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WO1992009601A1 - Procede de preparation de composes heterocycliques azotes substitues - Google Patents

Procede de preparation de composes heterocycliques azotes substitues Download PDF

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Publication number
WO1992009601A1
WO1992009601A1 PCT/US1991/008741 US9108741W WO9209601A1 WO 1992009601 A1 WO1992009601 A1 WO 1992009601A1 US 9108741 W US9108741 W US 9108741W WO 9209601 A1 WO9209601 A1 WO 9209601A1
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WO
WIPO (PCT)
Prior art keywords
reagent
reaction
triazine
dichloro
substituted
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/US1991/008741
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English (en)
Inventor
John Christopher Schmidhauser
Kathryn Lynn Longley
William Lee Gately
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General Electric Co
Original Assignee
General Electric Co
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Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of WO1992009601A1 publication Critical patent/WO1992009601A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • U.S. Patent 4,895,945 describes the reaction of cyanuric chloride and alkyl or aryl chlorocyanurates with glycidol to form mono- and diglycidoxy-substituted triazines. Said reaction is conducted in an organic solvent such as methylene chloride, by gradual addition of the glycidol and of aqueous base to a solution of a chloro-substituted triazi ⁇ e.
  • the present invention is based on the discovery of various modifications in the above-described reaction process which contribute materially to improvement of yield and to the ability to conduct the reaction in a minimum of time and under relatively simple conditions, incfuded are both mandatory and optional modifications.
  • the method has wide applicability to a number of halo-substituted aromatic nitrogen-heterocyclic compounds and a number of unsubstituted and substituted aliphatic alcohols.
  • the invention is a method for preparing a halo-displacement reaction product of (A) an aliphatic hydroxy compound and (B) an aromatic heterocyclic compound containing (1) at least two nuclear nitrogen atoms or (2) at least one nuclear nitrogen atom and at least one electron-withdrawing group, said atom or group activating a chloro- or bromo-substituted carbon atom adjacent to said nitrogen atom, which comprises effecting contact between reagents A and B in solution in a substantially water-immiscible organic solvent under alkaline conditions, in the presence of a phase transfer catalyst and in the substantial absence of water and inorganic salts other than those formed in the reaction.
  • Reagent A employed in the method of this invention is an aliphatic hydroxy compound. Any such compound may be employed; included are both unsubstituted and substituted alkanols.
  • Reagent A may be a simple alka ⁇ ol such as methanol, ethanol, 1-propanol, 2- propanot, 1-butanol, 1-hexa ⁇ ol or 2-ethylhexanol; an epoxy- substituted alkanol such as glycidol (2,3-epoxy-1-propanol); a halo- or phosphate-substituted alkanol such as 2-chloro-1 -ethanol, dimethyl 2-hydroxyethyl phosphate or di-n-butyl 2-hydroxyethyl phosphate; or a cyclic ortho ester such as 4-hydroxymethyl-2- methoxy-2-methyl-1 ,3-dioxolane and 4-hydroxy-1 -methyl-2,6,7- trioxab ⁇ cyclo[2.2.2]
  • Reagent B is an aromatic nitrogen-heterocyclic compound with certain molecular features including a chloro or bromo substituent on a carbon atom adjacent to a nitrogen atom and one of the following: (1) at least two nuclear nitrogen atoms or (2) at least one such atom in combination with at least one electron- withdrawing group activating said chloro or bromo substituent.
  • Suitable electron-withdrawing groups are nitro, carbalkoxy, perfluoroalkyl and acyl substituents and other nitrogen hetero atoms.
  • the heterocyclic compound usually contains a 6- membered ring.
  • a wide variety of such compounds may be employed including those having the following heterocyclic nuclei, all substituents except the chloro or bromo substituents being omitted in these formulas:
  • the preferred heterocyclic compounds are those containing at least 2 and preferably 3 nuclear (i.e., heterocyclic) nitrogen atoms, whereupon the second such nitrogen atom serves as the activating group for the chloro or bromo substituent.
  • 1 ,3,5- Triazines are especially preferred, with the alkoxy- or aryloxy- substituted chloro-1 ,3,5-triazines being most preferred; examples are 2,4-dichloro-4-n-butoxy-1 ,3,5-triazine and 2,4-dichIoro-4- (2,4,6-trimethylphe ⁇ oxy)-1 ,3,5-triazine.
  • the halo- displacement reaction between reagents A and B is conducted in a substantially water-immiscible organic solvent.
  • Suitable solvents include aromatic hydrocarbons such as toluene and xylene, chlorinated aromatic hydrocarbons such as chlorobenzene and o- dichlorobenzene, and chlorinated aliphatic hydrocarbons such as methylene chloride and chloroform. Methylene chloride and toluene are particularly suitable, with toluene frequently being preferred by reason of its relative environmental harmless ⁇ ess.
  • phase transfer catalyst Any such catalyst known in the art may be employed; examples of suitable types of compounds are quaternary ammonium and phosphonium salts, hexaalkylguanidinium salts and crown ethers. Quaternary ammonium salts are frequently preferred because of their effectiveness and relative availability. Particularly preferred are quaternary ammonium salts having a single alkyl group containing about 8-20 carbon atoms and having 1
  • Another essential feature is the substantial absence water and of inorganic salts, other than those formed in the reaction between reagents A and B.
  • inorganic salts such as those which may have been formed in the course of a previous reaction to prepare reagent B, should be removed by filtration, decantation of liquid or the like prior to the reaction.
  • the time required for the second reaction is relatively long when said sodium chloride and water are not removed from the reaction mixture prior to further reaction with glycidol. If salt and water removal takes place according to this invention, the reaction time can be decreased significantly, typically to 1/6 of the time required if separation does not take place. It is not necessary in this example, however, to continuously remove salts during the reaction of the intermediate with glycidol.
  • the method of this invention is conducted under alkaline conditions, most often in the presence of an aqueous metal hydroxide such as sodium hydroxide or potassium hydroxide. Fairly concentrated aqueous base solutions, most often at least about 40% by weight, are usually employed. The proportion of base is usually about 10-25% in excess of the stoichiometric amount. Most often, the base is added gradually or incrementally to the other reagents.
  • Reaction temperatures according to the invention may be in the range of about 0-70'C. Temperatures of about 10-25'C are generally preferred since they result in the formation of a minimum of by-products.
  • reagents A and B are present in the amount of at least about 25% by weight of the organic phase. That is, reagents A and B together constitute at least about 25% of the total weight of reagent A, reagent B and organic solvent. At such concentrations, the reaction rate is increased and the amount of time necessary for completion of the reaction is further diminished. The especially preferred proportion of reagents A and B is from about 25% to the amount affording a saturated solution. Following completion of the reaction, it is possible to recover product by conventional means including stripping of the organic solvent.
  • substituted chlorotriazines as capping agents for polyphenylene ethers in the form of a solution in an organic solvent, typically an aromatic hydrocarbon such as toluene.
  • an organic solvent typically an aromatic hydrocarbon such as toluene.
  • a chlorinated aliphatic hydrocarbon such as methylene chloride
  • methylene chloride may be replaced by toluene by first removing a major proportion of the methylene chloride by distillation at atmospheric pressure, followed by addition of toluene and vacuum stripping of the remaining methylene chloride.
  • a 100-gallon reactor fitted with an agitator, thermocouple probe, reflux condenser, addition funnel and nitrogen charge means was charged with 147 kg. of methylene chloride and 24.4 kg. (179.4 moles) of mesitol as a melt at 80"C.
  • the reactor was cooled to 5'C and there were added 31.5 kg. (170.8 moles) of cyanuric chloride and 920 grams of cetyltrimethylammonium chloride.
  • the reactor was further cooled to 2'C and 15 kg. (187.9 moles) of 50% aqueous sodium hydroxide solution was added slowly, with further cooling to maintain the temperature below 15'C.
  • the mixture was stirred under nitrogen for 1 hour following the completion of sodium hydroxide addition.
  • the precipitated salts were allowed to settle and the organic solution was separated.
  • the salts were treated with 38 liters of deionized water and 11.4 liters of methylene chloride.
  • the methylene chloride layer was combined with the reaction mixture in the cleaned reactor.
  • the mixture was again cooled to 5'C and 15.8 kg. (213.5 moles) of glycidol was added, followed by slow addition of an additional 16.4 kg. (205 moles) of sodium hydroxide solution.
  • the temperature was maintained below 25'C during sodium hydroxide addition, and then at 25'C for an additional hour.
  • Example 1 The reactor of Example 1 was charged with 96 kg. of toluene, and 14 kg. (102.9 moles) of mesitol was added as a melt. The solution was cooled to 5'C and there were added 18 kg. (97.6 moles) of cyanuric chloride and 500 grams of cetyltrimethylammonium chloride. There was then added under nitrogen, with stirring, 8.6 kg. (107.4 moles) of 50% aqueous sodium hydroxide solution over 2 hours, as the mixture was maintained at 5-15"C. The mixture was allowed to warm to room temperature and 76 liters of deionized water was added, with stirring, to dissolve inorganic salts.
  • Reagents A and B comprised about 29% by weight of total organic phase.
  • the solution was cooled to 0°C and 19.0 grams (238 mmol.) of 50% aqueous sodium hydroxide solution was added, with stirring, at a rate such that the temperature did not rise above 5°C. After base addition had been completed, the mixture was stirred at 0-5°C for 30 minutes, after which high pressure chromatographic analysis showed the reaction to be complete with a product distribution of about 95.6% mesitoxy dichlorocyanurate and 4.4% dimesitoxy chlorocyanurate.
  • the clear reaction solution was decanted away from the white mass of salt and water which clung to the sides of the reaction flask.
  • the flask was rinsed and cleaned, the solution was reintroduced and 20 grams (270 mmol.) of glycidol was added. Additional sodium hydroxide solution in the amount of 21 grams (262 mmol.) was then introduced at a rate to maintain the temperature at 15-20°C.
  • the mixture was stirred at room temperature for 1 hour, after which it was shown by analysis to contain the desired 2-chloro-4-mesitoxy-6-glycidoxy-1 ,3,5- triazine in a total yield of 90.8%.
  • the by-product dimesitoxy chlorocyanurate was present in the amount of 9.2%.
  • the mixture was washed with water three times, after which it separated cleanly into aqueous and organic layers.
  • the organic layer was removed and toluene was exchanged for the methylene chloride therein as described in Example 1.
  • the total isolated yield of product in the toluene solution was 75-80%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Produits de réaction de déplacement halo entre des composés hydroxy aliphatiques et des composés hétérocycliques azotés aromatiques à substitution chloro ou bromo. La réaction s'effectue en milieu alcalin en présence d'un catalyseur de transfert de phase, et en l'absence de sels inorganiques aqueux autres que ceux formés pendant la réaction. Ce procédé est particulièrement utile dans la préparation de chlorotriazines substituées. Dans une forme d'exécution préférée, les réactifs constituent au moins environ 25 % en poids de la phase organique du mélange de réaction.
PCT/US1991/008741 1990-12-03 1991-11-21 Procede de preparation de composes heterocycliques azotes substitues Ceased WO1992009601A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62067890A 1990-12-03 1990-12-03
US620,678 1990-12-03

Publications (1)

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WO1992009601A1 true WO1992009601A1 (fr) 1992-06-11

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EP (1) EP0513327A1 (fr)
JP (1) JPH05502246A (fr)
WO (1) WO1992009601A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588524A1 (fr) * 1992-09-17 1994-03-23 General Electric Company Procédé pour la préparation de dichlorotriazines
EP0592143A1 (fr) * 1992-10-07 1994-04-13 General Electric Company Procédé pour la préparation de monochlorotriazines disubstituées
WO2021219941A1 (fr) 2020-04-30 2021-11-04 Kemira Oyj Procédé de fabrication de résines résistantes à l'état humide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7151188B1 (en) * 2005-11-16 2006-12-19 General Electric Company Process for the production of mercaptoalkylalkoxysilanes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895945A (en) * 1988-01-19 1990-01-23 General Electric Company Epoxidized chlorotriazine compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895945A (en) * 1988-01-19 1990-01-23 General Electric Company Epoxidized chlorotriazine compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SYNTHESIS November 1980, STUTTGART pages 921 - 924; H. ALSAIDI ET AL.: 'CONVENIENT SYNTHESIS OF HETEROAPYL PHENYL ETHERS FROM CHLOROPYRIDINES AND CHLOROQUINOLINES USING PHASE-TRANSFER CATALYSIS' *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588524A1 (fr) * 1992-09-17 1994-03-23 General Electric Company Procédé pour la préparation de dichlorotriazines
EP0592143A1 (fr) * 1992-10-07 1994-04-13 General Electric Company Procédé pour la préparation de monochlorotriazines disubstituées
WO2021219941A1 (fr) 2020-04-30 2021-11-04 Kemira Oyj Procédé de fabrication de résines résistantes à l'état humide

Also Published As

Publication number Publication date
JPH05502246A (ja) 1993-04-22
EP0513327A1 (fr) 1992-11-19

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