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
  • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
  • C07D235/26—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/68—Benzothiazoles 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 in position 2

Definitions

• the compounds of formula II can be prepared by known methods e.g. from the corresponding 2-mercapto or 2-0xo compounds by halogenation or else from the 2-amino compounds by diazotization and subsequent Sandmeyer reaction (see CA 59, 396j; Am. Chem. J. 21 (1899) , 111).
• the compounds of the formula IV can be prepared by the process (a) by using 2 mol or more of the compound II per 1 mol of the compound III.
• reaction temperatures are between 80 ° and 250 ° C, preferably 90 ° to 150 ° C, optionally at the boiling point of the solvent used.
• compound IV is increasingly formed as an undesirable by-product per se. However, this converts back to I above 80 ° with further III (see variant b)).
• the reaction can also be carried out at temperatures above the boiling point in a closed vessel under autogenous pressure; this is necessary if the solvent used boils below 80 °.
• Polar aprotic solvents e.g.
• Acid amides such as dimethylformamide, dimmthylacetamide, diethylacetamide, N-methylpyrrolidone and hexamethylphosphoric triamide, also dimethyl sulfoxide; Nitriles such as acetonitrile or propionitrile, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
• Nitriles such as acetonitrile or propionitrile, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
• aliphatic alcohols and aromatic hydrocarbons such as toluene or xylene can also be used.
• Suitable basic compounds are the customary organic and inorganic bases such as, for example, tertiary amines such as pyridine, triethylamine, alcoholates such as Na, K methylate, -Ethylate, -butylate, but especially inorganic bases such as potassium or sodium hydroxide or the corresponding carbonates. They are used at least in stoichiometric, but preferably at least equimolar amounts or in an excess of 10-20% more. Larger excesses are possible, but offer no advantage and lead to an increased salt load.
• the molar ratio of reactants II: III and IV: III can be varied within wide limits.
• the compound III can be used in a double molar amount or more based on II.
• Working with approximately equimolar amounts has the additional advantage that the reaction products can be processed without further purification.
• the production process (a) is generally carried out by first heating the compound of the formula III with the basic compound in a suitable solvent to the reaction temperature, at least partially forming the salt of the compound III. Then the compound of formula II, optionally dissolved in the same solvent, is added and the mixture is stirred at elevated temperature until the reaction has ended.
• the salt (mono salt) of compound III can also be completely prepared first and reacted with II. It is also possible to add the reactants in a different order.
• the required reaction time depends on the reaction temperature, on the solvent and on the ratio II: III and decreases with increasing temperature and increasing excess of III. The reaction is usually complete after 30 minutes to 50 hours.
• the production process (b) is carried out analogously to (a) by using a compound of the formula IV instead of a compound II, which in turn can be obtained from II and III.
• the bases used here are used to prepare the salts of the compounds III, which in turn react with the bisethers of the formula IV to give the compounds (salts) of the formula I.
• Both reactions are expediently carried out under protective gas.
• protective gas are useful, for example, N 21 Ar, C0 2, preferably N 2.
• the reaction mixture is acidified, the salt formed is filtered off and, if appropriate after washing with water, the solvent is distilled off.
• excess III its removal is taken up in a water-immiscible solvent - for example in hot xylene - and washed several times with a little hot water, the organic phase is dried and the solvent is distilled off.
• Other processing methods are described in the examples.
• Processes (a) and (b) can advantageously also be applied to the reaction of 2-halogeno, in particular 2-chloro-benzothiazole, with hydroquinone.
• the compounds of formula I are precursors for active biocides, e.g. for herbicides, in particular for those as proposed in German patent application P 26 40 730.7.
• reaction with 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
• 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
• 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
• 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol and 2-bromopropionic acid ethyl ester in the presence of potassium carbonate the 2- [4 '- (6 "-chlorobenzthiazolyl-2" -oxy) -phenoxy] -propionic acid- ethyl ester.
• the invention therefore also relates to the use of compounds of the formula I for the preparation of biocides.
• the salt content is filtered off and the filtrate is stirred into about 2 l of ice water.
• the pH is adjusted to 2 with 10% sulfuric acid and the light precipitate is filtered off with suction, washed neutral with water and dried. After drying it is taken up in hot xylene and repeatedly with hot water to remove excess hydroquinone washed. Cooling the xylene phase and suctioning off the precipitate provides 106.8 g (81.7% of theory) of 4- (5'-chlorobenzoxazolyl-2'-oxy) phenol with an mp of 179.5 ° -181 ° C.

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)
• Thiazole And Isothizaole Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1977
  • 1977-08-30 DE DE19772738963 patent/DE2738963A1/de not_active Withdrawn
• 1978
  • 1978-08-17 EP EP78100686A patent/EP0000924B1/fr not_active Expired
  • 1978-08-17 DE DE7878100686T patent/DE2860652D1/de not_active Expired
  • 1978-08-28 IT IT27077/78A patent/IT1098396B/it active
  • 1978-08-28 US US05/937,092 patent/US4263440A/en not_active Expired - Lifetime
  • 1978-08-29 CA CA000310208A patent/CA1119604A/fr not_active Expired
  • 1978-08-29 JP JP10447978A patent/JPS5446783A/ja active Pending

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