alpha- and gamma-picoline, 2,3-, 2,4- and 3,5-lutidine.
  • N, N-diethylaniline is particularly preferred as the organic nitrogen base.
  • the reaction can be carried out in an inert organic solvent.
  • suitable organic solvents are benzene, toluene, ethylbenzene, o-, m- and p-xylene and their mixtures, for example technical xylene mixtures which can contain up to 25% by weight of ethylbenzene, chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride , Chlorobenzene, o-, m- and p-dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate and hydrocarbons such as hexane, petroleum ether, ligroin and cyclohexane.
  • Preferred solvents are toluene, o-, m- and p-xylene and their mixtures.
  • ⁇ -caprolactam and the tertiary aromatic A are introduced in stoichiometric amounts, ie 2 moles of the organic nitrogen base per mole of ⁇ -caprolactam, and phosgene is gassed in until the reaction is complete.
  • the reaction is usually carried out at a temperature of 0 to 90 ° C., preferably 20 to 50 ° C., for example 40 ° C.
  • the reaction time is generally 2 to 12 hours.
  • the N, N'-carbonylbis- ⁇ -caprolactam can be isolated in a manner known per se by extracting the product solution with water or aqueous mineral acid to remove the hydrochloride formed from the nitrogen base, then distilling off the solvent and purifying the N, N'-carbonylbis - ⁇ -caprolactam by recrystallization from a suitable solvent, for example isopropanol or cyclohexane.
  • a suitable solvent for example isopropanol or cyclohexane.
  • the reaction is preferably carried out in the presence of an inert organic solvent and the N, N'-carbonylbis- ⁇ -caprolactam is isolated from the product solution, the isolation comprising the steps:
  • Suitable organic solvents are those which form azeotropes with water, such as toluene, ethylbenzene, xylenes, dichloromethane, chloroform and mixtures of ethylbenzene with xylene isomers, o-, m- and p-xylene and their technical mixtures are particularly preferred, the up to May contain 25 wt .-% ethylbenzene.
  • the azeotropic distillation with xylene can be carried out at a pressure of 20 to 400 mbar and a temperature of 10 to 80 ° C.
  • the water distilled off in step (c) is preferably at least partially replaced.
  • step (b) it is also possible to add enough water in step (b) that even without replacement of water, after the inert organic solvent has been distilled off, a stirrable aqueous suspension of N, N'-carbonylbis- ⁇ -caprolactam remains.
  • Steps (a) to (e) are preferably preceded by one or more extraction steps in which the product solution is extracted with water or aqueous mineral acid in order to remove the hydrochloride of the organic nitrogen base.
  • step (b) Before adding water in step (b), part of the organic solvent can be distilled off in step (a).
  • the reaction with phosgene can be carried out batchwise or continuously.
  • Suitable reactors are stirred tanks, loop reactors, bubble columns, tubular reactors and stirred tank cascades.
  • the processing is generally carried out batchwise. Suitable extraction devices are, for example, stirred kettles, mixer-settlers and extraction columns.
  • the azeotropic distillation can be carried out in stirred tanks, stirred tanks with a distillation column or distillation columns. It is generally carried out under reduced pressure.
  • the N, N'-carbonylbis- ⁇ -caprolactam can be crystallized, for example, in Rhackkes, in fluidized-bed crystallizers or forced-circulation crystallizers.
  • the crystals can be separated off, for example, by means of suction filters or centrifuges, such as stirring pressure filters, filter presses, peeling centrifuges or pusher centrifuges.
  • the separation is generally followed by drying of the crystals, for example in a paddle dryer, conical screw dryer or fluidized bed dryer.
  • a base according to the invention with a pK a value between 5 and 7, a considerable increase in yield is achieved.
  • 900 ml of xylene are distilled off from this xylene CBC solution while stirring at 50 mbar pressure and 40 ° C. internal temperature. 1500 ml of water are added and the remaining xylene (approx. 700 ml) is distilled off azeotropically at a pressure of 50 mbar and an internal temperature of 40 ° C. The resulting CBC suspension is cooled to 25 ° C. with stirring and filtered. The filter cake is washed with 2 x 100 ml of 25 ° C warm water, filtered off and then vacuumed dry for 1 h. This gives 508 g of still moist CBC (approx. 10% residual moisture), which is dried at 100 mbar and 50 ° C. overnight. After drying, 455.6 g of CBC, corresponding to 89.5% isolated yield with a purity> 99% (HPLC), water content 0.18%.
  • xylene CBC solution is distilled off with stirring at 50 mbar pressure and 40 ° C internal temperature 900 ml of xylene. 1500 ml of water are added and the remaining xylene (approx. 700 ml) is distilled off azeotropically at a pressure of 50 mbar and an internal temperature of 40 ° C. The resulting CBC suspension is cooled to 25 ° C. with stirring and filtered. The filter cake is washed with 2 x 100 ml of 25 ° C warm water, filtered off and then vacuumed dry for 1 h. 255 g of still moist CBC (approx. 10% residual moisture) are obtained, which is dried at 100 mbar and 50 ° C. overnight. After drying, 228.3 g of CBC, corresponding to 43.0% isolated yield with a purity of 95% (HPLC), water content 0.17%.

