Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/32—Oximes
  • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
  • C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
  • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups

Definitions

• the present invention relates to a process for the preparation of 0- (2-hydroxyalkyl) oximes of the general formula I
• R 1 and R 2 each stand for an alkyl group having from 1 to 10 carbon atoms, or form, together with the carbon atom to which they are attached, a 5-membered to 7-membered cycloalkyl radical, and R 3 denotes an alkyl group having from 1 to 10 carbon atoms.
• 0- (2-hydroxyalkyl) oximes have great significance as intermediates for plant protectants (cf eg, the prior German Application DE-A 44 15 887) .
• Specially substituted O-hydroxyalkyloximes can be prepare by the reaction of 25 glycol vinyl glycidyl ethers with oximes in the presence of bases such as triethylamine or potassium hydroxide, for example.
• aldox- imes and ketoximes with unsubstituted or Ci-C ⁇ -alkyl-substituted ethylene or propylene carbonate can be hydroxyalkylated in the presence of catalytic amounts of an N-alkylated, stable organic base or of pyridine substituted by a secondary amine.
• Preferred process products I are those which can be produced by this process variant those are preferred in which R 1 and R 2 stand for C ⁇ c 4 alkyl groups and primarily C 1 -C 3 alkyl groups or form, together with the carbon atom to which they are attached, a cyclopentyl or cyclohexyl ring, and in particular those in which R 1 and R 2 stand for methyl and/or ethyl or form, together with the carbon atom to which they are attached, cyclohexyl.
• R3 preferably stands for a C ⁇ c 4 alkyl group, particularly for ethyl and more particularly for methyl.
• Most particularly preferred compounds I are those in which R 1 , R 2 and R 3 stand for methyl.
• ketoximes II are generally known or are obtainable by known methods, for example, by the reaction of the corresponding ketones with hydroxylamine.
• the olefin oxides III are also generally known or are obtainable by known methods.
• the carbonates iv are also generally known or can be produced by known methods (cf. eg, EP-A 543,249).
• R 3 tertiary amine C N 0 CH 2 CH - - OH
• the molar ratio of olefin oxide III to ketoxime II is preferably from 1:1 to 2:1 and in particular from 1.1:1 to 1.3:1.
• Suitable tertiary amines are primarily those having aliphatic and/or cycloaliphatic groups on the N atom such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, tri-n-dodecylamine, N-methyl- dicyclohexylamine, and N,N-dimethylcyclohexylamine and also heterocyclic nitrogen bases having from 5 to 10 carbon atoms such 0 as pyridine, 4- (N,N-dimethylamino)pyridine, 1,8-diazabi- cyclo[5.4.0]undec-7-ene, 1,4-diaza-bicyclo [2.2.2]octane, and 1-methylimidazole.
• aliphatic and/or cycloaliphatic groups on the N atom such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-
• reaction mixture 5 present at the end of the reaction is to be subjected to purifi ⁇ cation by distillation
• a tertiary aliphatic amine is used whose boiling point is between 50° and 250°C and in particular between 80° and 180°C.
• Triethylamine and N,N-dimethylcyclohexylamine are particularly preferred.
• the tertiary amine is usually employed in an amount of from 0.5 to 40 mol%, preferably from 0.9 to 10 mol% and more preferably from 1 to 5 mol%, based on the ketoxime II.
• reaction can be carried out without the use of solvent or in a suitable solvent or solvent mixture.
• Suitable solvents are alkanols such as ethanol and tert-butanol, ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as 0 acetone, esters such as ethyl acetate, nitriles such as acetoni- trile, N,N—dialkylamides such as dimethyl formamide and N,N-di- methylacetamide, N-alkylated lactams such as N-methyl-2-pyrroli- done, and N,N-dialkylated cyclic ureas such as N-N-dimethylethy- lene urea and N,N-dimethylpropylene urea. 5 Also suitable as solvent is an excess of one of the afore ⁇ mentioned tertiary amines which is in the liquid state at least under the reaction conditions.
• those of the aforemen ⁇ tioned solvents are preferred, broadly speaking, which have a similar boiling point to that of the amines used and/or form azeotropes with them such that their removal, by distillation, from the crude reaction mixture takes place in a particularly simple manner.
• N,N-dialkylamides and N-alkylated lactams especially dimethylformamide and N-methyl-2-pyrrolidone.
• the reaction is carried out at temperatures of from 40° to 130°C and mostly from 70° to 110°C and pressures of from 0.5 to 40 bar and mainly from standard pressure to 20 bar.
• the process is carried out by placing the ketoxime II and the tertiary amine, optionally in a solvent, in the reactor and metering in the olefin oxide III at the temperature of reaction.
• reaction times are normally from 2 to 24 h but mostly from 4 to 16 h.
• reaction products I takes place by methods known per se, preferably by distillation.
• the molar ratio of carbonate iv to ketoxime II is usually from 1:1 to 10:1 and in particular from 4:1 to 7:1.
• Suitable catalysts used either alone or in the form of a mix- ture, are
• alkali metal salts alkaline earth metal salts, and ammonium salts (NN +) , primarily the potassium salts and also the so ⁇ dium salts' with inorganic or organic anions such as alkali metal halides, hydroxides, carbonates, hydrogen carbonates, alcoholates, and alkali metal salts of organic monocarboxylic acids.
