EP1506150A1 - Procede pour produire des trifluoroethylenes substitues - Google Patents

Procede pour produire des trifluoroethylenes substitues

Info

Publication number
EP1506150A1
EP1506150A1 EP03740131A EP03740131A EP1506150A1 EP 1506150 A1 EP1506150 A1 EP 1506150A1 EP 03740131 A EP03740131 A EP 03740131A EP 03740131 A EP03740131 A EP 03740131A EP 1506150 A1 EP1506150 A1 EP 1506150A1
Authority
EP
European Patent Office
Prior art keywords
water
alkyl
substituted
formula
polar medium
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Withdrawn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
EP03740131A
Other languages
German (de)
English (en)
Inventor
Peter Wolfrum
Albrecht Marhold
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.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
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 Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1506150A1 publication Critical patent/EP1506150A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/06—Decomposition, e.g. elimination of halogens, water or hydrogen halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

Definitions

  • the present invention relates to a ner process for the production of substituted trifluoroethylenes.
  • Trifluorethylene have been known for some time. So are trifluoroethylenes such as l, l, 2-trifluoro-4-bromo-l-butene important intermediates for the production of agrochemicals, in particular insecticidal and nematicidal compounds (cf. US 3,513,172, WO 86/07590, EP 342 150 AI, EP 507 464 AI, WO 02/06260,
  • Trifluorethylene can e.g. by dehalogenation of trifluorodihalo-ethane derivatives.
  • Tarrant et al. J Org. Chem. 34 (2), 323 (1969)
  • Ethanol. EP 334 796 AI describes the dehalogenation of the same starting material electrochemically in methanol. Both ner drives have in common that the implementation takes place in a short-chain alcohol.
  • the previously known Nerfahren for preparing these intermediates have a number of ⁇ achtei- (len on For instance, the yields are relatively low. The present invention was therefore to make it a Nerfahren is available that the production of Trifluorethenen in good yields and. with simple purification.
  • R is optionally substituted by carboxy, halogen, -C 6 alkoxy, -C 6 alkoxycarbonyl or -C 4 alkylcarbonyloxy substituted -C 6 alkyl, or for the grouping
  • R 'un R "independently of one another are hydrogen or C 1 -C 6 -alkyl, or both together with the nitrogen atom to which they are attached are saturated cycloalkyl having 3 to 5 carbon atoms, in which case one ring member is replaced by oxygen or sulfur and which is optionally substituted one to four times by C 1 -C 4 alkyl, trifluoromethyl or C 1 -C 4 -alko y,
  • Shark represents chlorine, bromine or iodine, preferably chlorine or bromine, in a polar medium containing water in contact with a dehalogenating agent.
  • the formula (I) also includes the metal salts, in particular of the carboxylic acids according to the invention.
  • R preferably represents in each case optionally by carboxy, fluorine, chlorine,
  • R further preferably stands for the grouping
  • R 'and R independently of one another represent hydrogen, methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, or both together with the nitrogen atom to which they are attached, for one of the following cycles wherein
  • A represents methyl, ethyl or n-, i- or s-propyl
  • n 0, 1, 2, 3 or 4.
  • R particularly preferably represents in each case optionally by carboxy, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n- or i-pentoxy, methoxycarbonyl, ethoxycarbonyl , n- or i-Propoxycarbonyl, n-, i-, s- or t-butoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, n- or i-propylcarbonyloxy or n-, i-, s- or t-butylcarbonyloxy substituted methyl or ethyl ,
  • R further particularly preferably stands for the grouping
  • R 'and R "independently of one another represent hydrogen, methyl or ethyl, or both together with the nitrogen atom to which they are attached represent one of the following cycles
  • solubilizers e.g. the following compounds are used, the list being not exhaustive: ethers such as tetrahydrofuran, diethylene glycol monomethyl ether, dioxane or bis (2-methoxyethyl) ether (diglyme), amides such as formamide, DMF, diniemylacetamide or l- Methyl-2-pyrrolidinone (NMP), alcohols such as methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol or glycerin, acids such as acetic acid, propionic acid or methoxyacetic acid, ketones such as acetone or methyl ethyl ketone, esters such as ethyl acetate or methyl acetate, carbonates such as diethyl carbonate, Ethylene carbonate or propylene carbon
  • Particularly preferred solvents used in the process according to the invention are water or mixtures of water with ethers, e.g. Diethylene glycol monomethyl ether or polyalcohols, e.g. Diethylene glycol.
  • ethers e.g. Diethylene glycol monomethyl ether or polyalcohols, e.g. Diethylene glycol.
  • the ratio (v / v) of the water-containing polar medium to the solubilizer is preferably 1:10 to 1: 100, particularly preferably 1:15 to 1:40.
  • Suitable dehalogenating agents are, for example, metals such as iron, zinc, magnesium, aluminum, tin, copper or nickel. Iron and / or zinc are particularly suitable for use in the process according to the invention. It can too Mixtures of the metals or forms activated by metal additives are used according to the invention.
  • the reaction can take place in a wide temperature range. It is preferably carried out at temperatures from 0 to 100 ° C., temperatures from 10 to 90 ° C. being preferred.
  • the process according to the invention allows the desired product of the formula (I) to be isolated directly from the reaction solution by distillation.
  • azeotropically entrained water can be easily separated in the distillate by phase separation.
  • the compounds of formula (I) can then be easily dried, e.g. by adding some molecular sieve or other drying agents.
  • the starting compounds of formula (II) can be prepared by processes known per se, e.g. analogous to US 3,562,341; Chin. J. Chem. 281, (1990); J Org. Chem. 29, 1198 (1964); J. Fluorine Chem. 66, 171 (1994); Tetrahedron Lett. 31, 1307 (1990). -
  • Example 1 illustrate the process according to the invention using various starting compounds and various solvents and dehalogenating agents.
  • the process according to the invention can also be carried out in an analogous manner with other starting compounds, solvents and dehalogenating agents mentioned above. The examples are therefore not to be interpreted as limiting.
  • Example 1 illustrate the process according to the invention using various starting compounds and various solvents and dehalogenating agents.
  • the process according to the invention can also be carried out in an analogous manner with other starting compounds, solvents and dehalogenating agents mentioned above. The examples are therefore not to be interpreted as limiting.
  • Example 1 illustrate the process according to the invention using various starting compounds and various solvents and dehalogenating agents.
  • the process according to the invention can also be carried out in an analogous manner with other starting compounds, solvents and dehalogenating agents mentioned above. The examples are therefore not to be interpreted as limiting.
  • Example 1 illustrate the process according to the invention using various starting compounds and various solvents and dehalogenating agents.
  • the process according to the invention can also be
  • the yield of l, l, 2-trifluoro-4-bromo-l-butene is 312 g, content 90%, which means a yield of 90% of theory. Th.
  • the yield of l, l, 2-trifluoro-4-bromo-l-butene is 148 g, the content according to GC analysis 92.7%.
  • Example 3 Analogously to Example 3, 12.3 g of zinc dust are placed in 41 ml of water at 0 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé pour produire des trifluoroéthylènes substitués. Ce procédé consiste à mettre en contact avec un agent de déshalogénation dans un milieu polaire contenant de l'eau un composé de formule (II) dans laquelle R représente alkyle C1-C6 éventuellement substitué par carboxy, halogène, alkoxy C1-C6, alkoxycarbonyle C1-C6 ou alkylcarbonyloxy C1-C4 ou un groupe (III) dans lequel R' et R'' représentent indépendamment l'un de l'autre hydrogène ou alkyle C1-C6 ou représentent conjointement avec l'atome d'azote auquel ils sont liés un cycloalkyle saturé présentant de 3 à 5 atomes de carbone, un élément cyclique étant éventuellement remplacé par oxygène ou soufre et étant éventuellement substitué une à quatre fois par alkyle C1-C4, trifluorométhyle ou alkoxy C1-C4, et Hal représente chlore, brome ou iode, de préférence chlore ou brome.
EP03740131A 2002-05-13 2003-05-08 Procede pour produire des trifluoroethylenes substitues Withdrawn EP1506150A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10221120A DE10221120A1 (de) 2002-05-13 2002-05-13 Verfahren zur Herstellung von substituierten Trifluorethylenen
DE10221120 2002-05-13
PCT/EP2003/004809 WO2003095401A1 (fr) 2002-05-13 2003-05-08 Procede pour produire des trifluoroethylenes substitues

Publications (1)

Publication Number Publication Date
EP1506150A1 true EP1506150A1 (fr) 2005-02-16

Family

ID=29285319

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740131A Withdrawn EP1506150A1 (fr) 2002-05-13 2003-05-08 Procede pour produire des trifluoroethylenes substitues

Country Status (6)

Country Link
US (1) US20050222461A1 (fr)
EP (1) EP1506150A1 (fr)
JP (1) JP2005525419A (fr)
AU (1) AU2003267541A1 (fr)
DE (1) DE10221120A1 (fr)
WO (1) WO2003095401A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10319591A1 (de) 2003-05-02 2004-11-18 Bayer Cropscience Ag Wirkstoffkombinationen mit nematiziden, insektiziden und fungiziden Eigenschaften basierend auf Trifluorbutenyl-Verbindungen
CN105753632A (zh) * 2014-12-16 2016-07-13 浙江蓝天环保高科技股份有限公司 一种4-溴-1,1,2-三氟-1-丁烯的制备方法
JP7287391B2 (ja) * 2018-05-28 2023-06-06 Ａｇｃ株式会社 含フッ素プロペンの製造方法
AR116506A1 (es) * 2018-09-26 2021-05-12 Adama Makhteshim Ltd Proceso e intermediarios para la preparación de fluensulfona

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE816992C (de) * 1949-10-29 1951-10-15 Bayer Ag Verfahren zur Herstellung von Halogenfluoraethylenen
FR1058345A (fr) * 1951-06-14 1954-03-16 Hoechst Ag Hydrocarbures aliphatiques non saturés contenant du ? et leur procédé de préparation
US3513172A (en) * 1965-09-27 1970-05-19 Stauffer Chemical Co 3-phenyl-5-(3,4,4-trifluoro-3-butenylthio)1,2,4-thiadiazole
US3562341A (en) * 1968-07-29 1971-02-09 Us Army Polyfluorinated 1,3-dienes having fluorine substituents in the 1,1,2-position,their polymers,and methods for making the same
US4952580A (en) * 1985-06-20 1990-08-28 Fmc Corporation Pesticidal polyhaloalkene derivatives
EP0334796B1 (fr) * 1988-03-19 1993-05-12 Hoechst Aktiengesellschaft Procédé de préparation d'hydrocarbures halogénés insaturés
GB9205507D0 (en) * 1991-03-28 1992-04-29 Ici Plc Heterocyclic compounds
WO1995004727A1 (fr) * 1993-08-05 1995-02-16 Zeneca Limited Procede de preparation de derives fluoroathenylthio heterocycliques
US5514717A (en) * 1994-10-26 1996-05-07 Monsanto Company Fluoroalkenyl compounds and their use as pest control agents
DE19650199A1 (de) * 1996-12-04 1998-06-10 Bayer Ag Polyhalogenhexene, ihre Herstellung und die Herstellung von halogenierten C¶4¶-Carbonsäuren daraus
CA2312194A1 (fr) * 2000-06-13 2001-12-13 Mario Boucher Elastomeres reticulables fluores bromosulfones a faible tg a base de fluorure de vinylidene et ne contenant ni du tetrafluoroethylene ni de groupement siloxane
DE10034133A1 (de) * 2000-07-13 2002-01-24 Bayer Ag Heterocyclische Fluoralkenylthioether (l)
DE10034130A1 (de) * 2000-07-13 2002-01-24 Bayer Ag Heterocyclische Fluoralkenylthioether (lV)
DE10034131A1 (de) * 2000-07-13 2002-01-24 Bayer Ag Heterocyclische Fluoralkenylthioether (II)
DE10034132A1 (de) * 2000-07-13 2002-01-24 Bayer Ag Heterocyclische Fluoralkenylthioether (lll)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03095401A1 *