Landscapes

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

Abstract

L'invention concerne un procédé de production de N,N'-carbonylbis- epsilon -caprolactame, selon lequel on met à réagir sur un niveau du epsilon -caprolactame avec du phosgène, éventuellement dans un solvant organique inerte, en présence d'une base azotée organique sans atome d'azote pouvant être soumis à l'acylation. L'invention est caractérisée en ce que la base azotée organique a une valeur pKa entre 5 et 7. Comme base azotée organique, on utilise de préférence N,N-diméthylaniline.
PCT/EP2002/001137 2001-02-05 2002-02-04 PROCEDE DE PRODUCTION DE N,N'-CARBONYLBIS-ε-CAPROLACTAME Ceased WO2002062765A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10105030.5 2001-02-05
DE2001105030 DE10105030A1 (de) 2001-02-05 2001-02-05 Verfahren zur Herstellung von N,N'-Carbonylbis-Epsilon-caprolactam

Publications (1)

Publication Number Publication Date
WO2002062765A1 true WO2002062765A1 (fr) 2002-08-15

Family

ID=7672826

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/001137 Ceased WO2002062765A1 (fr) 2001-02-05 2002-02-04 PROCEDE DE PRODUCTION DE N,N'-CARBONYLBIS-ε-CAPROLACTAME

Country Status (2)

Country Link
DE (1) DE10105030A1 (fr)
WO (1) WO2002062765A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1670853A1 (de) * 1967-04-17 1971-02-18 Bayer Ag Verfahren zur Herstellung von Lactam-N-carbonsaeureamiden
JPH0217832A (ja) * 1988-05-16 1990-01-22 Aglo Sa 自動充電器
US5116958A (en) * 1989-01-13 1992-05-26 Ciba-Geigy Corporation Disperse dyes which are convertible into a thermomigration fast form
US5972237A (en) * 1995-05-17 1999-10-26 Basf Aktiengesellschaft Use of heterocyclic compounds as activators for inorganic peroxy compounds
EP1151996A2 (fr) * 2000-04-28 2001-11-07 Snpe Procédé de préparation des N,N'-carbonyl bis lactames

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1670853A1 (de) * 1967-04-17 1971-02-18 Bayer Ag Verfahren zur Herstellung von Lactam-N-carbonsaeureamiden
JPH0217832A (ja) * 1988-05-16 1990-01-22 Aglo Sa 自動充電器
US5116958A (en) * 1989-01-13 1992-05-26 Ciba-Geigy Corporation Disperse dyes which are convertible into a thermomigration fast form
US5972237A (en) * 1995-05-17 1999-10-26 Basf Aktiengesellschaft Use of heterocyclic compounds as activators for inorganic peroxy compounds
EP1151996A2 (fr) * 2000-04-28 2001-11-07 Snpe Procédé de préparation des N,N'-carbonyl bis lactames

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 68, no. 23, 3 June 1968, Columbus, Ohio, US; abstract no. 104571g, YO OKUDA ET AL.: "N,N'-Carbonylbiscaprolactam" XP002143357 *

Also Published As

Publication number Publication date
DE10105030A1 (de) 2002-08-08

Similar Documents

Publication Publication Date Title
EP0496306B1 (fr) Procédé pour la préparation du chlorhydrate de la 3-amino-9,13-b-dihydro-1H-dibenz-[c,f]imidazo[1,5-a]azépine
EP0595150B1 (fr) Procédé de préparation de composés aromatiques ayant des groupes bromomethyl
EP0719757B1 (fr) Procédé de préparation d'anhydride d'acide 3-chlorophtalique
DE602005003472T2 (de) Verfahren zur herstellung von 2-oxo-1-pyrrolidinderivaten durch intramolekulare allylierung
EP1470111A1 (fr) Procede de production et de purification de 1,7'-dimethyl-2'-propyl-2,5'-bi-1h-benzimidazol
DE3226723C2 (fr)
WO2002062765A1 (fr) PROCEDE DE PRODUCTION DE N,N'-CARBONYLBIS-ε-CAPROLACTAME
EP0856509B1 (fr) Procédé de préparation de diacylimides
DE69631608T2 (de) Herstellung von einem clavulansäuresalz
EP0082396B1 (fr) Procédé de préparation de cis-dicarboxy-4,5-imidazolid-2-on-1,3 disubstitués
CN107337628B (zh) 一种制备左乙拉西坦的方法
DE69100200T2 (de) Verfahren zur industriellen Herstellung von 3-Sulfamoyl-4-chlor-N-(2,3-dihydro-2-methyl-1H-indol-1-yl)-Benzamide ausgehend von 2,3-Dihydro-2-methyl-1H-indol und Hydroxylamine-O-sulfonsäure.
DE4316576A1 (de) Verbessertes Verfahren zur Herstellung von 1,3-Dipropyl-8-(3-Oxocyclopentyl)-xanthin
WO2002062754A1 (fr) PROCEDE DE PREPARATION DE N,N'-CARBONYLBIS-$G(e)-CAPROLACTAME
DE69219582T2 (de) Neue verbindung und trennungsreagenz
DE69906392T2 (de) Verfahren zur herstellung von n6-substituierten deaza-adenosinderivaten
DE69411387T2 (de) Verfahren zur Herstellung von pharmazeutisch aktiven Benzothiazepinderivaten.
DE69421137T2 (de) Verfahren zur Herstellung von 1,2-Diacyl-2-t-alkylhydroziden
CH663204A5 (de) Propannitrilderivate.
DE19630957C2 (de) Verfahren zur Reinigung von 1,3-Bis(3-aminopropyl)-1,1,3,3-tetraorganodisiloxan
DE4223013A1 (de) Verfahren zur Herstellung von 2,5-disubstituierten Pyridinen
DE69304581T2 (de) Verfahren zur Herstellung von 1,4-Dicyano-2-Buten und ein Katalysator dafür
EP0021039B1 (fr) Procédé de préparation d'azométhines aromatiques
DE2331665A1 (de) Dialkylaminoalkylester von arylaliphatischen saeuren und ihre saeureadditionssalze und verfahren zu deren herstellung
DE19947953A1 (de) Verfahren zur selektiven Spaltung cyclischer Carbonsäureanhydride

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP