Method of preparing polyfluoroallyloxycompounds

专利摘要:
<P> THE INVENTION RELATES TO THE CHEMISTRY OF FLUORINATED ORGANIC COMPOUNDS. </ P> <P> IT CONCERNS A NEW COMPOUND, PERFLUOROALLYL FLUOROSULFATE, WHICH IS PREPARED BY REACTING SO AND HEXAFLUOROPROPENE. </ P> P> <P> USE FOR THE SYNTHESIS OF POLYFLUOROALLYLOXYL COMPOUNDS. </ P>
公开号:SU795452A3
申请号:SU772550560
申请日:1977-12-02
公开日:1981-01-07
发明作者:Джордж Креспан Карл
申请人:Е.И.Дюпон Де Немур Энд Компани(Фирма)；
IPC主号:

专利说明:

The invention relates to a process for the preparation of new polyfluoroallyloxy compounds of general form. (F (-CF-0- -4 I) ZX B where X is C1 or F; W and Z are each HO-F, and together-CF-I, D - a group of the formula. -k. "L-" x / CF2 CFCF2-0 or RP, gdf RF - linear or branched perfluoroalkyl with 1-10 carbon atoms, interrupted not more than every second carbon atom with 1-4 oxygen atoms with function national groups in the form, COF, C02H, C02 R C1, DCF2Cr Cfi or OCFjR, where CH or E. -C.CF,, CFjCl, or CF (Gfe where R has the specific values of D h E together with the carbon atom form five - or six-member ring, i.e., a perfluoroalkylene chain with 4 or 5 members, interrupted by 1-2 oxygen atoms and having substituents in the form of CFo - groups or groups of the formula LC G -. F or CF3, which are used as monomers for polymeric materials. Similar in structure unsaturated compounds are used as monomers for various polymeric materials 1} The purpose of the invention is to obtain new compounds of the form. Copolymers on the basis of these polyfluoroallyillic compounds have lower melting points than the corresponding polyfluoroolefins and, therefore, they are easier to form into the desired products, LIA. Based on them, you can get colored Fluorocarbon polymers as well as polymers capable of ion exchange.
The method for producing the compounds according to the invention is based on the known reaction of obtaining unsaturated oxygen-containing compounds by reacting the corresponding oxygen-containing compounds and alkali metal fluoride 2}
According to the invention, compounds of formula 1 are prepared by reacting a carbonyl compound of formula
9
A - from - to (II)
where A is F, COCFj or RF, where Kp is a linear or branched perflator with 1-10 carbon atoms, interrupted no more often than through a second carbon atom 1-4 with oxygen atoms with functional groups in the form of S02.F, SO OCfjCHj, COF, Cl, OCF, CF CF, ji CQjR where or
B-F, CF-j, CFjCI, CFjCOjRS, where R has the above values, or CFjiORp, where Rp has the above values;
A and B together with a carbon atom form a five- or six-membered ring, i.e. denotes from perfluoro the ketene chain with 4 or 5 members, substituted or not substituted by trifluoromethyl groups,
with metal fluoride of the general formula MF, where M is K, RB, C S or RN, where R is the same or different, is alkyl with 1-6 carbon atoms, with (-20) - (+60) C. the reaction mass is subjected to interaction with perfluoro-araline compound of the general formula
Z i
CF C-CF (II
III
W x
where X, W, Z have the indicated values;
C1 or
at (-20) - (+ 80) С.
Preferably, the process is conducted in an anhydrous proton polar organic solvent.
According to the invention, a polyfluoroalcoholate anion is preliminarily prepared by adding a carbonyl compound to a stirred mixture of metal fluoride in an appropriate protic solvent. The end of the formation of the anion is usually set according to the degree of dissolution of the metal fluoride.
The presence of a twofold molar excess of metal fluoride does not have a negative effect.
Due to the limited thermal stability of polyftbralcohols, they are usually obtained at (-20) (+ 60) C, better with external cooling to maintain the temperature from 0 to.
The time required to complete the formation of the polyfluoroalkohlor varies depending on the carbonyl component, but the best time is from 0.5 to 2 hours, and in each case it is determined by how quickly the reaction mixture becomes homogeneous.
Examples of proton polar solvents for the preparation of polyfluoroalcoholates and their subsequent reaction with polyfluoroallyl chloride or fluorosulfate are N, N-dimethylformamide (DMF)., Acetonitrile, NiN-dimethylacetamide (DMAC),} -butyrolactone, 1,2-dimethoxyethane, , 1- (2-methoxyethoxy) -2-methoxyethane (diglyme)., 2,5,8,11-tetraoxadodecane (triglyme), dioxane, sulfolane, nitrobenzene and benzonitrile. The best of these are DMF, diglyme, triglyme and acetonitrile. Equipment, reagents and solvents must be dried well before use, since the presence of water hydrolyzes polyfluoroalcoholic.