Also Published As

Publication number Publication date
DE10221120A1 (de) 2003-11-27
JP2005525419A (ja) 2005-08-25
AU2003267541A1 (en) 2003-11-11
US20050222461A1 (en) 2005-10-06
WO2003095401A1 (fr) 2003-11-20

Similar Documents

Publication Publication Date Title
EP0444563B1 (fr) Sels de 3-hydroxy-2-cyclobutène-1-on, leur préparation et utilisation
EP1644314B1 (fr) Procede pour produire des alkylesters d'acide difluoroacetylacetique
WO2002002532A1 (fr) Esters d'acide 4-alcoxycyclohexan-1-aminocarboxylique, et leur procede de production
EP0370391A2 (fr) Procédé de préparation de 4,5-dichloro-6-éthylpyrimidine
EP1506150A1 (fr) Procede pour produire des trifluoroethylenes substitues
DE19820722C1 (de) Verfahren zur Herstellung von Benzoylpyrazolen
DE69926223T2 (de) Verfahren zur herstellung von zwischenprodukten
DE3038598A1 (de) Verfahren zur herstellung von (alpha)-hydroxy-carbonsaeureamiden, neue zwischenprodukte hierfuer und verfahren zu deren herstellung
EP1296920A2 (fr) Procede de production de 1,3-dicetones bicycliques
DE2932198A1 (de) Verfahren zur herstellung von o-(2,6-dichloranilino)-phenylessigsaeure und neue zwischenprodukte zur durchfuehrung des verfahrens
EP1833814B1 (fr) Procede pour produire des 2-alcoxycarbonyle-3-aminothiophenes substitues
DE69928454T2 (de) Pyridazinonderivate verwendbar als Zwischenprodukte für Herbizide
EP0089485B1 (fr) Procédé pour préparer des esters de l'acide 5-chloro-1H-tétrazolo-1-carboxylique, ainsi que procédé pour préparer les esters de l'acide dichloroisonitrile-carboxylique nécessaires
EP0299277A2 (fr) Procédé pour la préparation de pyridylalkylcétones substituées
WO2003095395A1 (fr) Procede pour produire des trifluoroethylenes substitues
CH409903A (de) Verfahren zur Herstellung von organischen Fluor-Verbindungen
EP0345464B1 (fr) Procédé pour la préparation d'esters d'acide 3-amino-2-(benzoyl) acrylique substitués ainsi qu'un procédé de préparation d'intermédiaires pour des constituants actifs antibactériens à partir de ces composés
DE69018619T2 (de) Alpha, beta-ungesättigte ketone und ketoximderivat.
EP0665212A1 (fr) Procédé pour la préparation de dérivés d'acide phénylacétique substitué et intermédiaires
DD209443A5 (de) Verfahren zur herstellung von acylaminoderivaten von 1-(aryl- oder subst.-aryl)amino-1-thioalkancarboxysaeuren
DE3723069A1 (de) 5-halogen-6-amino-nikotinsaeurehalogenide, ihre herstellung und ihre verwendung
WO2001036405A1 (fr) Procede de preparation de benzofuranonoximes
EP0021115A1 (fr) Procédé de préparation de dérivés de l'acide 3,3-diméthyl-cyclopropane-1,1,2-tricarboxylique, alpha-halogène-nitriles comme produits intermédiaires pour ce procédé et procédé pour leur préparation
DE3210296C2 (fr)
EP2563762B1 (fr) Procédé pour produire des pyridin- 2 - ones substituées

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20061201