EP1131284A1 - Procede et produits intermediaires destines a la production de bis(oxim)monoethers - Google Patents

Procede et produits intermediaires destines a la production de bis(oxim)monoethers

Info

Publication number
EP1131284A1
EP1131284A1 EP99972621A EP99972621A EP1131284A1 EP 1131284 A1 EP1131284 A1 EP 1131284A1 EP 99972621 A EP99972621 A EP 99972621A EP 99972621 A EP99972621 A EP 99972621A EP 1131284 A1 EP1131284 A1 EP 1131284A1
Authority
EP
European Patent Office
Prior art keywords
methyl
oxime
formula
hydrogen
alkyl
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.)
Withdrawn
Application number
EP99972621A
Other languages
German (de)
English (en)
Inventor
Wassilios Grammenos
Hubert Sauter
Andreas Gypser
Herbert Bayer
Norbert Götz
Roland Götz
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1131284A1 publication Critical patent/EP1131284A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
    • 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
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • 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
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton

Definitions

  • the present invention relates to a process for the preparation of bis (oxime) monoethers of the formula I,
  • R 1 unsubstituted C 1 -C 4 alkyl or methyl substituted by C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or phenyl;
  • R 2 , R 4 independently of one another are hydrogen or methyl
  • R 3 , R 5 independently of one another hydrogen or -CC 4 alkyl, trifluoromethyl or phenyl.
  • the invention relates to monooximes of the formula III and obtainable with this process
  • the object of the present invention was therefore to find a process by means of which compounds of the formula I and IV can be built up in a targeted manner.
  • Alcohols such as methanol and, in particular, water can be used as solvents. Under certain circumstances, it can be helpful to add solubilizers such as surfactants or ethylene glycol.
  • Suitable bases are in particular sodium and potassium hydroxide, which are generally used in an equimolar amount or in an up to 10-fold molar excess based on the acetoacetic ester II.
  • Nitrite is understood to mean, for example, an alkali metal nitrite, in particular sodium nitrite, which is generally used in an aquimolar amount or in an excess of up to 30 mol%, based on the acetoacetic ester II.
  • the reaction temperature should generally not exceed 40 ° C, otherwise undesirable side reactions occur. It is therefore preferred to work in water at -20 to 40 ° C., in particular at 0 to 15 ° C.
  • the reaction mixture usually clears up after a period of 10 to 48 hours.
  • a pH of 0 to 5 and preferably 1 to 3 is set with an acid such as hydrochloric acid or sulfuric acid.
  • the processing takes place according to common methods, for example by extraction.
  • the oxime can be converted into the corresponding salt with bases, for example, and then precipitated again with acid.
  • the acetoacetic ester II used for the reaction can be prepared as described in Tetrahedron (1985) 4633 (see Scheme 3).
  • alkenylalkyls of the formula A where R 2 to R 5 have the meaning given in claim 1 and L 1 represents halogen, acyloxy, alkylsulfonyloxy or arylsulfonyloxy, are known or can be synthesized by processes known from the literature (Z. Org. Khim. (1997) 486; Bull. Chem. Soc. Jpn. (1980) 2586; J. Am. Chem. Soc. (1984) 2211; J. Am. Chem. Soc. (1960) 1886; DE-A 19 556 66 ; DE-A 33 173 56; EP-A 271212; Tetrahedron Let. (1986) 6027; Tetrahedron Let. (1994) 1371 and 2679; J. Fluorine Chem. (1997) 67; Helv. Chim. Acta (1951) 1514 ; Organomet. Chem. (1985) 395).
  • the alkylation is usually carried out in the presence of an inert organic solvent.
  • an inert organic solvent aliphatic or aromatic hydrocarbons such as toluene, xylene, heptane or cyclohexane, aliphatic or cyclic ethers such as 1, 2-dimethoxyethane, tetrahydrofuran or dioxane can be used.
  • Polar aprotic solvents are preferably used: ketones such as acetone, nitriles such as acetonitrile, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone or ureas such as tetramethylurea.
  • a halide preferably a chloride or bromide, a sulfate, preferably dimethyl sulfate, a sulfonate, preferably a methanesulfonate (mesylate) or a toluenesulfonate (tosylate) is usually used as the alkylating agent.
  • the amount of base or alkylating agent, based on compound III, is preferably between one to two times the equimolar amount.
  • an inorganic base such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium hydrogen carbonate or an alkali metal alcoholate such as sodium methoxide or potassium tert. -butanolate worked.
  • the reaction temperature is generally between 0 ° C and 50 ° C - preferably between 0 ° C and 40 ° C and especially at room temperature.
  • the processing can take place, for example, by an extractive route.
  • Hydroxylamine is used either in the form of an acid addition salt or as a free base, the latter being able to be released from the salt by adding a strong base.
  • the acid addition salts of hydroxylamine are preferably used. All common acids are suitable for the production of the acid addition salts. The following are just a few examples: carboxylic acids such as acetic or propionic acid, dicarboxylic acids such as oxalic or succinic acid, mineral acids ren such as phosphoric or carbonic acid and especially hydrochloric acid or sulfuric acid.
  • carboxylic acids such as acetic or propionic acid
  • dicarboxylic acids such as oxalic or succinic acid
  • mineral acids ren such as phosphoric or carbonic acid and especially hydrochloric acid or sulfuric acid.
  • the acid addition salts of hydroxylamine are used, it is generally advantageous to add a base in order to bind the acid released during the reaction.
  • a pH of 3 to 7 and in particular 4 to 6 has proven to be advantageous for the oximation. Outside of these pH ranges, side reactions such as ring closure reactions can occur.
  • a base 1 to 2.5 molar equivalents of a base are added.
  • pyridines, trialkylamines, sodium hydroxide, sodium acetate and sodium methylate are suitable as bases.
  • sodium acetate glacial acetic acid is usually added.
  • hydroxylamine can also be used as the free base and one of the acids mentioned can be used to adjust the above-mentioned pH range.
  • solvents which can be used are those described in the previous step.
  • carboxylic acids such as acetic acid or water / pyridine mixtures are also suitable.
  • Alcohols such as methanol, ethanol, n-propanol or i-propanol and mixtures of these with water and / or pyridine are particularly suitable.
  • the reaction temperature is usually -20 to 100 ° C and preferably 0 to 40 ° C and in particular 20 to 25 ° C.
  • the reaction mixture is preferably worked up, as described in the previous step, by means of extractive methods.
  • R 1 is unsubstituted C ⁇ -C 4 alkyl or by C 2 -C 4 alkenyl, C 2 -C 4 -alkynyl or phenyl-substituted methyl;
  • R 2 , R 4 independently of one another are hydrogen or methyl
  • R 3 , R 5 independently of one another hydrogen or C ⁇ -C 4 alkyl, trifluoromethyl or phenyl.
  • Halogen fluorine, chlorine, bromine or iodine
  • C 2 -C alkenyl ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, but-1-en-1-yl, but-2-en-1 -yl, but-3-en-1 -yl, 1-methyl-prop-l-en-l-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-ene -l-yl and 2-methyl-prop-2 -en-l-yl;
  • C 2 -C alkynyl ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl;
  • R 1 is methyl, ethyl, benzyl or propargyl and in particular methyl or ethyl;
  • R 2 , R 4 independently of one another are hydrogen or methyl
  • R 3 , R 5 independently of one another are hydrogen, methyl or trifluoromethyl.

