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WO2006081165A1 - Procede ameliore pour preparer des benzoxazoles (dihalopropenyl)phenylalkyle substitues - Google Patents

Procede ameliore pour preparer des benzoxazoles (dihalopropenyl)phenylalkyle substitues Download PDF

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Publication number
WO2006081165A1
WO2006081165A1 PCT/US2006/002235 US2006002235W WO2006081165A1 WO 2006081165 A1 WO2006081165 A1 WO 2006081165A1 US 2006002235 W US2006002235 W US 2006002235W WO 2006081165 A1 WO2006081165 A1 WO 2006081165A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
catalyst
reacting
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
PCT/US2006/002235
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English (en)
Inventor
Jaidev S. Goudar
George Theodoridis
Guozhi Wang
Dominic Suarez
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 CropScience AG
FMC Corp
Original Assignee
Bayer CropScience AG
FMC Corp
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 CropScience AG, FMC Corp filed Critical Bayer CropScience AG
Publication of WO2006081165A1 publication Critical patent/WO2006081165A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2

Definitions

  • This invention is in the field of chemical processes; more specifically, an improved process for preparing (dihalopropenyl)phenylalkyl substituted benzoxazoles.
  • R 1 and R 2 are halogen; R 3 and R 4 are independently selected from halogen, alkyl and haloalkyl; R 5 is alkyl or haloalkyl; and n is 1, 2, 3, 4, 5 or 6; are useful insecticides and have been described in PCT published application WO 2004/099105. There is a need for processes to produce these compounds at higher yields, at optimal cycle times and with lower catalyst loadings.
  • the present invention relates to compounds known as disubstituted benzoxazoles, such as those represented by formula I:
  • R 5 is alkyl or haloalkyl; n is 1, 2, 3, 4, 5 or 6; X is halogen or hydroxyl and A is methyl or 4-methylbenzene; which are key intermediates in the process for preparing (dihalopropenyl)phenylalkyl substituted benzoxazoles.
  • the present invention also improves the process for preparing disubstituted benzoxazoles of formula I, formula II and formula III.
  • overall yield, cycle times and catalyst loading are improved for the production of (dihalopropenyl)phenylalkyl substituted benzoxazoles.
  • a disubstituted benzoxazole of formula I, formula II or formula III can be prepared in excellent yield and purity by a process comprising: a) reacting a compound of formula (A):
  • R 5 is as defined above;
  • Z is halogen
  • X is halogen or hydroxyl; and n is 1, 2, 3, 4, 5 or 6;
  • the modifier "about” is used herein to indicate that certain preferred jperating ranges, such as ranges for molar ratios for reactants, material amounts, and :emperature, are not fixedly determined. The meaning will often be apparent to one )f ordinary skill. For example, a recitation of a temperature range of about 120° C :o about 135° C in reference to, for example, an organic chemical reaction would be nterpreted to include other like temperatures that can be expected to favor a useful • eaction rate for the reaction, such as 105° C or 150° C.
  • alkyl As used in this specification and unless otherwise indicated the substituent :erms "alkyl”, “alkoxy”, and “haloalkyl”, used alone or as part of a larger moiety, includes straight or branched chains of at least one or two carbon atoms, as appropriate to the substituent, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms.
  • "Halogen”, 'halide” or “halo” refers to fluorine, bromine, iodine, or chlorine.
  • the term 'ambient temperature refers to a temperature in the range of about 20° C to about 30° C. Certain solvents, catalysts, and the like are known by their acronyms.
  • DMAC N,N-dimethylacetamide
  • DMF N 5 N-dimethylformamide
  • THF tetrahydrofuran.
  • the te ⁇ n “glymes” refers to a class of solvents comprised of monoglyme, diglyme, triglyme, tetraglyme, and polyglyme.
  • GC refers to gas chromatography or gas chromatographic methods of analyses.
  • the present invention relates to a process for preparing a disubstituted benzoxazole of formula I:
  • R 5 is alkyl or haloalkyl
  • R 5 is as defined above;
  • the reaction of step a) can be conducted in the presence of a solvent; in the presence of a catalyst.
  • the solvent can be tetrahydrofuran, toluene, xylene, 1,2- dichloroethane, triethylamine,/>-dioxane, N,N-dimethylacetamide, N,N- dimethylformamide, glymes, dimethylsulfoxide or mixtures thereof.
  • the solvent can be 1,2-dichloroethane.
  • the catalyst can be polyethylene glycol, dimethylaminopyridine, triethylamine, pyridine, phase transfer catalysts such as t- butyl ammonium chloride or t-butyl ammonium bromide or mixtures thereof.
  • the catalyst can be present in a concentration of from about 1% by weight to about 20% by weight.
  • the elevated temperature of step b) can be in the range of 70°C to 15O 0 C.
  • Step b) can be conducted in the presence of a solvent; in the presence of a catalyst.
  • the catalyst can be/?-toluenesulfonic acid, phosphorous pentoxide or mixtures thereof.
  • the catalyst can be present in a concentration of from about 1% by weight to about 5% by weight.
