Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
  • C07C239/08—Hydroxylamino compounds or their ethers or esters
  • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
• • 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
• • 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

Definitions

• the invention relates to a process for the preparation of aminoglycol by reacting ketoximes with ethylene oxide under basic conditions to give a substituted 2-hydroxyethyl ketoxime and its subsequent reaction with an acid to aminoglycol.
• Aminoglycol is an important synthetic building block for the preparation of herbicidally active agroactive substances, in particular for the preparation of dioxazine derivatives, in particular of dioxazine-pyridinyl-suflonylureas (US Pat. No. 5,476,936).
• EP0655437 teaches a process for preparing aminoglycol by reacting acetone oxime with ethylene carbonate in the presence of DBU, but only providing conversion yields of 65-75%.
• DBU is an expensive feedstock that can not be recovered.
• the present invention is therefore based on the object to provide a simpler and more economical process for the preparation of aminoglycol.
• the above-described object has been achieved according to the invention by a process for the preparation of aminoglycol of the formula (I)
• R 1 and R 4 independently of one another are unsubstituted or linear, (C 1 -C 2) -alkyl, phenyl or branched (C 3 -C 8 ) -alkyl, which is unsubstituted or halogen, CN, NO 2 , mono- or polysubstituted, but for the case that R1 or R is an unsubstituted or substituted by halogen, CN, NO 2 (d-C ⁇ J-alkyl, each of R1 or R is an unsubstituted or substituted by halogen, CN, NO 2 phenyl or a branched (C 3 -C 8 ) -alkyl and (b)
• Iminooxyethanols the general formula (III) in the presence of an acid to aminoglycol.
• R 1 and R preferably have the meaning of methyl, ethyl, propyl, phenyl, sec-butyl, tert-butyl, isobutyl, isopropyl or neopentyl, where the abovementioned radicals are each independently of one another unsubstituted or substituted by halogen, CN, NO 2 , mono- or polysubstituted, but in the case that R 1 or R is an unsubstituted or substituted by halogen, CN, NO 2 methyl, ethyl or propyl, the respective other radical corresponds to R 1 or R is an unsubstituted or substituted by halogen, CN 1 NO 2 phenyl, sec-butyl, tert-butyl, isobutyl, isopropyl or neopentyl.
• R.sup.1 and R.sup.3 have the meaning of methyl, ethyl, phenyl, sec-butyl, tert-butyl, isobutyl, isopropyl and neopentyl, in which case R.sup.1 or R.sup is a methyl or ethyl, the other radical R1 or R must be selected from the group phenyl, sec-butyl, tert-butyl, isobutyl or isopropyl.
• R1 is particularly preferably a methyl and R is a tert-butyl or isobutyl, or else R is a methyl and R1 is a tert-butyl or isobutyl.
• R1 corresponds to a methyl and R to a tert-butyl, or else R corresponds to a methyl and R1 to a tert-butyl.
• a further advantage of the process according to the invention consists (as shown in scheme (II) below) in that the product of the formula (III) is insoluble in water and thus isolated from the aqueous phase without separate extraction steps.
• the aminoglycol can be liberated quantitatively.
• the new process is thus the process known from the prior art both from economical (low cost of starting materials and auxiliaries, high product yield and recovery of the ketone (according to Scheme (II)), as well as from an ecological point of view, ie the emergence lower waste volumes, clearly superior.
• halogens includes those elements selected from the group consisting of fluorine, chlorine, bromine and iodine, fluorine, chlorine and bromine being preferred and fluorine and chlorine being particularly preferably used.
• Substituted radicals may be monosubstituted or polysubstituted, and in the case of multiple substitutions, the substituents may be identical or different.
• Both organic and inorganic bases can be used as bases.
• inorganic bases such as LiOH, NaOH, KOH, Ca (OH) 2 , Ba (OH) 2 , Li 2 CO 3 , K 2 CO 3 , Na 2 CO 3 , NaHCO 3 , or organic bases such as amines (such as preferably triethylamine, diethylisopropylamine), Bu 4 NOH, piperidine, morpholine, alkylpyridines.
• Particular preference is given to using inorganic bases, very particularly preferably LiOH, NaOH and KOH.
• acids both organic and inorganic acids can be used.
• inorganic acids such as, for example, HCl, HBr, HF, H 2 SO 4 , H 3 PO 4 or organic acids such as CF 3 COOH, CH 3 COOH, p-toluenesulfonic acid.
• inorganic acids very particularly preferably HCl and H 2 SO 4 .
• the process can be carried out both in water and in the presence of an inert organic solvent, preferably a polar aprotic solvent.
• organic solvents are aromatic or aliphatic solvents such as benzene, toluene, xylene, mesytilen, hexane, heptane, octane, cyclohexane, aliphatic and aromatic hydrogen halides such as methylene chloride, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, dibutyl ether, diisobutyl ether Methyl tert-butyl ether, isopropyl ethyl ether, tetrahydrofuran, and dioxane; also dimethylsulfoxide, and acid amide derivatives such as N, N-dimethylformamide, N, N-dimethylacet
• toluene particularly preferred are toluene, xylene, dichlorobenzene, chlorobenzene or ethyl acetate.
• the compounds of formulas II and III can be prepared as mixtures of various possible isomeric forms, in particular stereoisomers, e.g. E and Z, syn and anti, and optical isomers, but optionally also of tautomers. Both the E and the Z isomers, as well as the optical isomers, any mixtures of these isomers, as well as the possible tautomeric forms are claimed.
• Reaction step of the inventive method is between 1: 1 and 1:10, preferably between 1: 1 and 1: 5, more preferably between 1: 1 and 1: 3, while the base in a ratio of 0.05 to 1 molar equivalents, preferably from 0.05 to 0.5 molar equivalents, particularly preferably from 0.05 to 0.3 molar equivalents, in each case based on the ketoxime, is used.
• Preferred compounds of the general formula (III) are: 2-Hydroxyethylketoxime in which (a) R1 corresponds to a methyl and R is an isobutyl, (b) R1 corresponds to a methyl and R corresponds to a tert-butyl and (c) R1 Ethyl and R corresponds to a tert-butyl.
• the invention will be explained in more detail with reference to the following embodiments, but without limiting them to these. example 1

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

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• 2006
  • 2006-11-24 EP EP06024436A patent/EP1925610A1/de not_active Withdrawn
• 2007
  • 2007-11-03 US US12/515,820 patent/US7968747B2/en not_active Expired - Fee Related
  • 2007-11-03 EP EP07819563A patent/EP2104661A1/de not_active Withdrawn
  • 2007-11-03 JP JP2009537502A patent/JP2010510258A/ja not_active Abandoned
  • 2007-11-03 CN CNA2007800460573A patent/CN101558036A/zh active Pending
  • 2007-11-03 WO PCT/EP2007/009540 patent/WO2008061616A1/de not_active Ceased
  • 2007-11-22 TW TW096144271A patent/TW200837039A/zh unknown

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