Landscapes

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

Abstract

L'invention concerne un procédé de production de bis(oxim)monoéthers de la formule (I), où les substituants ont la signification suivante: R1 représente alkyle C¿1?-C4 non substitué ou méthyle substitué par un alcényle C2-C4, alkinyle C2-C4 ou phényle; R?2, R4¿ représentent, indépendamment l'un de l'autre, hydrogène ou méthyle; R3, R5 représentent, indépendamment l'un de l'autre, hydrogène ou alkyle C¿1?-C4, trifluorométhyle ou phényle. L'invention concerne également les produits intermédiaires obtenus par ce procédé.
EP99972621A 1998-11-20 1999-11-12 Procede et produits intermediaires destines a la production de bis(oxim)monoethers Withdrawn EP1131284A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19853705 1998-11-20
DE19853705 1998-11-20
PCT/EP1999/008742 WO2000031024A1 (fr) 1998-11-20 1999-11-12 Procede et produits intermediaires destines a la production de bis(oxim)monoethers

Publications (1)

Publication Number Publication Date
EP1131284A1 true EP1131284A1 (fr) 2001-09-12

Family

ID=7888523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99972621A Withdrawn EP1131284A1 (fr) 1998-11-20 1999-11-12 Procede et produits intermediaires destines a la production de bis(oxim)monoethers

Country Status (8)

Country Link
US (1) US6344589B1 (fr)
EP (1) EP1131284A1 (fr)
JP (1) JP2002530366A (fr)
CN (1) CN1326437A (fr)
AU (1) AU1383100A (fr)
BR (1) BR9915500A (fr)
HU (1) HUP0104064A3 (fr)
WO (1) WO2000031024A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842400A (en) * 1987-07-07 1989-06-27 Commissariat A L'energie Atomique Visual apparatus

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB821400A (en) 1958-01-17 1959-10-07 Du Pont Process of nitrosation
DE1168420B (de) 1960-11-10 1964-04-23 Hoechst Ag Verfahren zur Herstellung von Isonitroso-Carbonylverbindungen
DE1137434B (de) 1961-03-02 1962-10-04 Berlin Chemie Veb Verfahren zur Herstellung von Isonitrosoacetessigester
CA1132553A (fr) 1978-10-13 1982-09-28 Gary L. Olson Derives de l'isoquinoline
US4260762A (en) 1979-09-10 1981-04-07 Hoffmann-La Roche Inc. Octahydro-1H-pyrrolo[2,3-g]isoquinolines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0031024A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842400A (en) * 1987-07-07 1989-06-27 Commissariat A L'energie Atomique Visual apparatus

Also Published As

Publication number Publication date
HUP0104064A3 (en) 2002-12-28
AU1383100A (en) 2000-06-13
WO2000031024A1 (fr) 2000-06-02
BR9915500A (pt) 2001-08-07
HUP0104064A2 (hu) 2002-03-28
JP2002530366A (ja) 2002-09-17
US6344589B1 (en) 2002-02-05
CN1326437A (zh) 2001-12-12

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