DE1069143B - Process for the production of olefinic, fluorine-containing ethers or thioars - Google Patents
Process for the production of olefinic, fluorine-containing ethers or thioarsInfo
- Publication number
- DE1069143B DE1069143B DENDAT1069143D DE1069143DB DE1069143B DE 1069143 B DE1069143 B DE 1069143B DE NDAT1069143 D DENDAT1069143 D DE NDAT1069143D DE 1069143D B DE1069143D B DE 1069143DB DE 1069143 B DE1069143 B DE 1069143B
- Authority
- DE
- Germany
- Prior art keywords
- fluorine
- alcoholates
- olefins
- mercaptides
- olefinic
- 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.)
- Pending
Links
- 239000011737 fluorine Substances 0.000 title claims description 28
- 229910052731 fluorine Inorganic materials 0.000 title claims description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 10
- 150000002170 ethers Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 150000004707 phenolate Chemical class 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- -1 trifluorochloroethylene, 1,2-Difluoro-1,2-dichloroethylene, tetrafluoroethylene, trifluoroethylene, fluorine Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical class CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VILMUCRZVVVJCA-UHFFFAOYSA-M sodium glycolate Chemical compound [Na+].OCC([O-])=O VILMUCRZVVVJCA-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
Es ist bekannt, daß man bei der Einwirkung von hydroxylgruppenhaltigen Verbindungen, insbesondere von Alkoholen, in Anwesenheit von basischen Substanzen, vor allem Alkoholaten, auf fluorhaltige Olefine Anlagerungsverbindungen der allgemeinen FormelIt is known that the action of compounds containing hydroxyl groups, in particular from alcohols, in the presence of basic substances, especially alcoholates, to fluorine-containing olefins, addition compounds the general formula
HCX2-CX2-ORHCX 2 -CX 2 -OR
erhält, wobei ein X Halogen oder Wasserstoff sein kann und die restlichen X Fluor sind.obtained, wherein one X can be halogen or hydrogen and the remaining X are fluorine.
Weiterhin ist es bekannt, daß man in halogenierten Heptenen der Summenformeln C7H2Cl2F10 und C7H2Cl3F9 Chlor oder Fluor gegen Alkoxygruppen in Gegenwart freier Alkohole austauschen kann, wobei es jedoch offen bleibt, an welcher Stelle im Molekül dieser Austausch stattfindet, und man daher nur zu Verbindungen mit Undefinierten Strukturen gelangt.It is also known that in halogenated heptenes of the empirical formulas C 7 H 2 Cl 2 F 10 and C 7 H 2 Cl 3 F 9, chlorine or fluorine can be exchanged for alkoxy groups in the presence of free alcohols, although it remains open at which point this exchange takes place in the molecule, and one therefore only arrives at compounds with undefined structures.
Es ist ferner bekannt, daß man fluorhaltige Olefine mit Kaliumhydroxyd in Methanol umsetzt. Bei dieser Umsetzung entsteht jedoch stets Wasser nach der GleichungIt is also known that fluorine-containing olefins are reacted with potassium hydroxide in methanol. In this implementation however, water is always produced according to the equation
NaOH + CH3OH ===== NaOCH3 + H2ONaOH + CH 3 OH ===== NaOCH 3 + H 2 O
das ebenso wie Methanol und die Alkohole bei dem vorhergehend beschriebenen Verfahren zu unerwünschten Additionsreaktionen Anlaß gibt.like methanol and the alcohols in the process described above, this leads to undesired addition reactions Cause.