In the method according to the invention is used such fluorides metsshlov as potassium fluoride, rubidium, cesium fluoride and fluoride tetraalkylammonium (), for example tetraethylammonium fluoride RACs H) tetpabytila vvIOny fluoride (SN, NF, where R - identical or different, represent is alkyl with 1-6, better with 1-4 carbon atoms. It is better to use potassium fluoride because of its availability, economic advantage and ease of handling.
The polyfluorocarbonyl compounds used according to the method according to the invention are carboxylic acid ketones and fluorides and perfluorinated lactone-3, b-bis- (trifluoromethyl) -3,5,5,6-tetrafluoro-1, 4-dioxane-2- he. Ketones and lactone give branched products, and acid fluorides are predominantly primary fluorocarbon products, in which the new ester is located in the primary or secondary center.
To polyfluorinated ketones. Hexafluoroacetone, chloropentafluoroacetone, 1-3-dichlorotetrafluoroacetone, 1,1-difluoroethyl-2-oxopentafluoropropanesulfonate, dimethyltetrafluoroacetone-1, 3-dicarboxylate, 1,3-bis - (2-heptafluoropropoxymetrapphrasephrafluoroacetone, tetrafluoroacetone-1, 3-dicarboxylate, 1,3-bis - (2-heptafluoropropoxy) -etrafeftrapane-tetrafluoroacetone; .
Hexafluoro-2,3-butanedione is used in a special case (example 12), when the perfluoro alcohol formed at first reacts with perfluoroallyl fluorosulfonate and another 1 molar equivalent of hexafluoro-2,3-butadiene to form a mixture of two heterocyclic compounds. Polyfluorinated ACIDS fluorinated hydrides that can be used according to the invention are carbonyl fluoride, trifluoroacetyl fluoride, pentafluoropropionyl fluoride, heptafluorobutyroyl fluoride, nonafluoropentanoyl fluoride, tetrafluoridiglycol difluoride, etc. Ketone 1,1-difluoroethyl-2-oxopentafrpropanesulfonate (example 3) is a special example of the starting material, since it forms incitu and is a source of 2-oxopentafluoropropane sulfonyl fluoride, since the latter has not been improved. The preparation of polyfluoroalcoholate and its subsequent reaction with polyfluoroallyl chloride or fluorosulfate can be carried out sequentially without isolating intermediates in a glass device at atmospheric pressure, using the usual measures to eliminate moisture. Using cooling baths and low-temperature refrigerators (for example, with dry ice and acetone) to inhibit the reaction and facilitate the retention of volatile reagents and products. It is convenient to follow the evolution of the reaction by observing the occurrence of the precipitation of salt by gas-liquid separation chromatography (GHRH) and by the fluorine nuclear magnetic resonance (F NMR). Usually, the reaction mixture is cooled outside Od. O to 15 ° C during the addition of polyfluoroallyl chloride or fluoroacetate, then allowed to warm to 25-30 ° C during the remainder of the reaction. The time required to complete the reaction ranges from 1 to 24 hours, preferably from 2 to 4 hours. Typically, the reaction mixture is cooled outside for 5-45 minutes while adding polyfluoroallyl chloride or fluorosulfate, then it is stirred at room temperature for 2-3 hours. Products reactions are isolated by conventional means. In some cases, the reaction product is noticeably more volatile than a high boiling solvent (e.g., bp. Diglyme, DMF), and can be distilled into a trap / cooled to (-80fc by heating the reactor to 30-5 ° C under reduced pressure ( 1-200 mmHg.) The reaction mixture can also be separated into 5-10 times the volume of water, the insoluble bottom layer of the fluorinated product is separated, washed from the solvent with water, dried, and distilled off. In the examples given, the amount of compounds is given in parts by weight and ghyucentes, unless otherwise indicated. Example 1- (Heptafluoro-2-pro poxy) -1,1,3, 3-tetrafluoro-2-chloro-2-propene. (CFj) 2CO + CF CC1CP „C1 - (С F,), С FOCF, 6 2 16.6 g (0.10 mole) of hexafluoroacetone is distilled into a mixture of potassium fluoride (5.8 g; 0.01 mol) and 100 ml of 1- (2-methoxyethoxy) -2-methoxyethane (hereinafter referred to as diglyme) with stirring and a homogeneous solution is obtained. 25-30s and treated with 1,2-dichloro-1,1,3,3-tetrafluoropropene (18.3 g 0.10 mol). The mixture is stirred overnight, then poured into 500 ml of water. The bottom layer is washed with 250 ml of water, dried and distilled. 13 Og (0.039 mol; 39%) 1- (heptafluoro-2-propoxy) -1,1,3, 3-tetrafluoro-2-chloro-2-propene are obtained. bp 82-83 C, the structure of which is confirmed by the IR-I P-spectra. Found,%: C 21, A3; C1 10.89. Sbc F 0. Calculated,%: C 21.67; C1 10.66. Example 2. 