• potassium fluoride, potassium iodide, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium methylate, potassium ethylate, potassium tertbutylate, and potassium acetate potassium fluoride, potassium iodide, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium methylate, potassium ethylate, potassium tertbutylate, and potassium acetate;
• phosphines having at least one but preferably three c-organic radicals, in particular those selected from the group com ⁇ prising ci-cio alkyl, C 6 ⁇ ci 5 -aryl, C 6 -C 15 alkylaryl, and/or c -C ⁇ o-arylalkyl, such as, primarily tri-n-butylphosphine and triphenylphosphine; or ⁇ ) tertiary amines, preferably heterocyclics having from one to three N atoms as hetero atoms, such as, primarily, imida- zoles, particularly N-(c ⁇ c alkyl) imidazoles such as N-methy- limidazole, and also triazoles, pyridines, and bicyclic aza- 5 heterocyclics such as 1, 8-diazabicyclo [5.4.0]undec-7-ene and 1, 4-diazabicyclo [2.2.2]octan
• Preferred catalysts are those which are mentioned under ( ⁇ ) and ( ⁇ ) .
• the potassium salts are preferably used, 10 especially potassium fluoride or potassium hydrogen carbonate.
• triethylamine is most particularly preferred.
• the catalyst primarily the inorganic alkali metal salts and the alkali metal salts of carboxylic acids, can be bonded to a 15 support, if desired.
• suitable supports are aluminum oxide, silica gel, and kieselguhr.
• the amount of catalyst in these supported catalysts is usually from 10 to 50 wt%.
• the catalysts are usually employed in an amount of from 5 to 50 20 mol%, preferably from 5 to 30 mol%, and more preferably from 5 to 10 mol%, based on the ketoxime II.
• the reaction can be carried out in a single, preferably aprotic, organic solvent or in a solvent mixture.
• the process is 25 preferably carried out without the use of a solvent, in which case an excess of the carbonate IV can, in particular, serve as reaction medium.
• Suitable solvents are for example alkylbenzenes, such as, in par- 30 ticular, toluene and also the xylenes, furthermore dialkylketones such as methyl ethyl ketone, halobenzenes such as chlorobenzene, and ethers such as 1,4-dioxane.
• the amount of solvent used is usually from 1 to 9 times and in 35 particular from 2 to 7 times the weight of the ketoxime II. If the amount of solvent exceeds 9 times the weight of the ketoxime II, conversion and yield usually fall.
• the reaction is preferably carried out at temperatures of from 40 80°C to 1 50°C and mostly from 100°C to 140°C and pressures of from 0.5 to 1 bar and especially under standard pressure.
• phase transfer catalysts are quaternary ammonium or phosphonium salts, preferably tetraalkylammonium, tetraalkylphos- phonium, trialkylbenzyla monium, or trialkylbenzylphosphonium salts, especially triethylammoniu , tributylbenzylammonium, and tetrabutylammonium chlorides, bromides, and hydrogen sulfates, and also tributylhexaphosphonium bromide.
• the phase transfer catalyst is usually employed in an amount of from 0.5 to 2 mol% and preferably from 0.7 to 1 mol%, based on the ketoxime II.
• the reaction can be carried out batchwise or, preferably, contin ⁇ uously.
• reaction times are normally from 8 to 24 h but mostly from 8 to 16 h.
• reaction product I takes place by methods known per se, preferably by distillation.
• the distillation residues of the crude mixture contain substan ⁇ tially unconverted carbonate JV and the catalyst.
• the process is carried out by replenishing the ketoxime II and the carbonate IV at a rate equal to the rate of consumption thereof, following the destination of the product I from the reaction mixture, and the reaction is then repeated.
• reaction frequently also produces, as by-product, the regio- isomeric compound la
• the two isomeric compounds I and la are normally the first over- heads occurring during distillation of the crude product. If de ⁇ sired, the isomer la can be substantially separated from the compound I by methods known per se, preferably by fractional dis ⁇ tillation.
• the end products I are important intermediates for crop protec- tion agents, especially for herbicides of the cyclohexenone type (cf. DE-A 44 15 887) .
• Example 1 was repeated except that butylene-1 oxide was used instead of propylene oxide.
• butylene-1 oxide was used instead of propylene oxide.
• a mixture of 0- (2-hydroxybutyl)propan-2-one oxime and 0- (2-hydroxy-l-ethylethyl)propan-2-one oxime was obtained at 80-82°C/20 mbar in a yield of 59 %.
• the isomer ratio of I:la was 96.7:3.3.
• Example 1 was repeated starting from cyclohexanone oxime instead of acetone oxime. During fractional distillation of the crude product a mixture of 0- (2-hydroxypropyl) cyclohexanone oxime and 0- (2-hydroxy-l-methylethyl) cyclohexanone oxime was obtained at 10 74°C/0.2 mbar in a yield of 54 %. The isomer ratio of I:la was 96:4.
• Example 6 The process was carried out as in Example 4 but without the addi- 40 tion of toluene. Starting from 344 g (4.7 mol) of acetone oxime, 2420 g (23.5 mol) of propylene carbonate, and 47 g (0.47 mol) of potassium hydrogen carbonate there was obtained, in a total of 10 reaction cycles carried out, in each case, for a period of 8 h at 130°C, a mixture consisting of 0- (2-hydroxypropyl)propane-2-one 45 oxime and 0- (2-hydroxy-l-methylethyl)propane-2-one oxime in a per ⁇ centage ratio of I: la of 92:8 and in a yield of 89%.
• Example 6 Example 6

