DE857956C - Process for the production of fluorine-containing olefins - Google Patents
Process for the production of fluorine-containing olefinsInfo
- Publication number
- DE857956C DE857956C DEF1523A DEF0001523A DE857956C DE 857956 C DE857956 C DE 857956C DE F1523 A DEF1523 A DE F1523A DE F0001523 A DEF0001523 A DE F0001523A DE 857956 C DE857956 C DE 857956C
- Authority
- DE
- Germany
- Prior art keywords
- fluorine
- production
- containing olefins
- water
- alcohol
- 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.)
- Expired
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 8
- 239000011737 fluorine Substances 0.000 title claims description 8
- 150000001336 alkenes Chemical class 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000497 Amalgam Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 229910001023 sodium amalgam Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von fluorhaltigen Olefinen Gegenstand des Patents 847 442 ist ein Verfahren zur Herstellung von fluorhaltigen Olefinen bzw. ihren Derivaten aus fluorhaltigen Paraffinen, die im Molekül wenigstens r Fluoratom und an einander benachbarten Kohlenstoffatomen wenigstens je r Chloratom besitzen, das darin besteht, daß man die Paraffine in alkoholischem Medium mit Alkaliamalgam behandelt. Die Ausbeute an fluorhaltigen Äthylenen wird hierbei, wenn nicht besondere apparative Maßnahmen getroffen werden, durch eine Sekundärreaktion stark beeinträchtigt, indem das Athvlenderivat mit dem Alkohol unter Bildung von Äthern reagiert. Die Reaktionen verlaufen, wenn man i, r, 2-Trifluor-i, 2, a-trichloräthan in äthylalkoholischem Medium als spezielles Beispiel nimmt, nach folgenden Gleichungen: Die mit positiver Wärmetönuing verlaufende Sekundärreaktion kann unter besonders günstigen Umständen so stark überhandnehmen, daß die Aushetzte an Äthylenderivat auf Null absinkt. Eine lange Verweilzeit des Äthylenderivats im Reaktionsgefäß z. B. wirkt besonders nachteilig, ferner der katalytische Einfluß des Eisens der Gefäßwand.Process for the production of fluorine-containing olefins The subject of patent 847 442 is a process for the production of fluorine-containing olefins or their derivatives from fluorine-containing paraffins which have at least r fluorine atom in the molecule and at least r chlorine atom on adjacent carbon atoms, which consists in that one treated the paraffins in an alcoholic medium with alkali amalgam. The yield of fluorine-containing ethylenes is here, unless special equipment measures are taken, severely impaired by a secondary reaction in that the ethylene derivative reacts with the alcohol to form ethers. If one takes i, r, 2-trifluoro-i, 2, a-trichloroethane in an ethyl alcoholic medium as a special example, the reactions proceed according to the following equations: The secondary reaction, which proceeds with positive heat tinting, can, under particularly favorable circumstances, become so excessive that the exposure to ethylene derivative drops to zero. A long residence time of the ethylene derivative in the reaction vessel, for. B. has a particularly disadvantageous effect, as does the catalytic influence of the iron on the vessel wall.
Es «-urde.nun überraschenderweise gefunden, daß man die Ätherbildung in jedem Fall verhindern bzw. stark zurückdrängen kann, wenn man die Dech.lorierung nicht in wasserfreiem alkoholischem Medium durchführt, -sondern etwa 5 bis etwa 6o% Wasser zum Alkohol hinzufügt. Durch einen Zusatz von 5 % Wasser wird die Ätherbildung bereits bis auf 5 % zurückgedrängt. 300/0 Wasser im Alkohol haben sich als Optimum erwiesen. Bei einem Gehalt von 6o% Wasser im Alkohol wird zwar noch eine völlige Verhinderung der Ätherbildung erreicht, doch läßt die Geschwindigkeit der Dechlorierungsreaktion bei dieser Verdünnung bereits erheblich nach. Beispiele i. In einem eisernen Gefäß von 5oo ml Inhalt mit gasdichtem Rührer und aufgesetztem Rückflußkühler, der auf -20° gehalten wird, läßt man zu 30 ml Triflluortrichloräthan (C,C13F3) und 200 ml 70%igemwäßrigeinÄthylalkohol durch einenTropftrichter unter ständigem Rühren o,2%iges Natriumamalgam hinzufließen. In dem Maße, wie man Amalgam einlaufen läßt, entwickelt sich unter Selbsterwärmung des Reaktionsgemisches Trifluorchlorä.thylen (C F2 = C Cl F), welches durch den Rückflußkühler entweicht und in einem Gasometer über Wasser aufgefangen wird. Eine Ätherbildung findet unter diesen Bedingungen nicht statt. Die Verweilzeit spielt dabei keine Rolle.It has now been found, surprisingly, that ether formation can be prevented or strongly suppressed in any case if the dechlorination is not carried out in an anhydrous alcoholic medium, but rather about 5 to about 60% water is added to the alcohol. By adding 5% water, the ether formation is already pushed back to 5%. 300/0 water in alcohol have proven to be the optimum. With a content of 60% water in the alcohol, a complete prevention of the formation of ether is achieved, but the speed of the dechlorination reaction decreases considerably with this dilution. Examples i. In an iron vessel with a volume of 500 ml and a gas-tight stirrer and attached reflux condenser, which is kept at -20 °, o, 2% is added to 30 ml of trifluorotrichloroethane (C, C13F3) and 200 ml of 70% aqueous ethyl alcohol through a dropping funnel with constant stirring Add sodium amalgam. As the amalgam is run in, trifluorochloroethylene (C F2 = C Cl F) develops with self-heating, which escapes through the reflux condenser and is collected in a gasometer over water. Ether formation does not take place under these conditions. The dwell time does not matter.
Wird die gleiche Umsetzung unter Verwendung von absolutem Äthylalkohol durchgeführt, so vermindert sich die Ausbeute an Trifluorchloräthylen infolge Ätherbildung. Läßt man das Natriumamalgam so langsam hinzutropfe,n, daß die ReaktiOnszeit 2,5 Stunden beträgt und demnach die Verweilzeit des Trifluorchloräthylens im Reaktionsgefäß sehr lang ist, so sinkt die Ausbeute an Trifluorchloräthylen infolge Ätherbildung auf Null a1>.Will the same implementation using absolute ethyl alcohol carried out, the yield of trifluorochloroethylene is reduced as a result of ether formation. If the sodium amalgam is allowed to drop in so slowly that the reaction time is 2.5 Hours and therefore the residence time of the trifluorochloroethylene in the reaction vessel is very long, the yield of trifluorochloroethylene decreases as a result of ether formation to zero a1>.
2. Inder bei Beispiel i beschriebenen Weise wird Trifluortrichloräthan in einem Medium von 70»10 Methylalkohol und 30% Wasser dechloriert. Die Ausbeute an Trifluormonocllloräth_vlen beträgt 910/0.2. In the manner described in Example i, trifluorotrichloroethane is used dechlorinated in a medium of 70 »10 methyl alcohol and 30% water. The yield of Trifluormonocllloräth_vlen is 910/0.
Wird die gleiche Umsetzung in wasserfreiem Methylalkohol idurchgeführt, so sinkt unter gleichen Bedingungen die Ausbeute an Trifluormonochloräthylen auf 30% ab.If the same reaction is carried out in anhydrous methyl alcohol i, so the yield of trifluoromonochlorethylene decreases under the same conditions 30% off.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF1523A DE857956C (en) | 1950-03-03 | 1950-05-26 | Process for the production of fluorine-containing olefins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE681067X | 1950-03-03 | ||
| DEF1523A DE857956C (en) | 1950-03-03 | 1950-05-26 | Process for the production of fluorine-containing olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE857956C true DE857956C (en) | 1953-07-23 |
Family
ID=25946142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF1523A Expired DE857956C (en) | 1950-03-03 | 1950-05-26 | Process for the production of fluorine-containing olefins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE857956C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1246712B (en) * | 1963-10-01 | 1967-08-10 | Allied Chem | Process for the production of chlorotrifluoraethylene |
-
1950
- 1950-05-26 DE DEF1523A patent/DE857956C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1246712B (en) * | 1963-10-01 | 1967-08-10 | Allied Chem | Process for the production of chlorotrifluoraethylene |
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