WO2000031023A1 - Verfahren zur herstellung von alkenyl-substituierten bis(oximether)derivaten - Google Patents
Verfahren zur herstellung von alkenyl-substituierten bis(oximether)derivaten Download PDFInfo
- Publication number
- WO2000031023A1 WO2000031023A1 PCT/EP1999/008740 EP9908740W WO0031023A1 WO 2000031023 A1 WO2000031023 A1 WO 2000031023A1 EP 9908740 W EP9908740 W EP 9908740W WO 0031023 A1 WO0031023 A1 WO 0031023A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- methyl
- substituents
- phenyl
- cooch
- Prior art date
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- 0 CC(C(C(*)=C(*)C(*)*)=NO*)=NOCc1c(*)cccc1 Chemical compound CC(C(C(*)=C(*)C(*)*)=NO*)=NOCc1c(*)cccc1 0.000 description 2
- USZCZZKMHQHYRL-USDWKXBASA-N CC(C)=C/C(/C(/C)=N/OCc(cccc1)c1/C(/C(OC)=O)=C\OC)=N\OC Chemical compound CC(C)=C/C(/C(/C)=N/OCc(cccc1)c1/C(/C(OC)=O)=C\OC)=N\OC USZCZZKMHQHYRL-USDWKXBASA-N 0.000 description 1
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
- C07C249/12—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 alkenyl-substituted bis (oxime ether) derivatives of the formula I,
- 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 are independently hydrogen or -CC 4 alkyl, trifluoromethyl or phenyl and
- Alkenyl-substituted bis (oxime ether) derivatives of the formula I are described in the literature as interesting crop protection agents [cf. WO-A 95/21153, WO-A 95/21154, WO-A 96/16030 and WO-A 97/03057].
- the aim of the present invention was accordingly to provide an economical process which provides alkenyl-substituted bis (oxime ether) derivatives of the formula I in good yield starting from easily accessible starting materials.
- the isomerization can be carried out in the presence of a base and / or an isomerization catalyst.
- Suitable bases are metal hydrides such as sodium hydride or in particular alkali metal alcoholates such as potassium tert. -butanolate and preferably sodium or potassium methylate.
- the base is generally used in a molar ratio of 1 to 4, preferably 1 to 2, with respect to the starting compound II.
- An isomerization catalyst can also be used as an additive or as an alternative to the base.
- Particularly suitable isomerization catalyst is metallic palladium or also salts of palladium such as palladium (II) chloride or palladium (II) acetate.
- the isomerization catalyst is usually used in a concentration of 0.1 to 5 mol%.
- solvents which can be used are aliphatic or aromatic hydrocarbons such as toluene, xylene, heptane, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane or, in particular, polar aprotic solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide or dirne-thylaceta id .
- aliphatic or aromatic hydrocarbons such as toluene, xylene, heptane, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane or, in particular, polar aprotic solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide or dirne-thylaceta id .
- the reaction temperature is generally 20 to 120 ° C and preferably 20 to 40 ° C. In the case of the palladium-catalyzed reaction, higher temperatures of 20 to 160 ° C and preferably 80 to 140 ° C are used.
- Reaction A) is a nucleophilic substitution that can be carried out under the usual reaction conditions.
- the benzyl compounds III are compounds in which X has the meaning given in claim 1 and L 1 is a leaving group such as halogen, acyloxy, alkylsulfonyloxy or arylsulfonyloxy and in particular chlorine or bromine.
- the substituents R 1 to R 5 of the bis (oxime) monoethers of the formula IV are as defined in claim 1.
- reaction is conveniently carried out in an inert solvent such as an ether, e.g. Tetrahydrofuran or dioxane or a polar aprotic solvent, e.g. Acetone, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide.
- an inert solvent such as an ether, e.g. Tetrahydrofuran or dioxane or a polar aprotic solvent, e.g. Acetone, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide.
- Sodium or potassium carbonate, sodium hydride, sodium methylate or a tertiary amine is generally used as the base.
- the reaction temperature is usually -20 to 80 ° C.
- the reaction can also be carried out in a two-phase system (eg dichloromethane / water) with the aid of a suitable phase transfer catalyst.
- a two-phase system eg dichloromethane / water
- the reaction mixtures can be worked up, for example, by extractive means.
- the benzyl compounds of formula III are from EP-A 348766; EP-A 363818 or EP-A 624155 known.
- Stage a) is carried out analogously to the procedure described in US Pat. No. 4,707,484.
- 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 equimolar amounts or in an up to 10-fold molar excess based on the acetoacetic ester B.
- Nitrite is understood to mean, for example, an alkali metal nitrite, in particular sodium nitrite, which is generally used in equimolar amounts or in an excess of up to 30 mol%, based on the acetoacetic ester B.
- 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 B used for the reaction can be prepared as described in Tetrahedron 4633 (1985) (see Scheme 5).
- 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). Level b):
- 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, dirthylacetamide 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 the compound V, 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 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 oC and especially at room temperature.
- the processing can take place, for example, by an extractive route.
- the acid addition salts of hydroxylamine are preferably used. All common acids are suitable for the production of the acid addition salts.
- Carboxylic acids such as acetic or propionic acid, dicarboxylic acids such as oxalic or succinic acid, mineral acids 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.
- 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 50 ° 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.
- Scheme B illustrates - at least partially in the "transoid, cisoid” form or in the "transoid, cisoid” form
- Example 8 48.4 g of solid sodium methyl t in 400 ml of DMF were stirred at 23 ° C. for 3 hours before 174 g of amide from Example 8 were added dropwise in 250 ml of DMF. The mixture was then stirred at 23 ° C. for 18 hours and worked up analogously to Example 6. 154 g of the title compound were obtained as a colorless solid which, according to NMR, GC and HPLC analysis, contained about 12% of the starting compound (Example 8).
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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)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU0104376A HUP0104376A3 (en) | 1998-11-20 | 1999-11-12 | Method for producing alkenyl-substituted bis(oximether) derivatives |
JP2000583851A JP2002530365A (ja) | 1998-11-20 | 1999-11-12 | アルケニル置換ビス(オキシムエーテル)誘導体の製造方法 |
EP99958032A EP1131282A1 (de) | 1998-11-20 | 1999-11-12 | Verfahren zur herstellung von alkenyl-substituierten bis(oximether)derivaten |
US09/831,412 US6417388B1 (en) | 1998-11-20 | 1999-11-12 | Method for producing alkenyl-substituted bis(oxime ether) derivatives |
AU15530/00A AU1553000A (en) | 1998-11-20 | 1999-11-12 | Method for producing alkenyl-substituted bis(oximether) derivatives |
BR9915423-4A BR9915423A (pt) | 1998-11-20 | 1999-11-12 | Processo para preparar derivados de bis (éter de oxima) substituìdos por alquenila. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853704.2 | 1998-11-20 | ||
DE19853704 | 1998-11-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000031023A1 true WO2000031023A1 (de) | 2000-06-02 |
Family
ID=7888522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/008740 WO2000031023A1 (de) | 1998-11-20 | 1999-11-12 | Verfahren zur herstellung von alkenyl-substituierten bis(oximether)derivaten |
Country Status (8)
Country | Link |