Es wurde nun gefunden, daß man olefinische, fluorhaltige Äther oder Thioäther durch Umsetzung von absoluten Alkoholaten, Enolaten, Phenolaten oder Mercaptiden mit fluorhaltigen Olefinen und Abspaltung von Metallfluorid erhält. Durch die erfindungsgemäßen Maßnahmen werden andere Verbindungen als nach den-bekannten Verfahren erhalten. Der Ausdruck »absolute Alkoholate, Enolate, Phenolate oder Mercaptides soll bedeuten, daß bei dem vorliegenden Verfahren Substanzen mit aktivem Wasserstoff in der Reaktionsmischung nicht oder praktisch nicht vorhanden sind. It has now been found that you can olefinic, fluorine-containing ethers or thioethers by reacting absolute alcoholates, enolates, phenolates or mercaptides with fluorine-containing olefins and cleavage of Receives metal fluoride. The measures according to the invention result in other compounds than those known Procedure received. The expression »absolute alcoholates, enolates, phenolates or mercaptides is intended mean that in the present process substances with active hydrogen are not present or practically absent in the reaction mixture.
So erhält man bei der Umsetzung von Tetrafluoräthylen mit absoluten Alkoholaten einen ungesättigten Äther nach folgendem Schema:Thus, when tetrafluoroethylene is reacted with absolute alcoholates, an unsaturated ether is obtained according to the following scheme:
CF2 = CF2-I-MeOR -» CF2 = CF- OR + MeFCF 2 = CF 2 -I-MeOR - »CF 2 = CF-OR + MeF
(I) 1(I) 1
Es ist anzunehmen, daß die Reaktion zunächst zur Anlagerungsverbindung (II) führt und daß daraus das Metallfluorid abgespalten wird (III):It can be assumed that the reaction initially leads to the addition compound (II) and that from it the Metal fluoride is split off (III):
-CF2-OR-CF 2 -OR
Verfahren zur HerstellungMethod of manufacture
von olefinischen, fluorhaltigenof olefinic, fluorine-containing
Äthern oder ThioäthernEthers or thioethers
j-vietaimuona aDgespaiien wira ^jj-vietaimuona aDgespaiien wira ^ j
CF2 = CF2 + MeOR -> MeCF2 CF 2 = CF 2 + MeOR -> MeCF 2
(Π)"
MeCF2 — CF2 — OR ->
CF2 = CF — OR + MeF(Π) "
MeCF 2 - CF 2 - OR -> CF 2 = CF - OR + MeF
(III) 2(III) 2
Ein Anzeichen hierfür ist das intermediäre Auftreten einer Dunkelfärbung, ähnlich wie bei anderen Um-Anmelder: An indication of this is the intermediate appearance of a dark color, similar to that of other re-applicants:
Farbwerke Hoechst AktiengesellschaftFarbwerke Hoechst Aktiengesellschaft
vormals Meister Lucius & Brüning,formerly Master Lucius & Brüning,
Frankfurt/M., Brüningstr. 45Frankfurt / M., Brüningstr. 45
Dr. Gerhard Bier, Dr. Hermann FritzDr. Gerhard Bier, Dr. Hermann Fritz
und Dr. Hans-Helmut Frey, Frankfurt/M.-Höchst,and Dr. Hans-Helmut Frey, Frankfurt / M.-Höchst,
sind als Erfinder genannt wordenhave been named as inventors
Setzungen mit metallorganischen Verbindungen, die beim Destillieren zurückgeht.Settlements with organometallic compounds, which decrease during distillation.
Geht man nicht vom Tetrafluoräthylen, sondern von einem Olefin aus, das außer Fluor noch andere Halogenatome, z. B. Chlor, enthält, dann wäre zu erwarten, daß nicht Metallfluorid, sondern Metallchlorid abgespalten wird. Dies muß aber nicht unbedingt der Fall sein. So verläuft z. B. die Reaktion von Natriumalkoholat mit Trifluorchloräthylen nicht nach Gleichung 3, sondern nach Gleichung 4, d. h., es entsteht nicht Natriumchlorid, sondern Natriumfluorid als Reaktionskomponente.If one does not start from tetrafluoroethylene, but from an olefin which, in addition to fluorine, also contains other halogen atoms, z. B. contains chlorine, then it would be expected that not metal fluoride but metal chloride would be split off will. But this does not necessarily have to be the case. So z. B. the reaction of sodium alcoholate with Trifluorochloroethylene not according to equation 3, but according to equation 4, i. i.e. no sodium chloride is formed, but sodium fluoride as a reaction component.
CF2 = CFCl + NaOR
CF2 = CFCl + NaORCF 2 = CFCl + NaOR
CF 2 = CFCl + NaOR
C2F3OR + NaCl 3C 2 F 3 OR + NaCl 3
C2F2ClOR + NaF 4C 2 F 2 ClOR + NaF 4
Die nach Gleichung 4 erhaltene ungesättigte Verbindung kann die beiden folgenden Strakturformeln haben:The unsaturated compound obtained according to equation 4 can have the following two structural formulas:
undand
CFCl= CF- OR
CF2 = CCl-ORCFCl = CF-OR
CF 2 = CCl-OR
Aus theoretischen Überlegungen ist anzunehmen, daß die Formel a) zutrifft.From theoretical considerations it can be assumed that formula a) applies.
Es ist ferner außerordentlich überraschend, daß man auch Fluor in α-Stellung zu einer C-C-DoppelbindungIt is also extremely surprising that one can also use fluorine in the α-position to a C-C double bond
909 649/424909 649/424
mit Alkoholat unter relativ milden Bedingungen abspalten kann; denn es ist eine allgemeine Lehre der organischen Chemie, daß unter den Halogenen Fluor am stärksten an C gebunden ist und daß eine C-C-Doppelbindung die C-Halogenbindung weiter verstärkt.can split off with alcoholate under relatively mild conditions; because it is a general teaching of the organic chemistry that among the halogens fluorine is most strongly bonded to C and that a C-C double bond the C-halogen bond is further strengthened.
Man kann die Reaktion sowohl mit Alkoholaten von ein- als auch von mehrwertigen Alkoholen durchführen.The reaction can be carried out both with alcoholates of monohydric and polyhydric alcohols.
Die gefundenen ungesättigten, fluorhaltigen Verbindungen können wie andere Olefine weiter umgesetzt werden. Insbesondere können sie auch erneut nach dem vorliegenden Verfahren mit Alkoholaten, Enolaten, Phenolaten oder Mercaptiden reagieren. Sie können als Komponenten für Polymerisationen oder Mischpolymerisationen verwendet werden.The unsaturated, fluorine-containing compounds found can be reacted further like other olefins. In particular, they can also be repeated after existing processes react with alcoholates, enolates, phenolates or mercaptides. You can as Components for polymerizations or interpolymerizations are used.
Als fluorhaltige Olefine kann man alle olefinischen Verbindungen, die Fluor oder Fluor und andere Halogene enthalten, z. B. Vinylfluorid, 1,1-Difhioräthylen, Trifluorchloräthylen, l,2-Difluor-l,2-dichloräthylen, Tetrafluoräthylen, Trifluoräthylen, fluorhaltige Propylene, fluorhaltige Butylene, fluorhaltige Butadiene, verwenden.All olefinic compounds, fluorine or fluorine and other halogens can be used as fluorine-containing olefins included, e.g. B. vinyl fluoride, 1,1-difhioethylene, trifluorochloroethylene, 1,2-Difluoro-1,2-dichloroethylene, tetrafluoroethylene, trifluoroethylene, fluorine-containing propylenes, fluorine-containing ones Use butylenes, fluorine-containing butadienes.
Für die Umsetzung mit den fluorhaltigen Olefinen kommen in Frage die Metallverbindungen von Alkoholen, Enolen, Phenolen, Mercaptanen, z. B. Methylalkohol, Äthylalkohol, n-Propylalkohol, iso-PropylalkohoI, n-Butylalkohol, iso-Butylalkohol, sekundärer Butylalkohol, tertiärer Butylalkohol, Glykol, Trifmoräthylalkohol, Trifhiorpropylalkohol, ebenso die Metallverbindungen der entsprechenden Mercaptanverbindungen, Acetessigester, Phenole. Um gute Ausbeuten an Olefinäther zu erzielen, ist es erforderlich, bei der Umsetzung die Gegenwart von freiem Alkohol, Enol, Phenol, Mercaptan zu vermeiden, da sonst als Nebenreaktionen die eingangs beschriebene Anlagerung stattfindet. Als Metalle für die Darstellung der Alkoholate, Enolate, Phenolate, Mercaptide kommen vor allem die Alkalimetalle in Frage, aber auch andere, z. B. Magnesium, Calcium, Zink, Blei, Zinn, können verwendet werden.For the reaction with the fluorine-containing olefins, the metal compounds of alcohols, enols, phenols, mercaptans, eg. B. methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, glycol, trifmorethyl alcohol, trifluoropropyl alcohol, as well as the metal compounds of the corresponding mercaptan compounds, acetoacetic esters. In order to achieve good yields of olefin ethers, it is necessary to avoid the presence of free alcohol, enol, phenol, mercaptan during the reaction, since otherwise the addition described above takes place as side reactions. As metals for the presentation of the alkoxides, enolates, phenolates, mercaptides especially the alkali metals are suitable, but other such. B. magnesium, calcium, zinc, lead, tin can be used.
Die Doppelbindung entsteht in der Regel zwischen den gleichen Kohlenstoffatomen wie im Ausgangsolefin. Es können jedoch auch Umlagerungen eintreten.The double bond is usually formed between the same carbon atoms as in the starting olefin. It however, rearrangements can also occur.
Mit einer solchen Umlagerung ist z. B. bei der Reaktion mit 1,1,1-Trifhiorpropylen zu rechnen.With such a rearrangement z. B. to be expected in the reaction with 1,1,1-Trifhiorpropylen.
CF3-CH = CH2
-> CF3-CH-CH2 CF 3 -CH = CH 2
-> CF 3 -CH-CH 2
MeMe
h AIeOR -ORh AIeOR -OR
CF2=CH-CH2-OR + MeFCF 2 = CH-CH 2 -OR + MeF
In einen Autoklav werden 250 Gewichtsteile absoluter Diäthyläther, 12 Gewichtsteile metallisches Natrium ge- ![eben und dazu langsam 23 Gewichtsteile absoluter Äthylilkohol zugefügt. Der Autoklav wird bei dieser Reaktion iber einen Rückflußkühler mit einem Blasenzähler verbunden. Nach Beendigung der Wasserstoffentwicklung vird der Autoklav noch 3 Stunden auf 40° C erhitzt, verschlossen und 58 Gewichtsteile Trifluorchloräthylen über :ine Druckschleuse zugegeben. Nach 7 Stunden wird der Dräunlichgefärbte Inhalt des Autoklavs entnommen und iofort destilliert. Zwischen 80 und 83° C gehen 50 Gewichtsteile = 70% der Theorie über. Es handelt sich dabei um eine Verbindung der Summenformel250 parts by weight of absolute diethyl ether and 12 parts by weight of metallic sodium are placed in an autoclave. ! [just and slowly 23 parts by weight of absolute ethyl alcohol added. During this reaction, the autoclave is connected to a bubble counter via a reflux condenser. After the evolution of hydrogen has ended, the autoclave is heated to 40 ° C. for a further 3 hours and closed and 58 parts by weight of trifluorochloroethylene added via a pressure lock. After 7 hours the The dark colored contents of the autoclave were removed and immediately distilled. 50 parts by weight go between 80 and 83 ° C = 70% of theory over. It is a combination of the sum formula
C4H5OF2Cl
die wahrscheinlich die KonstitutionC 4 H 5 OF 2 Cl
which probably the constitution
CFCl = CF-O-C2H5
besitzt.CFCl = CF-OC 2 H 5
owns.
C4H5OF2Cl (142,5)C 4 H 5 OF 2 Cl (142.5)
Gefunden ... C 35,25, H 3,60, F 26,32, Cl 24,73;
berechnet ... C 33,70, H 3,54, V2h,bb, Cl 24,88.Found ... C 35.25, H 3.60, F 26.32, Cl 24.73;
calculated ... C 33.70, H 3.54, V2h, bb, Cl 24.88.
