CH321865A - Process for the preparation of polyhaloolefins containing fluorine - Google Patents
Process for the preparation of polyhaloolefins containing fluorineInfo
- Publication number
- CH321865A CH321865A CH321865DA CH321865A CH 321865 A CH321865 A CH 321865A CH 321865D A CH321865D A CH 321865DA CH 321865 A CH321865 A CH 321865A
- Authority
- CH
- Switzerland
- Prior art keywords
- polyhaloolefins
- group
- polyhalohydrocarbon
- preparation
- chf
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims description 6
- 229910052731 fluorine Inorganic materials 0.000 title claims description 6
- 239000011737 fluorine Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 2
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- LTMHDMANZUZIPE-PUGKRICDSA-N digoxin Chemical compound C1[C@H](O)[C@H](O)[C@@H](C)O[C@H]1O[C@@H]1[C@@H](C)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@@H]3C[C@@H]4[C@]([C@@H]5[C@H]([C@]6(CC[C@@H]([C@@]6(C)[C@H](O)C5)C=5COC(=O)C=5)O)CC4)(C)CC3)C[C@@H]2O)C)C[C@@H]1O LTMHDMANZUZIPE-PUGKRICDSA-N 0.000 claims 1
- -1 perfluoromethyl- Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical group FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 1
- 206010012335 Dependence Diseases 0.000 description 1
- UGJVZXBXVRMUSG-UHFFFAOYSA-K [B+3].[F-].[F-].[F-] Chemical compound [B+3].[F-].[F-].[F-] UGJVZXBXVRMUSG-UHFFFAOYSA-K 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de préparation de polyhalogénooléfines contenant du fluor
La présente invention a pour objet un procédé de préparation de polyhalogénooléfines contenant du fluor.
On a remarqué qu'un groupe organique polyfluoré peut avoir un effet marqué sur les propriétés chimiques de groupes fonctionnels organiques adjacents. Le procédé objet de la présente invention permet de préparer des polyhalogénooléfines, contenant du fluor, de formule générale
RFCH = CHF dans laquelle RF représente un groupement polyhalogénohydrocarboné ayant au moins deux atomes de fluor fixés à l'atome de carbone le plus près de la double liaison.
Ce procédé est caractérisé en ce que l'on effectue une réaction d'addiction entre de l'acide fluorhydrique anhydre et un acétylène-polyhalogénohydrocarbure substitué de formule RFC =- CH dans laquelle RF a la même signification que ci-dessus. Le groupement RF peut aussi contenir des atomes d'un halogène autre que le fluor. Les polyhalogénooléfines fluorés obtenables par le procédé de l'invention sont des composés nouveaux.
Le net effet du groupe polyfluorohydrocarbure RF ressort du fait que dans la réaction CH t CH + HF + RFCH = CHF l'addition se fait dans le sens opposé à celui
de l'addition qui se produit dans le cas d'un
acétylène ne contenant pas de groupe poly
fluorohydrocarbure proche de la liaison acéty
lénique.
La réaction d'addition peut être effectuée
simplement en mettant les réactifs en présence
à la température ordinaire ou à des tempéra
tures légèrement plus élevées, sous pression, ou
bien en la catalysant à l'aide de trifluorure de
bore.
En ce qui concerne le composé de départ
RFC E CH
il est préférable que RF soit un groupe per
fluorohydrocarbure, en particulier un groupe
perfluoroalcoyle, de préférence n'ayant pas
plus de 20 atomes de carbone, et leurs analo
gues et homologues. On peut citer comme
exemple de composés de départ
RrC a CH
les perfluorométhyl-, perfluoroéthyl-, perfluoro
propyl-, perfluoroisopropyl-, les divers per
fluorobutyl-, les divers perfluoroamyl-, les di
vers perfluorohexyl-, -acétylènes substitués, de
même que les perfluoro homologues de ces
composés.
Les nouveaux composés représentés par la formule générale
RFCH = CHF indiqués ci-dessus sont utilisables à des fins diverses, en particulier comme produits intermédiaires dans la préparation d'autres produits chimiques fortement fluorés, puisque dans chaque cas ces composés contiennent une liaison oléfine réactive.
On peut citer comme exemples de nouveaux composés préparés par le procédé de l'invention
CF3CR = CHF
C2F5CH = CHF
C5F7CH = CHF
C4FgCH = CHF C5F11CH = CHF
C6F13CR = CHF
L'exemple suivant, dans lequel les parties sont des parties en poids, montre comment le procédé selon l'invention peut être réalisé en pratique
Dans une bombe en nickel refroidie, on fait distiller de l'acide fluorhydrique anhydre (10 parties) et du trifluorométhylacétylène (0,94 partie). La bombe est scellée, chauffée à la température ordinaire et laissée au repos pendant 48 heures, la température étant ensuite portée à 600 C et maintenue à cette valeur pendant 4 heures.
Après refroidissement, les produits de réaction sont distillés dans de l'eau et la matière volatile résiduelle est condensée, lavée à nouveau avec de l'eau et transférée dans un appareil à vide. Le fractionnement donne le 1,3,3,3-tétrafluoropropène, rendement 92 /o.
(Trouvé : C 31,8 o/o ; H 2,20/o; M 114.
Calculé à partir de C3H2F4
C 31,60/o; H 1,75 o/o; M 114.)
Point d'ébullition - 160 C.
Process for the preparation of polyhaloolefins containing fluorine
The present invention relates to a process for preparing polyhaloolefins containing fluorine.
It has been observed that a polyfluorinated organic group can have a marked effect on the chemical properties of adjacent organic functional groups. The process which is the subject of the present invention makes it possible to prepare polyhaloolefins, containing fluorine, of general formula
RFCH = CHF in which RF represents a polyhalohydrocarbon group having at least two fluorine atoms attached to the carbon atom closest to the double bond.
This process is characterized in that an addiction reaction is carried out between anhydrous hydrofluoric acid and a substituted acetylene polyhalohydrocarbon of formula RFC = - CH in which RF has the same meaning as above. The RF group can also contain atoms of a halogen other than fluorine. The fluorinated polyhaloolefins obtainable by the process of the invention are new compounds.
The clear effect of the polyfluorohydrocarbon group RF emerges from the fact that in the reaction CH t CH + HF + RFCH = CHF the addition is made in the opposite direction to that
of the addition that occurs in the case of a
acetylene not containing poly group
fluorohydrocarbon close to the acety bond
lenic.
The addition reaction can be carried out
simply by putting the reagents together
at room temperature or at tempera
slightly higher tures, under pressure, or
well by catalyzing it using trifluoride
boron.
Regarding the starting compound
RFC E CH
it is preferable that RF is a per group
fluorohydrocarbon, in particular a group
perfluoroalkyl, preferably not having
more than 20 carbon atoms, and their analogs
gues and counterparts. We can cite as
example of starting compounds
RrC to CH
perfluoromethyl-, perfluoroethyl-, perfluoro
propyl-, perfluoroisopropyl-, the various per
fluorobutyl-, various perfluoroamyl-, di
to substituted perfluorohexyl-, -acetylenes, from
same as the perfluoro homologs of these
compounds.
The new compounds represented by the general formula
RFCH = CHF indicated above can be used for various purposes, in particular as intermediates in the preparation of other strongly fluorinated chemicals, since in each case these compounds contain a reactive olefin bond.
As examples of new compounds prepared by the process of the invention, mention may be made of
CF3CR = CHF
C2F5CH = CHF
C5F7CH = CHF
C4FgCH = CHF C5F11CH = CHF
C6F13CR = CHF
The following example, in which parts are parts by weight, shows how the process according to the invention can be carried out in practice.
Anhydrous hydrofluoric acid (10 parts) and trifluoromethylacetylene (0.94 parts) are distilled off in a cooled nickel bomb. The bomb is sealed, heated to room temperature and left to stand for 48 hours, the temperature then being raised to 600 ° C and held there for 4 hours.
After cooling, the reaction products are distilled from water and the residual volatile material is condensed, washed again with water and transferred to a vacuum apparatus. Fractionation gives 1,3,3,3-tetrafluoropropene, yield 92%.
(Found: C 31.8 o / o; H 2.20 / o; M 114.
Calculated from C3H2F4
C 31.60 / o; H 1.75 o / o; M 114.)
Boiling point - 160 C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB321865X | 1952-09-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH321865A true CH321865A (en) | 1957-05-31 |
Family
ID=10334621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH321865D CH321865A (en) | 1952-09-03 | 1953-09-01 | Process for the preparation of polyhaloolefins containing fluorine |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH321865A (en) |
-
1953
- 1953-09-01 CH CH321865D patent/CH321865A/en unknown
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