---|---|
US (1) | US6417388B1 (de) |
EP (1) | EP1131282A1 (de) |
JP (1) | JP2002530365A (de) |
CN (1) | CN1326436A (de) |
AU (1) | AU1553000A (de) |
BR (1) | BR9915423A (de) |
HU (1) | HUP0104376A3 (de) |
WO (1) | WO2000031023A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE42329E1 (en) | 2002-07-24 | 2011-05-10 | Lucas-Milhaupt, Inc. | Flux cored preforms for brazing |
WO2015197458A1 (en) * | 2014-06-27 | 2015-12-30 | Basf Se | Substituted 1-[2-[[[2-alkoxyimino-alkenylidene]amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds as phytopathogenic fungicides |
EP3029025A1 (de) | 2014-12-05 | 2016-06-08 | Basf Se | Verfahren zur Bekämpfung von Sojabohnenrost mit Behandlung von Sojabohnen mit (2e)-2-methoxyimino-2[2[[(e)-[(2e)-2-alkoxyimino-1-methyl-alk-3-enyliden]amino]oxymethyl]phenyl]-n-methyl-acetamiden |
EP3031325A1 (de) | 2014-12-10 | 2016-06-15 | Basf Se | Verfahren zur Bekämpfung von Sojabohnenrost mittels Behandlung von Sojabohnen mit (2E)-2-[2-[[1-(2,4-substituierten-Phenyl)Pyrazol-3-yl]Oxymeth¬yl]-3-substituierten-Phenyl]-2-Methoxymin-N-Methyl-Acet-Amiden |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997005103A1 (de) * | 1995-07-27 | 1997-02-13 | Basf Aktiengesellschaft | Phenylessigsäurederivate, verfahren und zwischenprodukte zu ihrer herstellung und ihre verwendung als schädlingsbekämpfungsmittel und fungizide |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU219157B (hu) * | 1994-01-05 | 2001-02-28 | Novartis Ag. | Peszticid hatású [dioxa-diaza/vagy oxa-triaza/-heptadienil-fenil]-akrilsav- és glioxilsav-származékok, előállításuk és alkalmazásuk |
-
1999
- 1999-11-12 AU AU15530/00A patent/AU1553000A/en not_active Abandoned
- 1999-11-12 EP EP99958032A patent/EP1131282A1/de not_active Withdrawn
- 1999-11-12 WO PCT/EP1999/008740 patent/WO2000031023A1/de not_active Application Discontinuation
- 1999-11-12 BR BR9915423-4A patent/BR9915423A/pt not_active Application Discontinuation
- 1999-11-12 US US09/831,412 patent/US6417388B1/en not_active Expired - Fee Related
- 1999-11-12 JP JP2000583851A patent/JP2002530365A/ja not_active Withdrawn
- 1999-11-12 HU HU0104376A patent/HUP0104376A3/hu unknown
- 1999-11-12 CN CN99813411A patent/CN1326436A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997005103A1 (de) * | 1995-07-27 | 1997-02-13 | Basf Aktiengesellschaft | Phenylessigsäurederivate, verfahren und zwischenprodukte zu ihrer herstellung und ihre verwendung als schädlingsbekämpfungsmittel und fungizide |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE42329E1 (en) | 2002-07-24 | 2011-05-10 | Lucas-Milhaupt, Inc. | Flux cored preforms for brazing |
WO2015197458A1 (en) * | 2014-06-27 | 2015-12-30 | Basf Se | Substituted 1-[2-[[[2-alkoxyimino-alkenylidene]amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds as phytopathogenic fungicides |
EP3029025A1 (de) | 2014-12-05 | 2016-06-08 | Basf Se | Verfahren zur Bekämpfung von Sojabohnenrost mit Behandlung von Sojabohnen mit (2e)-2-methoxyimino-2[2[[(e)-[(2e)-2-alkoxyimino-1-methyl-alk-3-enyliden]amino]oxymethyl]phenyl]-n-methyl-acetamiden |
EP3031325A1 (de) | 2014-12-10 | 2016-06-15 | Basf Se | Verfahren zur Bekämpfung von Sojabohnenrost mittels Behandlung von Sojabohnen mit (2E)-2-[2-[[1-(2,4-substituierten-Phenyl)Pyrazol-3-yl]Oxymeth¬yl]-3-substituierten-Phenyl]-2-Methoxymin-N-Methyl-Acet-Amiden |
Also Published As
Publication number | Publication date |
---|---|
HUP0104376A2 (hu) | 2002-03-28 |
HUP0104376A3 (en) | 2002-12-28 |
EP1131282A1 (de) | 2001-09-12 |
JP2002530365A (ja) | 2002-09-17 |
US6417388B1 (en) | 2002-07-09 |
AU1553000A (en) | 2000-06-13 |
CN1326436A (zh) | 2001-12-12 |
BR9915423A (pt) | 2001-08-07 |
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