In einem Druckgefäß werden bei einer Temperatur von 50° C 10 ecm Trifluorchloräthylen, 10 ecm absoluter Diäthyläther und 5 g Mononatriumglykolat 10 Stunden lang geschüttelt. Das Reaktionsgemisch wird nach Abdampfen des überschüssigen Trifluorchloräthylens in Wasser geschüttet. Es werden zwei Phasen erhalten. Die wäßrige Schicht enthält viel Fluorionen und nur sehr geringe Mengen Chlorionen. Die untere, nicht wäßrige Phase wird abgesaugt, und nach Abdestillieren des Diäthyläthers werden 8 g Rückstand erhalten, der bei der Destillation im Vakuum 7 g einer wasserhellen Flüssigkeit mit dem Siedepunkt 75° C bei einem Vakuum von 10 mm Hg liefert.10 ecm of trifluorochloroethylene and 10 ecm of absolute diethyl ether are placed in a pressure vessel at a temperature of 50 ° C and 5 g of monosodium glycolate shaken for 10 hours. The reaction mixture is after evaporation of the excess trifluorochloroethylene poured into water. Two phases are obtained. the The aqueous layer contains a large amount of fluorine ions and only very small amounts of chlorine ions. The lower one, not watery Phase is filtered off with suction, and after distilling off the diethyl ether, 8 g of residue are obtained, which at the Distillation in vacuo 7 g of a water-white liquid with a boiling point of 75 ° C at a vacuum of 10 mm Hg supplies.
Die Zusammensetzung der Substanz entspricht der Summenformel C6H5O2F5Cl2 mit der vermutlichen Konstitution The composition of the substance corresponds to the empirical formula C 6 H 5 O 2 F 5 Cl 2 with the presumed constitution
CFClH — CF9 — O — CH9 — CH9 — O — CF = CFClCFClH - CF 9 - O - CH 9 - CH 9 - O - CF = CFCl
Analyse: Berechnet gefundenAnalysis: calculated found
45 .. Mol 275, F 34,5, Cl 25,8, C 26,2, H 1,8; .. Mol 288, F 35,1, Cl 24,9, C 25,0, H 1,9. 45 .. Mol 275, F 34.5, Cl 25.8, C 26.2, H 1.8; .. Mol 288, F 35.1, Cl 24.9, C 25.0, H 1.9.
Claims (4)
USA.-Patentschrift Nr. 2 574 649;
Chem. Zentralblatt, 1953, S. 360;
"Journ. amer. chem. Society, Bd. 74, S. 4104 und 4105, 1952.Considered publications:
U.S. Patent No. 2,574,649;
Chem. Zentralblatt, 1953, p. 360;
"Journ. Amer. Chem. Society, Vol. 74, pp. 4104 and 4105, 1952.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1069143B true DE1069143B (en) | 1959-11-19 |
Family
ID=594342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1069143D Pending DE1069143B (en) | Process for the production of olefinic, fluorine-containing ethers or thioars |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1069143B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1145166B (en) | 1957-02-28 | 1963-03-14 | Du Pont | Process for the preparation of alkenyl and alkynyl trifluorovinylaethers |
| FR2386507A1 (en) * | 1977-04-04 | 1978-11-03 | Akad Wissenschaften Ddr | PROCESS FOR PREPARING PERFLUORATED DERIVATIVES OF STRAIGHT-CHAINED OLEFINS |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2574649A (en) * | 1951-11-13 | Alkyl ether of chlorofluoro |
-
0
- DE DENDAT1069143D patent/DE1069143B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2574649A (en) * | 1951-11-13 | Alkyl ether of chlorofluoro |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1145166B (en) | 1957-02-28 | 1963-03-14 | Du Pont | Process for the preparation of alkenyl and alkynyl trifluorovinylaethers |
| FR2386507A1 (en) * | 1977-04-04 | 1978-11-03 | Akad Wissenschaften Ddr | PROCESS FOR PREPARING PERFLUORATED DERIVATIVES OF STRAIGHT-CHAINED OLEFINS |
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