  • the solvent can be tetrahydrofuran, toluene, xylene, 1,2- dichloroethane, triethylamine,/>-dioxane, N,N-dimethylacetamide, N,N- dimethylformamide, glymes, dimethylsulfoxide or mixtures thereof.
  • the solvent can be 1,2-dichloroethane.
  • R > 5 is alkyl or haloalkyl; n is 1, 2, 3, 4, 5 or 6; and X is halogen or hydroxyl;
  • R is as defined above;
  • Z is halogen; and n and X are as defined above;
  • the reaction to form a compound of formula II can be conducted in the presence of a solvent; at elevated temperature; in the presence of a catalyst; in the presence of a carbonate.
  • the solvent can be tetrahydrofuran, toluene, xylene, 1,2- dichloroethane, triethylamine, ju-dioxane, N,N-dimethylacetamide, N 5 N- dimethylformamide, glymes, dimethylsulfoxide or mixtures thereof, preferably the solvent can be 1,2-dichloroethane;
  • the elevated temperature can be in the range of 50°C to 100°C;
  • the catalyst can be polyethylene glycol, triethylamine, pyridine, phase transfer catalysts such as t-butyl ammonium chloride or t-butyl ammonium bromide or mixtures thereof;
  • the carbonate can be sodium carbonate or potassium carbonate.
  • the catalyst can be present in a concentration of from about 1% by
  • R 5 is alkyl or haloalkyl; n is 1, 2, 3, 4, 5 or 6; and
  • A is methyl or 4-methylbenzene
  • R 5 and n are as defined above; and X is hydroxyl;
  • the reaction to form a compound of formula III can be conducted in the presence of a sblvent; in the presence of a catalyst.
  • the solvent can be tetrahydrofuran, toluene, xylene, 1,2-dichloroethane, triethylamine, j>dioxane, N,N- dimethylacetamide, N,N-dimethylformamide, glymes, dimethylsulfoxide or mixtures thereof, preferably the solvent can be 1,2-dichloroethane;
  • the catalyst can be dimethylaminopyridine, triethylamine, methylamine, phenylamine, pyridine, phase transfer catalysts such as t-butyl ammonium chloride or t-butyl ammonium bromide or mixtures thereof.
  • the catalyst can be present in a concentration of from about 1% by weight to about 5% by weight.
  • R 5 is alkyl or haloalkyl
  • n is 1, 2, 3, 4, 5 or 6
  • X is halogen or hydroxyl
  • R 5 is alkyl or haloalkyl; n is 1, 2, 3, 4, 5 or 6; and
  • A is methyl or 4-methylbenzene.
  • N-(2,4-Dihydroxy-phenyl)-2,2,2- trifluoro-acetamide (C) underwent a ring closure reaction in the presence of a solvent and a catalyst at a temperature in the range of from about 90 0 C to about 150 0 C to form 2-(trifluoromethyl)benzoxazol-6-ol (I), a dark solid.
  • NMR data was consistent with the expected product (I).
  • step (c) of Example 2 (trifluoromethyl)benzoxazol- ⁇ -ol (I) was cross- coupled with a l-bromo-3-halopropane (D), for example l-bromo-3-chloropropane, in the presence of a carbonate, for example potassium carbonate, a solvent and a catalyst at a temperature from about 50 0 C to about 100°C to afford a 3-halo-l-[2- (trifluoromethyl)benzoxazol-6-yloxy]propane (II), for example 3-chloro-l-[2- (trifluoromethyl)benzoxazol-6-yloxy]propane, an amber oil. NMR data was consistent with the expected product (II).
  • D l-bromo-3-halopropane
  • a carbonate for example potassium carbonate
  • a solvent and a catalyst at a temperature from about 50 0 C to about 100°C to afford a 3-halo-l-[
  • step (d) of Example 3 3-hydroxy-l-[2-(trifluoromethyl)benzoxazol-6- yloxy]propane can be reacted with a substituted chlorosulfone, for example chloromethylsulfone, in the presence of a solvent and a catalyst at ambient temperature to form a l-(substitutedsulfonyl)-3-[2-(trifluoromethyl)benzoxazol-6- yloxyjpropane (HI), for example l-(methylsulfonyl)-3-[2-
  • step (ab) of Example 4 amino-resorcinol hydrochloride (A) was cross- coupled with 2,2,2-trifluoroacetic acid (Bl) and then condensed in the presence of a solvent and molecular sieves at a temperature in the range of from about 70 0 C to about 140 0 C to form 2-(trifluoromethyl)benzoxazol-6-ol (I), a dark solid. NMR data was consistent with the expected product (I).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé amélioré pour préparer des benzoxazoles (dihalopropényl)phénylalkyle substitués, ce procédé comportant des opérations pour réaliser des produits intermédiaires clés, notamment des benzoxazoles disubstitués de formules I, II et III, où R5 signifie alkyle ou haloalkyle, n est 1, 2, 3, 4, 5 ou 6, X représente hydroxyle ou halogène et A désigne méthyle ou 4-méthylbenzène.
PCT/US2006/002235 2005-01-27 2006-01-23 Procede ameliore pour preparer des benzoxazoles (dihalopropenyl)phenylalkyle substitues Ceased WO2006081165A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64773105P 2005-01-27 2005-01-27
US60/647,731 2005-01-27

Publications (1)

Publication Number Publication Date
WO2006081165A1 true WO2006081165A1 (fr) 2006-08-03

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PCT/US2006/002235 Ceased WO2006081165A1 (fr) 2005-01-27 2006-01-23 Procede ameliore pour preparer des benzoxazoles (dihalopropenyl)phenylalkyle substitues

Country Status (2)

Country Link
TW (1) TW200631946A (fr)
WO (1) WO2006081165A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376428B1 (en) * 1994-10-14 2002-04-23 Sumitomo Chemical Company, Limited Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376428B1 (en) * 1994-10-14 2002-04-23 Sumitomo Chemical Company, Limited Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production

Also Published As

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