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Medicinal Preparation (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Citations (2)

• 1995
  • 1995-07-28 IL IL11477695A patent/IL114776A/xx not_active IP Right Cessation
  • 1995-07-28 BR BR9508498A patent/BR9508498A/pt not_active IP Right Cessation
  • 1995-07-28 AU AU33813/95A patent/AU3381395A/en not_active Abandoned
  • 1995-07-28 EP EP95930419A patent/EP0775107B1/en not_active Expired - Lifetime
  • 1995-07-28 CN CN95194843A patent/CN1086383C/zh not_active Expired - Lifetime
  • 1995-07-28 MX MX9700809A patent/MX9700809A/es not_active IP Right Cessation
  • 1995-07-28 WO PCT/EP1995/003001 patent/WO1996004238A1/en not_active Ceased
  • 1995-07-28 JP JP50618096A patent/JP4017022B2/ja not_active Expired - Lifetime
  • 1995-07-28 AT AT95930419T patent/ATE185553T1/de active
  • 1995-07-28 ES ES95930419T patent/ES2139935T3/es not_active Expired - Lifetime
  • 1995-07-28 DE DE69512786T patent/DE69512786T2/de not_active Expired - Lifetime
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  • 1995-07-28 HU HU9700313A patent/HU216742B/hu not_active IP Right Cessation
  • 1995-07-28 CA CA002196452A patent/CA2196452A1/en not_active Abandoned
  • 1995-07-28 DK DK95930419T patent/DK0775107T3/da active
  • 1995-08-01 ZA ZA9506402A patent/ZA956402B/xx unknown
• 1999
  • 1999-10-14 GR GR990402548T patent/GR3031531T3/el unknown

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