1- (1,1,1,2,3,3. -Hexafluoro-3-chloro-2-propoxy) -pentafluoro-2-propene. A. Penta () Top-2-propenyl fluorosulfate (perfluoroallyl fluorosulfate). CFg- (JMFJ ((P2-S SOj-II - CF2 dF-CPgOSo F 0 -S02 Mixture of technical sour sulfur dioxide (10 ml) and 45 g (0.3 mol) of hexafluoropropene for "; dig in the Carius tube at liquid nitrogen, stirred well at 25 ° C, kept for 4 days at and, finally, heated on a steam bath for 6 hours. Of these two tubes, the 2,2- dioxane 3- (trifluoromethyl) -3,4,4 was obtained by distillation. trifluoro-1-oxa-2-thiacyclobutane (sulfone-2-hydroxy-2-trifluoromethyl-1, 2.2, trifluoroethanesulfonic acid), bp and 75 g (63%) of pentafluoro-2-propenyl fluorosulfate, t .Kip. 58-60 C. B. 1- (1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy) -pentafluoro-2-propene. CF CCCFj CI + KF + CF CFCF2 OS02 F-iCF CFOCFj CF CF2 A suspension of 5.80 g (0.01 mol) of potassium fluoride in 100 ml of diglyme is stirred at a cooling bath at the distillation of 18, 18 3 (0.10 mol) of lorpentafluoroacetone. After dissolving potassium fluoride, 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate is quickly added with cooling. The exothermic reaction that proceeds is followed by precipitation of the precipitate. The mixture was stirred at 25 ° C for 1 h, then the volatile components were sent to a trap cooled to -80 ° C by heating the reaction mixture at mm Hg. The volatile product is distilled from phosphorus pentoxide and 19.6 g (0.059 mol) of the desired product are obtained, b.p. 85-86 0. Yield 50%. Found,%: C 21.34; CI 10.21, CfcClF, 0. Calculated,%: C 21.67; C1 10.66. Froze 2- (1-penta L-2-propenyloxy) -hexafluoropropane-1-sulfonyl fluoride (2-perfluoro-allyloxypropan-1-sulfonyl fluoride) A. 2-Oxopentafluoropropanesulfonic acid, -t-SO CF, s, + CF CFJO4 CFjtC SO. OC, jHg + С 0: CFjCCF SOpH-tCPgCCtjCjHg Adding in drops of 12.8.g (0.16 mol) of sulfur trioxide to 29.0 g (0.165 mol) of 2-ETOXY-1,1,3,3,3 -pentafopropene causes an exothermic reaction. The black reaction mixture is distilled and 6.3 g (0.036 mol) (22% yield) of 2-ethoxy-1, 1,3,3,3-pentafluoropropene, identified by IR spectrum, and 20. 2 g (O , 078 mol) ethyl-2-oxopentafluoropropanesulfonate (conversion 49% yield 63%), bp 47-48 C / 12 mm Hg. The above reaction is repeated at O-5 ° C with sulfur trioxide (88 g 1, 1 mol) and 176 g (1.0 mol) of 2-etox l, 1, 3, 3, 3-pentafluoropropene. The colorless reaction mixture, which darkened on standing overnight, was distilled to give 28.6 g (0.16 mol) of 2-etoxy-1,1,3 3,3-pentafluoropropene in 16% yield and t .Kip. 4648 C, 145.1 g (0.57 mol) of ethyl 2-oxopentafluoropropanesulphonate with a co-version of 57%, yield of 68%, and so on. Boot 48 52 C / 12 mm Hg. and a higher boiling fraction, mainly consisting of 2-oxopentafluoropropane phosphate. The crude acid was again distilled at 31-82 s / 6.2 mm Hg. You move 35.6 g (0.16 mol) (convert 16 yield 19%) of pure acid. Found,%: C 15.95; OH 0.55; F, 55; S 13.89. C% H Fj 048. Calculated,%: C 15.80; OH 0.44; F k, 6S) - S T), 65. 25.6: g (0.10 mol of ethyl 2-oxopentafluoropropane sulfonate rtAnauanruTiainT lgms of the process of 17.1 G (o, 15 mol) of trifluoroacetic acid. The mixture is kept overnight, then it is heated with reverse distillation (BS)) a flask with a spiral. Fractionated distillation of the mixture at a temperature in the flask below 10 ° C gives a 2-oxopentafluoropropane acid (18.4 g, 0.081 mol, 81%). Boil., 6 mm Hg B. 1.1-Difluoroethyl -2-oxopentafluoropropanesulfonate, O. CF, C CFj SO, OH + CF2 CH CF cF, SOjjOCFv CHj, a metal tube with 23.8 g (0.1 mol) of 2-pxapentafluoropropane in it, is cooled below and introduced t in not 13 g (0.20 mol) of vinylidene fluoride (1,1-difluoro-ethane). The mixture is shaken and heated until it is kept at this temperature for 4 hours. Distillation of the liquid product gives 20.4 g (0.07 mol; 70% ) 1,1-difluoroethyl-2-oxopentafluoropropanesulfonate, bp 62-63 C / 50 mm Hg, cent. Found,%: C, 20.73; H, 1.03; F 452.2., Calculated,%: C 20.56 N, 1.03 F; 45.52. The same experiment, but using 0.8 mol, gives a product yield of 86%; bp Product mm Hg This substance is in. avoidance of damage is stored in polytetrafluoroethylene bottles, 2- (1-Pentafluoro-2-propenyloxy) hexafluoropropane-1-sulfonylfluoride. CPjCCF.jS02CICF, CHj-KP4CF, CPCF, OSQjP-CP-CPOCP, j, CP CF, + CHjCOF-KOSOjP. A suspension of 5.80 g (0, lo mol) of dry potassium fluoride in 100 ml of 2.5, 8,11-tetraoxadodecane (triglyme) is stirred and cooled while adding 29.2 g (0.1 mol) of I, α-difluoroethyl 2-oxopentafluoropropane. When almost all potassium fluoride is dissolved, at Ofc, 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate, prepared as in 2A, is added, and the resulting mixture is sewn at 20-26 seconds for 3 hours. Volatile components are removed distillation at a temperature in the flask of 25 C / lNW.rt.st. The distillate is washed with a cold solution of ammonium hydroxide, dried and distilled. 13.0 g (0.034 mol) of 2- (1-pentafluoro-2-propenyloxy) -hexafluoropropane-1-sulfonyl fluoride is obtained with a yield of 34%. Its boiling point is 47-48 ° C / / 60 MM DT.CT. Found,%: C 10.24; F 60, On; S 8.26. H FII "3 S Calculated,%: C 18, 59.98; S 8, and. In a similar reaction, as in Example 33, according to IR analysis, the emitted gases consist mainly of acetylfluoride and small amounts of hexaflupropane and sulphuryl fluoride. PREMIR 4. 4. 1-JJL, 3-bis (2-heptafluoropropoxy) -2-pentafluoropropoxy-pentafluoro-2-propene. A. 1,3-Bis (2-heptafluoropropoxy) -tetrafluoropropanone. 0 2 (CFa,) CO + KF + C1F2 C &amp; CF. CFOCFjC CFj, OCF (CF) 2 A mixture of 21 g (0.36 mol) of dry potassium fluoride, 150 ml of dry DMF 59.8.g (0.36 mol) of hexafluoroacetone and 35.8 g (0.18 mol) 1, 3-Dichlo tetrafluoroacetone is heated by reverse distillation (40-60 C) for 3 days. Distilling into a trap cooled to gives regenerated hexafluoroacetone (15.6 ml, 46%) and 63. liquids with a boil up. 30-145 ° C. The high boiling point substance is again distilled from sulfuric acid and 18.7 g (0.037 mol) of 1,3-bis (2-heptafluoropropoxy) tetrafluoropropanone are obtained (conversion of si 21%, hexafluoroacetan yield 39%), t .kip. 117-118s. Found%: 21.60 F 68.59. CAF ,, 0., Calculated,%: C 21.70; F 68.66. B. 1-1,3-bis (2-heptafluoropropoxy) -2-pentafluoropropoxy 3-pentafluoro-2-propene 9 (CF) .CFOCF2 C CFjOCF (CFj) j + KF: + CF- -CFCFjOSbjF- CF2 CFCF / OCFiCFj | , OCF (CF | Mixture of 20.0 g (0, 04 mol) 1,3-bis (2-heptafluoropropoxy) -tetrafluoropropanol, 100 ml of diglyme and 2.32 g (0.04 mol) of potassium fluoride are mixed and heated to 55c The two liquid phases and the solid become homogeneous and remain so during cooling. Then 10, O (0.043 mol) of perfluoroallyl fluorosulfur sulfate, prepared as in Example 2A, are quickly added at 10 ° C and the mixture is allowed to heat. A weakly exothermic reaction accompanied by sedimentation and The second liquid phase is stirred for 2 hours, then poured into 350 ml of water. The bottom layer is dabbed with 75 ml of water, dried over phosphorus dimetry, distilled and 16.1 g (L, 0024 mol) -, 3 -bis (2-heptafluoropropoxy) -2-pentaft | n opxy-pentafluoro-2-propene with a yield of 62%. Its boiling point is 6457 s / 25 mm Hg. Found: C 22.66; F 70.27. 24 O Calculated,%: C 22.24; F 70.35. EXAMPLE 5. 3- (1-Pentafluoro-2-propenyloxy) -tetrafluoropropionyl fluoride. A.Difluormalonyl difluoride, OCF2CF COF. .FC CFjCF 81 g (0.45 mol) of 3-methoxytetrafluoropropionyl fluoride was slowly added to 80 g (1.0 mol) of sulfur trioxide at 4 ° C and the resulting difluoromalonyl difluoride with a boiling point. -9 ° C is continuously distilled through a low-temperature column. Yield 58 g (0.40 mol), 90%. B. 3- (2-Pentafluoro-2-propenyloxy) tetrafluoropropionyl fluoride. 009 FCCF CP-t-KF + CF, jr CFCF, .OSQjF, CF..fij A mixture of 7.5 g (0.13 mol) of dry potassium fluoride to 100 ml of diglyme was stirred at and 18.5 g were distilled off (18 0.13 mol) of difluormalonyl difluoride from A. A. After 20 minutes, potassium fluoride dissolves almost completely and 29.9 g (0.13 mol) of perfluoroallyl fluorosulfate, prepared as in the example 2A. The mixture is stirred for 3 hours, then the volatile components are distilled off at the temperature in the flask. 32 ° C / 4.8 VW Hg Distillation of distillate gives 14.9 g (0.051 mol) of 3- (1-pentafluoro-2-propenyloxy) - etrafluoropropionyl fluoride, mp. 70-71 ° C, with a yield of 39% and a small amount of a high boiling substance. Found,%: C 24.56. C (, R about gCalculated,%: C 24.51. Example. PerFluoro-3.6, dioC-0 &amp; a) dichlorotetrafluorodihydrofuran, 157.8 g (3.9 mol) H40H, 312 g (1.97 mol) of potassium permanganate and 1500 ml of water are heated at boiling for 17 h. Fast steam distillation yields 10.6 g (3%) of dihydrofuran The reaction mixture is filtered and the filter cake is rubbed with 2x400 ml of water.
One solution is evaporated to 1500 ml, 300 ml of condensed sulfuric acid is processed in the cold and extracted extravagantly with ether for a day. The extracts are evaporated until the ester is released. 5 g (0.06 mol) of pyidine and 416.5 g (3.5 mol) of thionyl chloride are added to the crude verde diacid (279 g; yield up to 3%). The emitted gases are passed through the trap at 4 hours after the formation of gas weakens and the contents of the trap (10 ml) are returned to the flask. The mixture is then heated at the boil until gas evolution ceases. Distillation gives 215.2 g (61% of dihydrofuran) of terafluorodiglycol chloride, b.p. 94-97 0. B. Tetrafluoromethyl glycol difluoride
C1 C SRd OCRD i C1 - FC CRjOCF tV
A mixture of 215 g (0.885 mol) of tetrafluoride glycolyl dichloride 140.5 g (3.35 mol) of NaF and 1200 ml of anhydrous acetonitrile are stirred overnight, then distilled and the fraction collected at 35-79 C. Distillate is treated with 20 g of NenF and after distillation get 105 g of tetrafluorodigly of Clyldifluoride, bp. 32-33C. Processing 10 g NciF and distillation, give another 37.0 g of difluoride, so kip. 32-3.3 C. A total of 142 g are obtained (76%).
B. perfluoro-3,6-dioxanone-8-enoyl; hF
9 . FC C OCFjiCF + KF + CF CF CFgOCFj CFj
A mixture of 38.9 g (0.67 mol) KF, 141.5 g (0.67 mol) of Tetrafluorodiglycol difluoride a and 500 ml of dry diglyme is stirred for 30 minutes at 5 ° C; during this time, almost all of the KF is dissolved. Then quickly, 154.1 g (0.67 mol) of prefluoroallylfluorosulfate is added and the mixture is stirred at 0-5 ° C for 3 hours, at 25 ° C for another 2 hours and over night The volatiles are evaporated to the temperature of the reverse distillation of di. Glyme VW ° C / 3 mm Hg. Stripping of volatile materials yields 28.2 g (20%) of difluoroanhydride wild dyslot with b.p. 32-33 ° С and 125 g (52%) of monoacid fluoride.
PRI me R 7. 2- (Pentafluoro-2-propenyloxy) -tetrafluoroethanesulfonyl-fluoride.
FSOjCFj CF + KF + CF, i CFCF2 - FS02CF2.CF20CF2 CF CF.j,
A suspension of potassium fluoride (5.8 g, 0.10 mol) in 100 ml of diglyme is stirred and cooled while simultaneously adding 18.0 g (0.10 mol) of fluorosulfonyl difluoroacetylfluoride. The mixture is stirred at 20-30 ° C
within 1 min during this time, the KF is dissolved. It is then treated with 25.0 g (0.11 mol) of perfluoroallyl fluorosulfate, prepared as in Example 2A, for 5 minutes at 200 ° C and stirred for 2 hours. The volatile components are distilled into a trap cooled to, and Distillate is treated with 10 ml of concentrated sulfuric acid to remove diglyme. Get 19,9 (0.06 mol)
“2- (pentafluoro-2-propenyloxy) -tetrafluoroethanesulfonyl fluoride, bp.5556 C / 150 mm Hg Yield 60%.
Found: C, 18.35; F, 57.40; S 9.69.
5С5Р4оО., 5.
Calculated,%: C 18.19; F57.55j S 9.71.
Example8. 2 1-Pentafluoro-2-propenyloxy-tetrafluoroethanesulfo-nilfluoride.
RSO С F, С F + KF + C F .., С FC Fjj 050 F- RS02CF2CF2 0CF2 CF CF
Example 7 is repeated, but instead of diglyme, acetonitrile is taken as the solvent. The yield of the target product is 40-50%.
Example 9. 1- D .- (Pentafluoro-2-propenyloxy)} - hexafluoropropane-2-sulfonylfluoride J
FSCt.CF CbF + KF + CFj CFCF; j, OSO F -CF,
- FSOjCFCFjOCFj,,. .
A mixture of potassium fluoride (5.8 g, 0.10 mol) and 100 ml of diglyme was stirred at and 23.0 g (0.10 mol) of 2-fluorosulfonyltetrafluoropropionyl fluoride was added. The resulting solution was treated at 10 ° C with perfluoro-alkyl fluorosulfate, prepared as in Example 2A, and after the addition was complete, the mixture was stirred at 25 ° C for 3 hours, then poured into 500 ml of water. 25.7 (.0.068 mol) of pentafluoro-2-propenyloxy)} - hexafluoropropane-2-sulfonyl fluoride are obtained, b.p. 50 ° C / 60 mmHg, with a yield of 68%.
Found,%: C 18.70; F 60.9; S 8,08.
F ..
Calculated,%: C, 18.96; F, 59.98; S, Q.kk.
Example: 10, 2-D .- (l, 2,3,4,45-pentafluoro-2-diclobutenyloxy)} heterofluoroethanesulfonyl fluoride.
OSOaF
4-KF FCOCF.j602F
Ll-OCF CF eo F
A suspension of 5.8 g (0.10 mol) of potassium fluoride in 100 ml of diglyme is stirred and cooled to 15 ° C, then 18.0 g (0.10 mol) of Ltorsulfonyl difluoroacetylfluoride is added. The mixture is treated at 10-15 With 24.2 g ( 0.10 mol) 1- (1, 2.3. ", -Pentafluoro-2-diclobutenyl) fluorosulfate, stirred at 3 hours and poured into 500 ml of water; 24.0 g (0.07 mol) 2-tl - (1 2, 3, "," - pentafluoro-2-cyclobutenyloxy)) - tetrafluoroethanesulfonyl fluoride, bp. 62C / 100 mm Hg, with a yield of 70%. .
Found,%: C 21.38; S 9.44 Calculated,%: C 21.07; 5th, 37. Example 11. 2- (1-Pen1e1f or-2-propenyloxy) - 3,6-bis (trifto1 hetyl) -2,3,5, 5, b-pentafluoro-1,4-diox
 ) About About CF,
Fa
ABOUT,
CF
F
Cfi
CT -CFCFjOp
A mixture of 5.8 g (0.1 mol) of potassium fluoride and 100 ml of diglyme is treated at 25 ° C with 31.0 g (0.10 kül). 3,6-bis- (trifluoromethyl) -3.S 5,6-tetrafluoro-1, 4-dioxan-2-one, stirred for 1 hour, then treated with dropwise 23.0 g (0.10 mol) of perfluoro-methyl fluorosulfate obtained as in example 2A. The temperature of the exothermic reaction is maintained at 35-4 ° C. Next, the mixture is stirred overnight at and, after this, poured out in 500 ml of aqueous solution. 2- (1-pentafluoro-2-propenyloxy) -3 g of 6-bis (trifluoromethyl-2,3,5,5,6-pentafluoro-1, 4-dioxane are obtained in the form of a mixture of isomers, bp. 55-57 C / 60 mm Hg
Found,%: C 23.71-, F 6fe, 17.
SF FI% l
Calculated,%: C 23.50j F 66.07.
PRI m e p.l2. (Pentafluoro-, -2-propenyloxy)} 2,3,5,6-tetrakis (trifluoromethyl) -5-fluoro-1 / 4,7-trioxabicyclo 2,2,1-heptane and (pvntafluoro-2-propenyloxy) - tetrafluoroethyl-4-Xl (pentafluoro-2-propenyloxy) r2, 4,5-tris (trifluoromethyl) -5-fluoro-1,3-dioxolane.
Oh oh - / - X-dF

CPz CPj OCF2tF CF2

(CPH
CF-OCFiCF tF
(JF2 tFCr20
iF3
A suspension of 5.8 g (0.10 mol) of anhydrous Kgfi fluoride. in 100 ml of diglyme, it is stirred at and at this time 19.4 g (0.10 mol) of hexafluoro-2,3-butanedione are introduced. The mixture is stirred until almost complete dissolution of potassium fluoride, and then rapidly treated with 23.0 g (0.10) of perfluoroallyl fluorosulfate, prepared as in Example 2A, at 15 ° C. The mixture was stirred overnight at which time it was distilled. 3.0 g (O, 0055 mol) 2- {: 1-pentafluoro-2-propensh1oxy) | -2, 3,5,6-tetrakis- (trifluorometi) -5fluoro-1, 4,7-trioxabicyclo 2.2, Heptan (t.k.50-51 C / 15 mm Hg. yield 11%) contains one main component according to GLC. An analytical sample of the product is obtained by preparative gzh.
Found,%: C 24.57; F 63.60. From 04
Calculated,%: C 24.55} P63.55. A mixture of isomers 7, 2 g (0.01 mol) (pentaftop-2-propenyl) and tetrafluoroethyl 2-4- (1-pentafluoro-2-propenyloxy) -2,4,5-tris (trifluoromethyl) -5-fluoro- 1,3-dioxolane. Yield 21%.
Found.%: C 24.78; F 66.48.
7-4 24 4
Calculated,%: C 24.44; F 66.26.
PRI me R 13. Perfluoro-1,6-yois (2-propenyloxy) -hexane.
About About PC (CFj} CF + KP + CF2 CFCPiOSOj F-
- (CFj-CFCF, jOCP, CF2CP2), 2 + CF2 "
-CFCF20 (CF2) COF
Diglyme CF2-CFCFj, 0 (CF.j) 5COF + H2 -
SS
- eP2 CFCF20 (CF2) 5 -3/2. Diglyme
A mixture of 11.62 g (0.20 mol) of potassium fluoride with 200 ml of diglyme and 28.2 g (0.086
(I) mol) octafluoroaliphenyl difluoride
(PCR) was stirred for 1.5 hours. The mixture was kept while adding dropwise 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate,
45 obtained as in example 2A. After the addition is complete, the mixture is stirred for 30 minutes, then it is allowed to warm up and stirred for an additional 3 hours. Lower Boiling Fraction with so Kip. 84-8b / 20mm Hg represents 21.1 g (0.0355 mol) perfluoro-1, b-bis {2-propenyloxy) -hexane. Yield 37%. Found,%: C 24.43; F 70.38. C ° 2 Calculated,%: C 24.26; p70.35. The higher boiling fraction is a complex of 2: 17.9 (0.0155 mol) perfluoro-6- (2-propentoxy) -caproic acid with diglyme (16%) with a boiling point. 109-110 C / 5 mmHg formed by hydrolysis of pefluoro-b- (2-propenyloxy) -hexanoyl fluoride in aqueous solutions of diglyme. PRI me R 14. Methylperfluoro 3,6-dioxanone-8-enoate. CFj, C FC F C Fj OC Fj C F Bt with Fa CFCF2 OCF, CF A suspension of 42 g (1.0 mol) of sodium fluoride in 100 ml of methanol is stirred at and 114 g (0.317 mol) of acid fluoride is quickly added to it. After the addition is complete, the mixture is stirred overnight at 25 ° C, filtered and the precipitate washed with ether. Obtain 102 g (8b%) methylperfluoro-3, 6-dioxanone-8-enoate with so kip. 60-61 C / 20 mmHg, containing small amounts of impurities Repeated distillation yields a slightly more pure ester (1-2% of impurities according to this gas chromatography), i.e. p.b1-62C / 20 mmHg. Found,%: C 26,17; H 0.66; F 56.24. SvN-4R-ts04. Calculated,%: C 25.82; H 0.81; F 56.17. PRI me R 15. A. Bis (2-methoxy tetrafluoroethyl) -ketone. A mixture of 27.0 g (0.50 mol) of sodium methoxide, 56.0 g (0.62 mol) of dimethyl carbonate and 100 ml of dry tetrahydrofuran is stirred in a 350 ml tube under pressure of tetrafluoroethylene 1-3 atm. Tetrafluoroethyl is fed under pressure as it is consumed to absorb 110 g (1.1 mol. After the addition is completed, the reaction mixture is heated for 1 hour. After filtration and distillation, 87.6 (52%) 1,3,3,5 tetramethoxy octafluoropentane are obtained. b.p. 54 ° C / 0.3 mm Hg, 1.3605. B. Dimethyltetrafluoroacetone-1,3-di-carboxylate To 50 ml of concentrated sulfuric acid is added dropwise 33.6 g (0 , 10 mol) of tetraether. The mixture is heated at 70 ° C / 50 mm Hg to dispense volatile products, then distilled at about 50 ° C / 1 mm Hg. The more distant distallate is dispersed and 16.9 g are produced. (69%) dimethyltetrafluoroacetone-1, 3-dicarboxylate, bp 56 ° C / 2 mm Hg, p 1.3713 Dishyl ether is obtained in 82% yield. Dimethylperfluoro-3-alloxyglutaate CH OC CF2 COCH-H-C , .O (CH OC-CF2) 2 CFOCF2.CF C F2 To 27.3 G (O, 18 mol) of dry cesium fluoride, in a 100 ml of diglyme, 43.5 g (0.19 mol) (CF2COGCH3) 2 are added at and stirred for 1 hour, while 41.4 g (0.18 mol) of CF2 is added. CfCF2 0S02F and the mixture is stirred for another 3 hours. The reaction mass is poured into 1 liter of water, the lower layer is separated. After treatment with 20 ml of sulfuric acid and extraction with freon 113, 4.54 g (yield 7.2%) of the desired product is obtained, t. Bale 51.5 ° C / 0.1 mm Hg. Found,%: C 30.45; F (8.10; H 1.48. C-) o FIOCH 6 OtCalculated, C 30.32; F47.96; H 1, 53. Example 16. Perfluoro-3- (2-propoxy-2-methylethoxy) -propene. A mixture of 6.96 g (0.12 mol) of potassium fluoride, 150 ml of diglyme and 29.4 g (0.089 mol) of 2- (1 -heptafluoropropoxy) -tetrafluoropropionyl fluoride (dimer of hexafluoropropene oxide obtained by treatment with fluoride ion) is stirred for 1 h at 5 ° C. Then at 5 ° C, 27.6 g (0.12 mol) of perfluoroallyl fluorosulfate, prepared as in Example 2A, are added dropwise. Next, the mixture is stirred at during 3 h and at during the night. 25.2 g (0.052 mol) of perfluoro-3- (2-propoxy-2-methylethoxy) -propene / t. Boil. 62-63 C / 100 mm Hg Found: C 22.18; F 70.96 O2 Calculated,%: C 22.42; F 70.9. PRI me R 17. Perfluoro-1,3-bis (2-propenyloxy) propane. A mixture of 15.3 g (0.26 mol) of potassium fluoride, 200 ml of diglyme and 17.3 g (O, 12 mol) of difluoromalonyl difluoride, obtained as in Example 5A, is stirred at 15 minutes. 57.5 g (0.25 mol) of perfluoroellyl fluorosulfate are added at 45-10C over 45 minutes and the mixture is stirred at 5 h for 1 h, then at 25 ° C etae for 2 h. 12.0 g (0.027 mol) of perfluoro-1 is obtained. , 3-bis (2-propenyloxy) -propane, bp.88-90 C / 200 mm Hg
Found,%: C 24.67; F68.36.
CgH j OiCalculated,%: C 24.34; F 68.45
Example 18. Perfluoro-3- (butoxy) -propene.
A mixture of 7.5 g (0, 13 mol) of dry potassium fluoride, iOO ml of diglyme and 28.1 g (0.13 mol) of heptafluorobutyroyl fluoride (obtained from acid by treatment with sulfur tetrafluoride) was mixed for 30 minutes. Then, perfluoroallyl fluorosulfate is added dropwise. Get 30,3 g (0,083 mol) of perfluoro-3- (butoxy-propene. Yield 64%, BP. 8084 C.
From 23.20:: 72.80,
Found%
S-, O
Calculated,%: 22.97; 72.66,
Example19. Perfluoro-3-foTyloxy) -propene.
A mixture of 5.8 g (O, 10 mol) of potassium fluoride, 150 ml of diglyme and 25.0 g (0.06 mol) of pentadecofluorooctanoyl fluoride obtained from technical perfluoroacrylic acid with sulfur tetrafluoride is stirred at 5 ° C for 1 hour. Then 23.0 g are added dropwise (0.10 mol of perfluoroallyl fluorosulfate, the mixture is stirred at 5 ° C for 4 hours and at 25 ° C for another 3 hours. 27.1 g (0.048 mol) of perfluoro-3- (octyloxy) are obtained propene. Yield 80%, bp 69-70 C / / 20 mmHg
Found,%: C 22.99; F 73,
.
Calculated,%: 23.34; F 73.8if.
Example 20. 2-Trifluoromethoxypentafluoropropene (perfluoro-methyl methyl ether.
A mixture of 18.0 g (0.27 mol) of carbonyl fluoride, 38.0 g (0.25 mol) of cesium fluoride and 300 ml of dry diglyme is stirred at (-20) - (-10) C for 2 h, then the mixture is held at -10 ° C or lower, and 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate is added. The mixture was stirred at -10 ° C for 2 hours, for 2 hours, then at 25 ° C overnight. Obtain 3.2 g (2.0 ml at -80 ° C, 0.014 mol, 7%) of the target product, so kip. 11-12 ° C.
Example21. Perfluoro-6- (2-propenyloxy) -caproic acid and its methyl ester.
A mixture of 11.7 g (0.20 mol), 250 ml of diglyme and 58.8 g (0.20 mol) of octafluoroelipollyldifluoride (PCR) was stirred for 30 minutes. The mixture was kept while adding dropwise 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate (Example 2A). After the addition is complete, the mixture is stirred at 0-5 ° C for 2 hours, then allowed to warm up to i25c and stirred for another 4 hours. 13.6 g (0.023 mol) perfluoro1,6-bis (2-propenyloxy) -hexane are obtained. (example 13, yield 23%), t. kip 61 C / 6 mmHg and 2: 1 complex perfluoro-6- (2-propenyloxy) -caproic acid with diglyme (Example 13; 52, V g, 0.109 mol, yield 54.5%), bp .8284 ° C / 0, 8 mm Hg
The diglym complex of the higher boiling fraction is distilled off with concentrated sulfuric acid (40 ml) and
0 get perfluoro-6- (2-propenyloxy) -caproic acid containing 12% of its methyl ester.
Example 22. Perfluoro-6- (2-propenyloxy) -caproic acid.
five
Lead the reaction as in example 21. Get the same two products as in example 21, the Fraction with so Kip. 45-53 C / / 6 mm Hg cleaned from diglyme with water and get crude perfluoro-1, 6-bis (2-propenyloxy) -hexane
0 (9.5 g, 0.01 P mole, yield 16%).
The higher boiling complex pertopf6- (2-propenyloxy) -caproic acid with diglyme is dissolved in 50 ml of 1,1,2-trichloro-1,2,2-trifluoro 5 ethylene, extracted with 50 and 25 ml of concentrated sulfuric acid. 42.2 g (O, 098 mol) of pure perfluoro-6- (2-propenyloxy) -caproic acid are obtained, b.p. mmHg. You move 49%.
Example 23. To a suspension of 58.1 (1.0 mol) calcined KF in 1400 ml of dry diglyme is quickly added with stirring at 333 g (0.67
5 mol) of a fluorinated trimer of hexafluoropropylene oxide. The two-phase system is stirred for 2 hours at 25.degree. The reaction mixture is stirring. at 5-10 ° C, 230 g (1.0 mol) of perfluoro-alkyl fluorosulfate is added to it
0 and stirred for an additional 2.5 hours, then left overnight at. In the course of distillation, water is obtained as the main fractions of the polyfluoroallyloxy compound and the methoxyproduct 5 with a bp. 55-71s / 20 mmHg and 140 g of crude with t. Kip. about 101-104 ° C / 20 mm Hg Re-distillation yields 80 g of a crude methoxy derivative with a bp. 81-8bs / 80mm
0 Hg and 33 g (8%) of the desired polyfluoro-alloxy compound with a bp 9495 C / 80 mm Hg.
Found%: C 22.50, F 71.78.
44
calculated% 22.24; F 70.36.

权利要求:
Claims (2)
[1]
Invention Formula
1, method of producing polyfluoroallyloxy compound of the general formula
0
D
W
I
(1P-0-C-ft
(I) i ii
L x e
where X is t1 or F; W and Z are each separately-F, a together- 0 is a group of the formula
CF,
 one "
-iv
f t or Rr, where RF linear or branched perfluoroalkyl with 1-10 carbon volumes, the chain of which closes no more often than every second carbon atom with 1-4 oxygen atoms with functional groups
in the form of SO, F, COF, COOH, COOK, -C1, OCFaCF-CFj or OCF2 R, where or С Н;
E-F, CF,, CF COOR, where R is as defined above, or RfOCF (G) i;
O and E together with the carbon atom form a five or six membered ring, i.e. denote a perfluoroalkylene chain with 4-5 members, which is mo. can be interrupted by 1-2 oxygen atoms and has substituents in the form of CF “groups or groups of the formula
dF dF:
G - F or CFJ, differing from the fact that the carbonyl compound of the formula
ABOUT
A - (; - in
I. Ig
where A is F, COCFj or Rp, where R is a linear or branched perfluoroalkyl with 1-10 carbon atoms, the chain of which is interrupted not more often than through every second carbon atom with 1-4 oxygen atoms with functional groups in
S020CF2, CH ,, COF, Cl OCF CF CF where CH, or CjHy;
B-F, CF, CF, jCl. -CFiCOjR, G R has the above values, CFjORJr, where Rp is the above
value;
A and B together with a carbon atom form a five or six membered ring, i.e. designate a perfluoroalkylene chain with 4-5 members, substituted or unsubstituted with trifluoromethyl
5 groups, with Methyl fluoride of the general formula MF, where H - K, Rb.Cs or R4.N, where R is the same or different, are C-C-Shkil, at (-20) - (+ 60) ® C. the resulting reaction mass is subjected to interaction
with a perpendicular compound of the general formula
Z I "RS-CP
I J I WAY
where X, W, Z-have the above values;
a-C1 or - SOjF, d at a temperature of (-20) - (80) C.
[2]
2. A method according to claim 1, characterized in that the process is carried out in an anhydrous proton polar organic solvent medium.
Sources of information taken into account in the examination
1. Patent SFRY 32718, CL.39-21, published. 04/30/74.
2.M.E. Redwood, C.I., WiIis. Fully fluorinated alkylene oxides Canad Journ. Chem ,, 45, 1967, p. 389.

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同族专利:

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公开号 | 公开日

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BR7708025A|1978-08-08|

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JPS5896630A|1983-06-08|

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MX147703A|1983-01-06|

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NL7713275A|1978-06-06|

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JPS5382713A|1978-07-21|

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FR2478625A1|1981-09-25|

---

IL53504D0|1978-03-10|

---

ZA777158B|1978-09-27|

---

GB1571356A|1980-07-16|

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IT1089314B|1985-06-18|

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JPS5762249A|1982-04-15|

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SE7712836L|1978-06-03|

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JPS6314707B2|1988-04-01|

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IL62812D0|1981-07-31|

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BE861430A|1978-06-02|

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JPS6345737B2|1988-09-12|

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JPS5891708A|1983-05-31|

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FR2478625B1|1983-12-23|

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FR2390430A1|1978-12-08|

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NZ185830A|1980-05-08|

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JPS5943936B2|1984-10-25|

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DE2760046C2|1988-07-21|

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DE2753886A1|1978-06-08|

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AU509777B2|1980-05-22|

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FR2388061A1|1978-11-17|

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IL53504A|1982-07-30|

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FR2388061B1|1984-01-13|

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AU3116977A|1979-06-07|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US74702976A| true| 1976-12-02|1976-12-02|

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