DE19956364A1 - Preparation of (a)symmetric bis(lower fluoroalkyl) sulfite esters, useful as solvent in lithium battery electrolyte, comprises reacting thionyl chloride and fluoroalkanol(s) in absence of acid acceptor - Google Patents
Preparation of (a)symmetric bis(lower fluoroalkyl) sulfite esters, useful as solvent in lithium battery electrolyte, comprises reacting thionyl chloride and fluoroalkanol(s) in absence of acid acceptorInfo
- Publication number
- DE19956364A1 DE19956364A1 DE1999156364 DE19956364A DE19956364A1 DE 19956364 A1 DE19956364 A1 DE 19956364A1 DE 1999156364 DE1999156364 DE 1999156364 DE 19956364 A DE19956364 A DE 19956364A DE 19956364 A1 DE19956364 A1 DE 19956364A1
- Authority
- DE
- Germany
- Prior art keywords
- absence
- preparation
- thionyl chloride
- fluoroalkanol
- solvent
- 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- Withdrawn
Links
- 239000002253 acid Substances 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 title abstract description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000002904 solvent Substances 0.000 title description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 title description 2
- 229910052744 lithium Inorganic materials 0.000 title description 2
- 239000003792 electrolyte Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims description 9
- -1 perfluoro-t-butyl Chemical group 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- HVNOLEGWKGMONA-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) sulfite Chemical compound FC(F)(F)COS(=O)OCC(F)(F)F HVNOLEGWKGMONA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C301/00—Esters of sulfurous acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung bezieht sich auf die Herstellung von Fluoralkylsulfitestern.The invention relates to the production of Fluoroalkyl sulfite esters.
Fluoralkylsulfitester können als Lösungsmittel in Elek trolythen für Lithium-Batterien eingesetzt werden (siehe z. B. japanische Patentanmeldung JP 09/167635).Fluoroalkyl sulfite esters can be used as solvents in Elek trolythene can be used for lithium batteries (see e.g. B. Japanese patent application JP 09/167635).
Die Herstellung von Alkylestern der schwefeligen Säure wird von W. E. Bissinger und F. E. Kung in J. Am. Chem. Soc. 69 (1947), Seiten 2158 bis 2163 beschrieben. Thionylchlorid und Alkohol werden in verschiedenen Lösungsmitteln miteinan der umgesetzt. Es sind zahlreiche Nebenreaktionen zu beobach ten. R. A. De Marco, T. A. Kovacina und W. B. Fox beschreiben in J. Fluorine Chem. 5 (1975), Seiten 221 bis 230 die Her stellung von Estern aus Thionylchlorid und fluorierten Alko holen. Dabei wird Triethylamin als Säurefänger eingesetzt; es wird als wichtig bezeichnet, daß Alkohol und Amin als Gemisch eingesetzt werden.The production of alkyl esters of sulfurous acid is described by W. E. Bissinger and F. E. Kung in J. Am. Chem. Soc. 69 (1947), pages 2158 to 2163. Thionyl chloride and alcohol are mixed together in different solvents the implemented. Numerous side reactions can be observed ten. R. A. De Marco, T. A. Kovacina and W. B. Fox in J. Fluorine Chem. 5 (1975), pages 221 to 230 the Her provision of esters from thionyl chloride and fluorinated alcohol to fetch. Triethylamine is used as an acid scavenger; it is said to be important that alcohol and amine as a mixture be used.
