EP1506150A1 - Method for the production of substituted trifluoroethylenes - Google Patents

Method for the production of substituted trifluoroethylenes

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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
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European Patent Office
Prior art keywords
water
alkyl
substituted
formula
polar medium
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EP03740131A
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German (de)
French (fr)
Inventor
Peter Wolfrum
Albrecht Marhold
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Bayer CropScience AG
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Bayer CropScience AG
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    • 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.

Abstract

The invention relates to a method for the production of substituted trifluoroethylenes, wherein a compound of formula (II), wherein R represents optionally carboxy, halogen, C1-C6-alkoxy, C1-C6-alkoxycarbonyl or C1-C4-alkylcarbonyloxy substituted C1-C6-Alkyl, or a group (III) wherein R' and R'', independently from each other, represent hydrogen or C1-C6-alkyl, or both, together with the nitrogen atom to which they are bonded, jointly represent cycloalkyl with 3-5 carbon atoms, wherein optionally one ring member is replaced with oxygen or sulphur and which is optionally substituted one to four times by C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy, and Hal represents chlorine, bromium or iodine, preferably chlorine or bromide, are brought into contact in a polar medium, containing water, with a dehalogenating agent.

Description

Nerfahren zur Herstellung von substituierten Trifluorethylenen Nerfahren for the production of substituted trifluoroethylene
Die vorliegende Erfindung betrifft ein Nerfahren zur Herstellung von substituierten Trifluorethylenen.The present invention relates to a ner process for the production of substituted trifluoroethylenes.
Trifluorethylene sind seit geraumer Zeit bekannt. So sind Trifluorethylene wie z.B. l,l,2-Trifluor-4-brom-l-buten wichtige Zwischenprodukte für die Herstellung von Agrochemikalien, insbesondere insektizid und nematizid wirkenden Nerbindungen (vgl. US 3,513,172, WO 86/07590, EP 342 150 AI, EP 507 464 AI, WO 02/06260,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,
WO/0206256, WO 02/06257 und WO 02/06259).WO / 0206256, WO 02/06257 and WO 02/06259).
Trifluorethylene lassen sich z.B. durch Dehalogenierung von Trifluordihalo-ethan- derivaten herstellen. So beschreiben Tarrant et al. (J Org. Chem. 34 (2), 323 (1969)) die Dehalogenierung von l,4-Dibrom-2-chlor-l,l,2-trifluorbutan mittels Zink inTrifluorethylene can e.g. by dehalogenation of trifluorodihalo-ethane derivatives. For example, Tarrant et al. (J Org. Chem. 34 (2), 323 (1969)) the dehalogenation of 1,4-dibromo-2-chloro-1,2,2-trifluorobutane using zinc in
. Ethanol. In EP 334 796 AI wird die Dehalogenierung des gleichen Ausgangsmaterials elektrochemisch in Methanol beschrieben. Beiden Nerfahren ist gemeinsam, dass die Umsetzung in einem kurzkettigen Alkohol erfolgt. Die bislang bekannten Nerfahren zur Herstellung dieser Zwischenprodukte weisen jedoch eine Reihe von Νachtei- ( len auf. So sind z.B. die Ausbeuten relativ niedrig. Aufgabe der vorliegenden Erfindung war es deshalb ein Nerfahren zur Verfügung zu stellen, das die Herstellung von Trifluorethenen in guten Ausbeuten und mit einfacher Aufreinigung ermöglicht., 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. However, the previously known Nerfahren for preparing these intermediates have a number of Νachtei- (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.
Es wurde nun ein verbessertes Nerfahren zur Herstellung von substituierten Trifluor- ethylenen der Formel (I) gefunden,An improved process for the preparation of substituted trifluoroethylene of the formula (I) has now been found
in welcher R für gegebenenfalls durch Carboxy, Halogen, Cι-C6-Alkoxy, Cι-C6-Alkoxy- carbonyl oder Cι-C4-Alkylcarbonyloxy substituiertes Cι-C6-Alkyl, oder für die Gruppierungin which 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
steht, in welcherstands in which
R' un R" unabhängig voneinander für Wasserstoff oder Cι-C6-Alkyl stehen, oder beide gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für gesättigtes Cycloalkyl mit 3 bis 5 Kohlenstoffatomen stehen, worin gegebenenfalls ein Ringglied durch Sauerstoff oder Schwefel ersetzt ist und welches gegebenenfalls ein- bis vierfach durch Ci-C^Alkyl, Trifluormethyl oder Cι-C4-Alko y substituiert ist,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,
welches dadurch gekennzeichnet ist, dass man eine Nerbindung der Formel (II)which is characterized in that a compound of the formula (II)
in welcherin which
R die vorstehend angegebene Bedeutung hat, undR has the meaning given above, and
Hai für Chlor, Brom oder Iod, bevorzugt fär Chlor oder Brom steht, in einem polaren Medium, das Wasser enthält, mit einem Dehalogenierungsmittel in Kontakt bringt.Shark represents chlorine, bromine or iodine, preferably chlorine or bromine, in a polar medium containing water in contact with a dehalogenating agent.
Non Formel (I) sind auch die Metallsalze insbesondere der erfindungsgemäßen Car- bonsäuren umfasst.The formula (I) also includes the metal salts, in particular of the carboxylic acids according to the invention.
Besonders bevorzugte Definitionen der Nerbindungen der Formel (I), die mit dem erfindungsgemäßen Nerfahren hergestellt werden, sind nachfolgend aufgeführt.Particularly preferred definitions of the compound compounds of the formula (I) which are prepared using the ner process according to the invention are listed below.
R steht bevorzugt für jeweils gegebenenfalls durch Carboxy, Fluor, Chlor,R preferably represents in each case optionally by carboxy, fluorine, chlorine,
Brom, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, n- oder i- Pentoxy, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, n-, i-, s- oder t-Butoxycarbonyl, Methylcarbonyloxy, Ethylcarbonyloxy, n- oder i-Propylcarbonyloxy oder n-, i-, s- oder t-Butylcarbonyloxy substituiertes Methyl, Ethyl, n- oder i-Propyl oder n-, i-, s- oder t-Butyl.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, ethyl, n- or i-propyl or n-, i-, s- or t-butyl.
R steht weiter bevorzugt für die GruppierungR further preferably stands for the grouping
in welcherin which
R' und R" unabhängig voneinander für Wasserstoff, Methyl, Ethyl, n- oder i-Propyl oder n-, i-, s- oder t-Butyl stehen, oder beide gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen der folgenden Cyclen stehen worinR '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 für Methyl, -Ethyl oder n-, i- oder s-Propyl steht, undA represents methyl, ethyl or n-, i- or s-propyl, and
n für 0, 1, 2, 3 oder 4 steht.n stands for 0, 1, 2, 3 or 4.
R steht besonders bevorzugt für jeweils gegebenenfalls durch Carboxy, Fluor, Chlor, Brom, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, n- oder i-Pentoxy, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbo- nyl, n-, i-, s- oder t-Butoxycarbonyl, Methylcarbonyloxy, Ethylcarbonyloxy, n- oder i-Propylcarbonyloxy oder n-, i-, s- oder t-Butylcarbonyloxy substituiertes Methyl oder Ethyl.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 steht weiter besonders bevorzugt für die GruppierungR further particularly preferably stands for the grouping
in welcherin which
R' und R" unabhängig voneinander für Wasserstoff, Methyl oder Ethyl stehen, oder beide gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen der folgenden Cyclen stehen 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
Als polares Medium (Lösungsmittel) kommen neben Wasser auch Mischungen von Wasser mit einem Lösungsvermittler in Frage. Als Lösungsvermittler (Ko-Lösungs- mittel) können z.B. die folgenden Verbindungen verwendet werden, wobei die Aufzählung nicht abschließend ist: Ether wie Tetrahydrofuran, Diethylenglykol-mono- methylether, Dioxan oder Bis-(2-methoxyethyl)-ether (Diglyme), Amide wie For- mamid, DMF, Diniemylacetamid oder l-Methyl-2-pyrrolidinon (NMP), Alkohole wie Methanol, Ethanol, Ethylenglykol, Diethylenglykol, Propylenglykol oder Gly- cerin, Säuren wie Essigsäure Propionsäure oder Methoxyessigsäure, Ketone wie Aceton oder Methylethylketon, Ester wie Essigsäureethylester oder Essigsäure- methoxyethylester, Carbonate wie Diethylcarbonat, Ethylencarbonat oder Propylen- carbonat, Harnstoffe wie N,N-Dimethylethylehharnstoff oder N,N-Di-methylpropy- len-harnstoff, Sulfone wie Tetramethylensulfon, Sulfonsäureamide wie N,N-Di- methy nethansulfonsäureamid oder N,N-Dimethylethansulfonsäureamid.In addition to water, mixtures of water with a solubilizer are also suitable as the polar medium (solvent). As solubilizers (co-solvents) 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 carbonate, ureas such as N, N-dimethylethyl urea or N, N-dimethylpropylene urea, sulfones such as tetramethylene sulfone, sulfonic acid amides such as N, N-dimethyl methanesulfonic acid amide or N, N-dimethylethanesulfonic acid amide.
Besonders bevorzugte Lösungsmittel, die im erfindungsgemäßen Verfahren verwendet werden, sind Wasser oder Mischungen von Wasser mit Ethern, z.B. Diethylen- glykolmonomethylether oder Polyalkoholen, z.B. Diethylenglykol.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.
Das Verhältnis (v/v) des Wasser enthaltenden polaren Mediums zum Lösungsver- mittler beträgt dabei vorzugsweise 1:10 bis 1:100, besonders bevorzugt 1:15 bis 1:40.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.
Als Dehalogenierungsmittel kommen z.B. Metalle wie Eisen, Zink, Magnesium, - uminium, Zinn, Kupfer oder Nickel in Frage. Besonders geeignet zur Verwendung im erfmdungsgemäßen Verfahren sind Eisen und/oder Zink. Es können auch Mischungen der Metalle oder durch Metallzusätze aktivierte Formen erfindungsge- mäß eingesetzt werden.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.
Die Umsetzung kann in einem breiten Temperaturbereich erfolgen. Bevorzugt erfolgt sie bei Temperaturen von 0 bis 100°C, wobei Temperaturen von 10 bis 90°C bevorzugt werden.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.
Das erfindungsgemäße Verfahren erlaubt in allen Fällen, in denen das Produkt leicht flüchtig ist, durch Destillation das gewünschte Produkt der Formel (I) direkt aus der Reaktionslösung zu isolieren. Beispielsweise azeotrop mitgerissenes Wasser lässt sich im Destillat einfach durch Phasentrennung abtrennen. Die Verbindungen der Formel (I) können anschließend leicht getrocknet werden, so z.B. durch Zugabe von etwas Molekularsieb oder anderen Trocknungsmitteln.In all cases in which the product is volatile, the process according to the invention allows the desired product of the formula (I) to be isolated directly from the reaction solution by distillation. For example, 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.
Die Ausgangsverbindungen der Formel (II) lassen sich nach an sich bekannten Verfahren herstellen, z.B. analog 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). -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). -
Die folgenden Beispiele illustrieren das erfindungsgemäße Verfahren anhand verschiedener Ausgangsverbindungen sowie verschiedener Lösungs- und Dehaloge- nierungsmittel. In analoger Weise kann das erfindungsgemäße Verfahren auch mit anderen, vorstehend genannten Ausgangsverbindungen, Lösungs- und Dehalogenie- rungsmitteln erfolgen. Die Beispiele sind deshalb nicht limitierend auszulegen. Beispiel 1:The following examples 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:
In einer Rührapparatur werden 131 g (2 mol) Zink-Staub in 1000 ml Diethylenglykol und 50 ml Wasser vorgelegt und durch Rühren suspendiert. Nach Erwärmen auf 50°C werden innerhalb von 2 Stunden 500 g (1,64 mol) l,4-Dibrom-2-chlor- 1,1,2- trifhiorbutan zudosiert. Es zeigt sich eine leicht exothermische Reaktion und die Dosiergeschwindigkeit wird so reguliert, dass die Innentemperatur ohne weitere Erwär- mung von außen bei 50 - 55°C gehalten wird. Nach Ende des Dosierens wird noch für weitere 30 Min. gerührt, dann Vakuum angelegt und das Produkt destilliert. Der Hauptteil geht bei einem Siedepunkt von 46 - 48 °C / 200 mbar über.131 g (2 mol) of zinc dust in 1000 ml of diethylene glycol and 50 ml of water are placed in a stirring apparatus and suspended by stirring. After heating to 50 ° C., 500 g (1.64 mol) of 1,4-dibromo-2-chloro-1,1,2-trifhiorbutane are metered in over the course of 2 hours. A slightly exothermic reaction is shown and the metering speed is regulated so that the inside temperature is kept at 50 - 55 ° C without further heating from the outside. After metering has ended, the mixture is stirred for a further 30 minutes, then vacuum is applied and the product is distilled. The main part passes over at a boiling point of 46 - 48 ° C / 200 mbar.
Die Ausbeute an l,l,2-Trifluor-4-brom-l-buten beträgt 312 g, Gehalt 90 %, was ei- ner Ausbeute von 90 % d. Th. entspricht.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.
Beispiel 2:Example 2:
In einer Rührapparatur werden 104 g (1,59 mol) Zink, 1 g ZnCl2 und 500 ml Diethylenglykohnonomethylether zusammen mit 20 ml Wasser vorgelegt. Bei einer Innentemperatur von 45°C werden 250 g (0,82 mol) l,4-Dibrom-2-chlor-l,l,2-tri- fluorbutan zugetropft. Nach Anstieg der Reaktionstemperatur auf 50 °C wird die Dosiermenge so reguliert, dass die Reaktion bei 50 bis 52° C abläuft. Nach Ende der Zugabe wird für 40 Min. nachgerührt, anschließend der Druck reduziert bis das Produkt über eine Brücke abdestilliert.104 g (1.59 mol) of zinc, 1 g of ZnCl 2 and 500 ml of diethylene glycol mononomethyl ether are placed in a stirring apparatus together with 20 ml of water. At an internal temperature of 45 ° C 250 g (0.82 mol) l, 4-dibromo-2-chloro-l, l, 2-trifluorobutane are added dropwise. After the reaction temperature has risen to 50 ° C, the metered amount is regulated so that the reaction takes place at 50 to 52 ° C. After the end of Addition is stirred for 40 minutes, then the pressure is reduced until the product is distilled off via a bridge.
Die Ausbeute an l,l,2-Trifluor-4-brom-l-buten beträgt 148 g, der Gehalt nach GC- Analyse 92,7 %.The yield of l, l, 2-trifluoro-4-bromo-l-butene is 148 g, the content according to GC analysis 92.7%.
Beispiel 3:Example 3:
In einer Rührapparatur werden 100 g Eisen (Pulver und feine Späne gemischt) in 700 ml Wasser vorgelegt, auf 90°C erhitzt und anschließend bei dieser Temperatur 255 g 4-Brom-3-chlor-3,4,4-trifluorbutancarbonsäure zudosiert. Die Temperatur wird bei etwa 90°C gehalten, nach Ende der Zugabe wird noch für 4 Stunden nachgerührt, abgeMhlt, durch Zugabe von konz. Schwefelsäure auf pH 1 gestellt und das Produkt zweimal mit je 300 ml Dichlormethan extrahiert. Nach Abdestillieren des Lösungsmittels verbleiben 101 g 3,4,4-Trifluor-3-buten-carbonsäure.100 g of iron (powder and fine chips mixed) are placed in 700 ml of water in a stirring apparatus, heated to 90 ° C. and then 255 g of 4-bromo-3-chloro-3,4,4-trifluorobutane carboxylic acid are metered in at this temperature. The temperature is kept at about 90 ° C, after the end of the addition, stirring is continued for 4 hours, cooled, by adding conc. Adjusted sulfuric acid to pH 1 and extracted the product twice with 300 ml dichloromethane. After the solvent has been distilled off, 101 g of 3,4,4-trifluoro-3-butenecarboxylic acid remain.
Beispiel 4:Example 4:
Analog zu Beispiel 3 werden 12,3 g Zink-Staub in 41 ml Wasser bei 0°C vorgelegt,Analogously to Example 3, 12.3 g of zinc dust are placed in 41 ml of water at 0 ° C.
48,5 g 4-Brom-3-chlor-3,4,4-tri--luorbutancarbonsäure zugetropft. Die Reaktion ist leicht exotherm, die Temperatur steigt auf 10°C. nach Ende der Zugabe werden nochmals 4,3 g Zink-Staub nachgegeben. Es wird für 2 Stunden nachgeruhrt, dann mit 6 N Salzsäure auf pH 2 gestellt, mit Dichlormethan zweimal extrahiert, dann die vereinigte organische. Phase mit 6 N Salzsäure gewaschen und anschließend über Magnesiumsulfat getrocknet. Nach Abdestillieren des DichlormeÜians verbleiben 19,8 g Rohprodukt, die laut GC-Analyse 17,1 g Produkt enthalten (Ausbeute 63,9 % der Theorie). 48.5 g of 4-bromo-3-chloro-3,4,4-tri-luorbutane carboxylic acid were added dropwise. The reaction is slightly exothermic, the temperature rises to 10 ° C. after the addition, 4.3 g of zinc dust are added. The mixture is stirred for 2 hours, then adjusted to pH 2 with 6N hydrochloric acid, extracted twice with dichloromethane, then the combined organic. Phase washed with 6 N hydrochloric acid and then dried over magnesium sulfate. After the dichloromethane has been distilled off, 19.8 g of crude product remain, which according to GC analysis contain 17.1 g of product (yield 63.9% of theory).

Claims

Patentansprüche claims
1. Verfahren zum Herstellen von Verbindungen der Formel (I)1. Process for the preparation of compounds of formula (I)
in welcherin which
R für gegebenenfalls durch Carboxy, Halogen, Cι-C6-Alkoxy, Cι-C6-Al- koxycarbonyl oder Cι-C -Alkylcarbonyloxy substituiertes Cι-C6-Al- kyl, oder für die GruppierungR is optionally substituted by carboxy, halogen, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl or C 1 -C 6 -alkylcarbonyloxy, C 1 -C 6 -alkyl, or for the grouping
steht, in welcherstands in which
R' und R" unabhängig voneinander für Wasserstoff oder Cι-C6-Alkyl stehen, oder beide gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für gesättigtes Cycloalkyl mit 3 bis 5 Kohlen- Stoffatomen stehen, worin gegebenenfalls ein Ringglied durchR 'and R "independently of one another represent hydrogen or C 1 -C 6 -alkyl, or both together with the nitrogen atom to which they are attached represent saturated cycloalkyl having 3 to 5 carbon atoms, in which a ring member may be through
Sauerstoff oder Schwefel ersetzt ist und welches gegebenenfalls ein- bis vierfach durch Ci-C^AJkyl, Trifluormethyl oder Ci-C-j-Alkoxy substituiert ist, welches dadurch gekennzeichnet ist, dass man eine Verbindung der FormelIs oxygen or sulfur and which is optionally substituted one to four times by Ci-C ^ AJkyl, trifluoromethyl or Ci-C-j alkoxy, which is characterized in that a compound of the formula
(π)(Π)
in welcherin which
R die vorstehend angegebene Bedeutung hat, undR has the meaning given above, and
Hai für Chlor, Brom oder Iod steht,Shark represents chlorine, bromine or iodine,
in einem polaren Medium, das Wasser enthält, mit einem Dehalogenierungs- mittel in Kontakt bringt.in a polar medium containing water in contact with a dehalogenating agent.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass als polares Medium Wasser verwendet wird.2. The method according to claim 1, characterized in that water is used as the polar medium.
3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Wasser enthaltende, polare Medium einen Lösvmgsvermittler enthält.3. The method according to claim 1 or 2, characterized in that the water-containing polar medium contains a solvating agent.
4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass das Verhältnis (v/v) des Wasser enthaltenden polaren Mediums zum Lösungsvermittler 1:10 bis 1:100 beträgt.4. The method according to claim 3, characterized in that the ratio (v / v) of the water-containing polar medium to the solubilizer is 1:10 to 1: 100.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Dehalogenierungsmittel Zink verwendet wird.5. The method according to any one of claims 1 to 4, characterized in that zinc is used as the dehalogenating agent.
6. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Dehalogenierungsmittel Eisen verwendet wird. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man anschließend die Verbindungen der Formel (I) durch Destillation aus der Reaktionsmischung isoliert und gegebenenfalls nach Phasentrennung trocknet. 6. The method according to any one of claims 1 to 4, characterized in that iron is used as the dehalogenating agent. Process according to one of Claims 1 to 6, characterized in that the compounds of the formula (I) are then isolated from the reaction mixture by distillation and, if appropriate, dried after phase separation.
EP03740131A 2002-05-13 2003-05-08 Method for the production of substituted trifluoroethylenes Withdrawn EP1506150A1 (en)

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WO2019230456A1 (en) * 2018-05-28 2019-12-05 Ａｇｃ株式会社 Method for producing fluorine-containing propene
AR116506A1 (en) 2018-09-26 2021-05-12 Adama Makhteshim Ltd PROCESS AND INTERMEDIARIES FOR THE PREPARATION OF FLUENSULFONE

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