Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
  • C07C211/29—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis

Definitions

• the present invention relates to a process for making polyfluorinated benzyl alcohols which are useful in the synthesis of pyrethroid pesticides, and to intermediates useful in said process.
• a method for producing 4-methyl-2,3,5,6- tetrafluorobenzyl alcohol comprising: a) hydrogenating 4-methyl-2,3,5,6-tetrafluorolbenzonitrile to 4-methyl-2,3,5,6-tetrafluoro- benzylamine; and b) converting 4-methyl-2,3,5,6-tetrafluorobenzylamine to 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol.
• the hydrogenation process of step a) may be carried out according to any of the procedures in EP99622.
• a particularly suitable method employs hydrogen and a metal catalyst such as palladium.
• the reaction may be carried out at from 0°C to about 60°C and from ambient pressure to lObar of over pressure.
• Suitable solvents for use in the reaction include alcohols, carboxylic acids, such as formic acid, acetic acid, or mixtures of either class with water.
• a preferred solvent for the reaction is acetic acid or aqueous acetic acid.
• the mol ratio of acetic acid is suitably 2-10: 1 but is preferably 4-6:1.
• Step b) is preferably affected by diazotisation and in-situ hydrolytic decomposition of the diazonium salt.
• the reaction is suitably performed using aqueous sodium nitrite and acid at a temperature of 0-100°C , preferably 50-80°C.
• the acid for step b) is advantageously provided by carrying forward a solution of the benzylamine acetate salt from the hydrogenation step in a carboxylic acid such as acetic acid, after removal of the hydrogenation catalyst e.g. by filtration.
• the concentration of the amine in the reaction is suitably 5 - 30%, preferably 5-15%.
• the mol ratio of nitrite to amine is suitably l-2:lbut 1: 1 is preferred.
• the product may contain some of an ester (e.g. acetate) ester of the desired benzyl alcohol product.
• the acetate ester structure is shown below.
• reaction mass is adjusted to between pH 7-10, preferably to between pH 9-10 prior to extraction of the product into a solvent for purification or for use in subsequent processes.
• 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol is reacted with cis-Z 3-(2-chloro-l,l,l-trifluoro-2-propenyl)-2,2-dimethylcyclopropane carbonyl chloride
• This Example describes the preparation of 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol Step a. Preparation of 4-methyl-2,3,5,6-tetrafluorobenzylamine.
• Step b Preparation of 4-methyl-2,3,5,6-tetrafIuorobenzyl alcohol 400g of the 3.84% 4-methyl-2,3,5,6-tetrafluorobenzylamine solution from above (0.0795 moles) was added to a 1 litre jacketed reaction flask along with 0.2g silicone anti-foaming agent. To this agitated solution, 28.6g of 36 wt% aqueous sodium nitrite solution (0.149 moles) was added over 30 minutes and the temperature increased from 25°C to 70°C during the addition. The reaction was then held at 70°C for a further 35 minutes.
• the reaction was adjusted pH 11 - 12 by addition of 98g 47wt% sodium hydroxide solution and heated to 90°C for 1 hour. Cooling was then applied to bring the temperature to 60°C and the pH adjusted to 8 by addition of 9g 37% hydrochloric acid. The reaction mixture was then cooled to 25°C and the 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol product extracted into 150ml of dichloromethane, taking care to thoroughly wash-out the reaction vessel with the solvent. The solvent was removed by evaporation to yield 17.
• EXAMPLE 2 This Example describes the preparation of 4-methyl-2,3,5,6-tetrafluorobenzyl cis-3- ⁇ Z)-2- chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropane carboxylate (tefluthrin) Cis-Z 3-(2-chloro-l,l,l-trifluoro-2-propenyl)-2,2-dimethylcyclopropane carbonyl chloride (257 g) was charged to a reactor fitted with an agitator, thermometer, sub-surface nitrogen inlet and jacketed dropping funnel. Nitrogen sparging was applied to the acid chloride and maintained throughout subsequent processing.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

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• 2000
  • 2000-10-27 GB GBGB0026348.3A patent/GB0026348D0/en not_active Ceased
• 2001
  • 2001-10-18 EP EP01978595A patent/EP1332125B1/en not_active Expired - Lifetime
  • 2001-10-18 AT AT01978595T patent/ATE277885T1/de not_active IP Right Cessation
  • 2001-10-18 JP JP2002537701A patent/JP3984913B2/ja not_active Expired - Fee Related
  • 2001-10-18 CN CNB018180205A patent/CN1213992C/zh not_active Expired - Fee Related
  • 2001-10-18 AU AU2002210695A patent/AU2002210695A1/en not_active Abandoned
  • 2001-10-18 KR KR1020037005664A patent/KR100788927B1/ko not_active Expired - Fee Related
  • 2001-10-18 IL IL15520001A patent/IL155200A0/xx unknown
  • 2001-10-18 WO PCT/GB2001/004692 patent/WO2002034707A1/en not_active Ceased
  • 2001-10-18 HU HU0301158A patent/HU228240B1/hu not_active IP Right Cessation
  • 2001-10-18 BR BRPI0114931-8A patent/BR0114931B1/pt not_active IP Right Cessation
  • 2001-10-18 DE DE60106073T patent/DE60106073T2/de not_active Expired - Lifetime
  • 2001-10-18 US US10/415,262 patent/US6894195B2/en not_active Expired - Fee Related
  • 2001-10-22 TW TW090126037A patent/TWI229065B/zh not_active IP Right Cessation
• 2003
  • 2003-04-02 IL IL155200A patent/IL155200A/en not_active IP Right Cessation

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