Aufgabe der vorliegenden Erfindung ist es, ein einfa ches, technisch durchführbares Verfahren zur Herstellung von Estern des Thionylchlorids anzugeben. Diese Aufgabe wird durch das in den Ansprüchen angegebene Verfahren gelöst. Das erfindungsgemäße Verfahren zur Herstellung von Ver bindungen der allgemeinen Formel (I), R1O-S(O)-OR2, worin R1 und R2 gleich oder verschieden sein können und jeweils für durch mindestens 1 Fluoratom substituiertes C1-C3-Alkyl ste hen, sieht vor, daß man Alkohole der Formel R1OH und R2OH mit SOCl2 in Abwesenheit eines Lösungsmittels und in Abwesenheit eines Säurefängers miteinander umsetzt. Symmetrische Ester werden natürlich dann in besonders hoher Ausbeute erhalten, wenn R1 und R2 gleich sind und man das SOCl2 somit nur mit einem Alkohol umsetzt. Das Molverhältnis von SOCl2 und Alko hol liegt im Bereich von 1 : 1,6 bis 1 : 2,4. Bevorzugt stehen R1 und R2 für Trifluorethyl, Perfluor-t-butyl, Hexafluorisopro pyl oder Pentafluor-n-propyl. Zweckmäßig geht man so vor, daß man Alkohol und Thionylchlorid bei niedriger Temperatur, bei spielsweise bei 0°C oder darunter langsam miteinander ver mischt und die Temperatur dann langsam ansteigen läßt. Man kann dann bis hin zur Rückflußtemperatur erhitzen. Zum Aus treiben des sich bildenden HCl-Gases kann man Stickstoff oder Inertgas oder auch Luft durch die Reaktionsmischung durchbla sen.The object of the present invention is to provide a simple, technically feasible process for the preparation of esters of thionyl chloride. This object is achieved by the method specified in the claims. The process according to the invention for the preparation of compounds of the general formula (I), R 1 OS (O) -OR 2 , in which R 1 and R 2 can be identical or different and in each case for C 1 -C 3 - substituted by at least 1 fluorine atom Alkyl stand, provides that alcohols of the formula R 1 OH and R 2 OH are reacted with SOCl 2 in the absence of a solvent and in the absence of an acid scavenger. Symmetrical esters are of course obtained in a particularly high yield if R 1 and R 2 are the same and the SOCl 2 is thus only reacted with an alcohol. The molar ratio of SOCl 2 and alcohol is in the range from 1: 1.6 to 1: 2.4. R 1 and R 2 are preferably trifluoroethyl, perfluoro-t-butyl, hexafluoroisopropyl or pentafluoro-n-propyl. Appropriately, the procedure is such that alcohol and thionyl chloride are slowly mixed together at low temperature, for example at 0 ° C. or below, and the temperature is then allowed to rise slowly. You can then heat up to the reflux temperature. To drive off the HCl gas formed, nitrogen or inert gas or air can be blown through the reaction mixture.
Das erfindungsgemäße Verfahren gestattet die Herstellung von Fluoralkylestern der schwefeligen Säure mit guter Ausbeu te und in technisch einfacher Weise. Weder muß man Lösungs mittel aufarbeiten noch fällt Hydrochlorid an. Angesichts des Standes der Technik war nicht zu erwarten, daß die Umsetzung in technisch brauchbarer Weise ablaufen könnte.The method according to the invention permits production of fluoroalkyl esters of sulfurous acid with good yield te and in a technically simple way. Neither do you have to find solutions work up medium hydrochloride is still produced. Given the The state of the art was not expected to be implemented could run in a technically useful manner.
Das folgende Beispiel soll die Erfindung weiter erläu tern, ohne sie in ihrem Umfang einzuschränken.The following example is intended to explain the invention further ters without restricting their scope.
2 CF3 2 CF 3
CH2 CH 2
+ SOCl2 + SOCl 2
⇒ (CF3 ⇒ (CF 3
CH2 CH 2
O)2 O) 2
SO + 2 HClSO + 2 HCl
In einem 250 ml Dreihalskolben mit Thermometer und Rückfluß kühler wurde Trifluorethanol (60 g; 0,6 Mol; 100 g Mol-1) vorgelegt und im Eisbad gekühlt. Unter weiterer Kühlung wurde Thionylchlorid (36,6 g; 0,33 Mol; 111 g Mol-1) hinzugefügt.Trifluoroethanol (60 g; 0.6 mol; 100 g mol -1 ) was placed in a 250 ml three-necked flask with a thermometer and a reflux condenser and cooled in an ice bath. With further cooling, thionyl chloride (36.6 g; 0.33 mol; 111 g mol -1 ) was added.
Das Eisbad wurde entfernt und die Reaktionsmischung langsam erhitzt, so daß an der am Rückflußkühler angeschlossenen Waschflasche ein gleichmäßiger HCl-Strom entwich. Die Reak tion setzte zwischen 20 bis 30°C ein. Mit nachlassendem HCl- Strom wurde die Temperatur sukzessive gesteigert, um den HCl- Strom konstant zu halten. Nach Abschluß der Gasentwicklung wurde noch 1 h bei 110°C am Rückfluß erhitzt und das erhal tene Rohprodukt destillativ gereinigt.The ice bath was removed and the reaction mixture slowly heated, so that connected to the reflux condenser A constant flow of HCl escaped from the wash bottle. The Reak tion started between 20 and 30 ° C. With decreasing HCl The temperature was gradually raised to reduce the HCl To keep current constant. After gas evolution is complete was heated under reflux at 110 ° C for 1 h and obtained tene crude product purified by distillation.
Bis-[trifluorethyl]-sulfit:
Ausbeute: 36,8 g (50%; bezogen auf eingesetztes
Trifluorethanol)
Kp: 48 bis 50°C bei 10 mbar
1H-NMR: 4,33 ppm (Multiplett, CH2)
13C-NMR: 58,95 ppm (Quartett, CH2),
123,29 ppm (Quartett, CF3)
19F-NMR: -79,19 ppm (Triplett, CF3)Bis- [trifluoroethyl] sulfite:
Yield: 36.8 g (50%; based on the trifluoroethanol used)
Kp: 48 to 50 ° C at 10 mbar
1 H-NMR: 4.33 ppm (multiplet, CH 2 )
13 C-NMR: 58.95 ppm (quartet, CH 2 ),
123.29 ppm (quartet, CF 3 )
19 F NMR: -79.19 ppm (triplet, CF 3 )
Claims (4)
R1O-S(O)-OR2
worin R1 und R2 gleich oder verschieden sein können und je weils für durch mindestens 1 Fluoratom substituiertes C1-C3- Alkyl stehen, wobei man SOCl2 mit den Alkoholen R1OH und R2OH in Abwesenheit eines Säurefängers umsetzt.1. Process for the preparation of compounds of general formula (I)
R 1 OS (O) -OR 2
wherein R 1 and R 2 may be the same or different and each represent C 1 -C 3 alkyl substituted by at least 1 fluorine atom, SOCl 2 being reacted with the alcohols R 1 OH and R 2 OH in the absence of an acid scavenger.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999156364 DE19956364A1 (en) | 1999-11-24 | 1999-11-24 | Preparation of (a)symmetric bis(lower fluoroalkyl) sulfite esters, useful as solvent in lithium battery electrolyte, comprises reacting thionyl chloride and fluoroalkanol(s) in absence of acid acceptor |
| AU17027/01A AU1702701A (en) | 1999-11-24 | 2000-11-17 | Production of fluoroalkyl sulfates |
| PCT/EP2000/011457 WO2001038296A1 (en) | 1999-11-24 | 2000-11-17 | Production of fluoroalkyl sulfates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999156364 DE19956364A1 (en) | 1999-11-24 | 1999-11-24 | Preparation of (a)symmetric bis(lower fluoroalkyl) sulfite esters, useful as solvent in lithium battery electrolyte, comprises reacting thionyl chloride and fluoroalkanol(s) in absence of acid acceptor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19956364A1 true DE19956364A1 (en) | 2001-05-31 |
Family
ID=7930064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1999156364 Withdrawn DE19956364A1 (en) | 1999-11-24 | 1999-11-24 | Preparation of (a)symmetric bis(lower fluoroalkyl) sulfite esters, useful as solvent in lithium battery electrolyte, comprises reacting thionyl chloride and fluoroalkanol(s) in absence of acid acceptor |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU1702701A (en) |
| DE (1) | DE19956364A1 (en) |
| WO (1) | WO2001038296A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021055560A1 (en) * | 2019-09-17 | 2021-03-25 | E3Trigen, Inc. | Fluorinated electrolyte additives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE487253C (en) * | 1927-07-06 | 1929-12-12 | Walter Voss Dr | Process for the preparation of dialkyl sulfites |
| US2553721A (en) * | 1947-08-20 | 1951-05-22 | Pittsburgh Plate Glass Co | Process of producing sulfite esters |
| US2968667A (en) * | 1956-12-10 | 1961-01-17 | Pennsalt Chemicals Corp | Bis (perfluoroalkylmethyl) sulfites and their preparation |
-
1999
- 1999-11-24 DE DE1999156364 patent/DE19956364A1/en not_active Withdrawn
-
2000
- 2000-11-17 AU AU17027/01A patent/AU1702701A/en not_active Abandoned
- 2000-11-17 WO PCT/EP2000/011457 patent/WO2001038296A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001038296A1 (en) | 2001-05-31 |
| AU1702701A (en) | 2001-06-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |