CA2049771A1 - Process for the preparation of tertiary alcohols containing fluorine - Google Patents
Process for the preparation of tertiary alcohols containing fluorineInfo
- Publication number
- CA2049771A1 CA2049771A1 CA002049771A CA2049771A CA2049771A1 CA 2049771 A1 CA2049771 A1 CA 2049771A1 CA 002049771 A CA002049771 A CA 002049771A CA 2049771 A CA2049771 A CA 2049771A CA 2049771 A1 CA2049771 A1 CA 2049771A1
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- Canada
- Prior art keywords
- mol
- free
- reaction
- isopropanol
- employed
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 8
- 239000011737 fluorine Substances 0.000 title claims abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000003509 tertiary alcohols Chemical class 0.000 title claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 perfluoroalkyl radical Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- 150000002976 peresters Chemical class 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 description 22
- 239000000203 mixture Substances 0.000 description 14
- 150000003333 secondary alcohols Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical group FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 229940060037 fluorine Drugs 0.000 description 5
- 235000019000 fluorine Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- 101001015038 Albizia kalkora Kunitz-type trypsin inhibitor alpha chain Proteins 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000228957 Ferula foetida Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241001237728 Precis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/38—Halogenated alcohols containing only fluorine as halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure Process for the preparation of tertiary alcohols containing fluorine In the process described tertiary fluoroalcohols of the following formula
Description
HOECHST AKTI~NGESELLSCHAFT HOE 90/F 910 Dr.GL-nu Werk Gendorf Process for the preparation of tertiary alcohols contain-ing fluoxine Description The invention relates to a process for the preparation of tertiary alcohols, containing fluorine, of the formula 1 below Rf-CH2-CH2-C-OH~ ( 1 ) in which R~ is a perfluoroalkyl radical having 4 to 20 carbon atoms, R1 is CH3 and R2 i6 CH3 or C2Hs.
US Patent 3,532,659 di~closes primary and secondary fluorine-containing alcohol~ of the following formula:
R'f-CH2-CH2-CH-OH
. R' in which R~ is a perfluoroalkyl radical having 5 to 13 carbon atoms and R' is an alkyl radical having 1 to 5 carbon atoms or is H; compare column 2, equation (c) in connection with column 1, lines 27 to 30 and Example 17.
The primary alcohols containing fluorine are prepared by reacting perfluoroalkylethylenes of the formula R'~-CH=CH2 in which R'~ has the meaning indicated above, with the primary alcohol methanol, and the secondary alcohols containing fluorine are prepared by reacting the said perfluoroalkylethylenes with an aliphatic, primary alcohol belonging to the group comprising ethanol, propanol, butanol or pentanol. The reaction is carried out in the presence of a free-radical initiator and using a varyingly large excess of primary alcohol. Particularly - 2 - ~049~771 in respect of yield, this process leaves something to be desired.
It has now been found that the reaction of perfluoro-alkylethylenes with an aliphatic alcohol results in fluoroalcohols (tertiary fluoroalcohols) in a high yield if æecondaxy alcohols are employed as the aliphatic alcohol (in contrast with the known process, in which only primary aliphatic alcohols are employed, resulting in primary and secondary fluoroalcohols), specifically isopropyl alcohol or secondary butyl alcohol.
The process according to the invention for the preparation of the tertiary alcohols, containing fluor-ine, mentioned initially, therefore comprises reacting perfluoroalkylethylenes of the formula 2 below R~-CH=CH2 (2) in which Rf has the meaning indicated, with excess iso-propanol or excess sec.-butanol in the presence of free-radical initiators.
The process according to the invention is therefore based on equations 1 and 2 below, the secondary starting alcohol being isopropanol in equation 1 and secondary butanol in equation 2:
Equation 1:
R~-CH~CH2 + CH-OH -- > Rf-CH2-C~2-C-O~
Equation 2:
1 2CH3 CH2C~3 Rf-CH=CH2 + CH-OH - > Rf-CH2-CH2-C-OH
_ 3 _ Z04~
Surprisingly, the two reactions proceed virtually quanti-tatively, as a result of which the desired tertiary fluoroalcohol is obtained in a high yield. It could not have been expected that a perfluoroalkylethylene would react so smoothly with preci~ely the secondary alcohols in question.
Isopropanol and sec.-butyl alcohol thus constitute the first reactant, and perfluoroalkylethylenes of the formula Rs-CH=CH2 constitute the second reactant, of the process according to the invention.
The perfluoroalkyl group Rr having 4 to 20 carbon atoms, preferably 6 to 16 carbon atoms, can be linear or branched, saturated or unsaturated (preferably having 1 to 3 double bonds), saturated groups being preferred. In the case of a branched perfluoroalkyl group the termin-ally branched group iB preferred. ~he perfluoroalkyl radical is often a mixture of perfluoroalkyl having the said number of carbon atoms, namely 4 to 20 carbon atoms (C4F8 to C20F4l), preferably 6 to 16 carbon atoms (C6Fl3 to Cl6F33), or having 6 to 12 carbon atoms ~C6Fl3 to C12F25~.
The secondary alcohol reactant is employed in excess, i.e. in an amount of such an excess that the perfluoro-alkylethylene reactant i5 thoroughly dissolved. It has been found that, in the absence of excess ~econdary alcohol, side reactions take place and side products are thus formed. The excess amount of secondary alcohol in compari~on with the perfluoroalkylethylene is not criti-cal and is determined more by economic considerations. In general, at least 3 mol of secondary alcohol, preferably 5 to 20 mol of secondary alcohol, will be employed for 1 mol of perfluoroalkylethylene.
Furthermore the reaction according to the invention is carried out in the presence of an initiator which forms free radicals (free-radical initiator). The amount of free-radical initiator can be varied within wide limits.
- 4 - ~049~7~
It depends particularly on the capacity for decompogition by heat (half-life) of the initiator compound and on the ~tability ~lifetLme) of ~he free radicals formed, and i8, as a rule, O.0005 to 0.1 mol per mol of perfluoroalkyl-ethylene, preferably 0.001 to O.OS mol per mol of per-fluoroalkylethylene. The nature of the free-radical initiator is not critical. Thus it i8 possible to employ inorganic or organic initiators. As a rule, compounds which exhibit advantageouE decomposition phenomena under the action of heat and provide reactive free radicals will be selected. Peroxo-acids, peroxoborates, peroxo-carbonates, peroxophosphates and peroxodisulfates may be mentioned a6 representatives of inorganic free-radical initiators. The organic peroxides (for example dial~yl peroxides, diacyl peroxides, per-acids and per-esters) and the azo compounds may be mentioned as representatives of organic free-radical initiators. Organic free-radical initiators are preferred. The following organic peroxides may be mentioned individually: di-tert.-butyl peroxide, tert.-butyl hydroperoxide, tert.-butyl perbenzoate, benzoyl peroxide, diacetyl peroxide and lauroyl peroxide.
~he following azo compounds may be mentioned individu-ally:azobisisobutyronitrile,2,2'-azobis(2-methylbutyro-nitrile),2,2'-azobis(2,4-dimethylvaleronitrile),azobis-isobutyramidine and 4,4'-azobis(4-cyanopentanoic acid~.
The reaction according to the invention i8 carried out without using a separate solvent and in an essentially anhydrous medium. The presence of a small amount of water, i.e. water up to about 5% by weight, relative to the total weight of R~-CH=CH~ product, secondary alcohol and free-radical initiator does not, in general, cause problems, 80 that, for example, it is also pos6ible to emplby technical isopropanol. The reaction temperature is advantageously within the range from 50 to 160C, prefer-ably sa to 14Q~C. At a temperature below 50C th~ reac-tion only takes place very slowly, and at over 160C very high pressures build up. It is self-explanatory that the free-radical initiator employed is one having a - 5 ~ 771.
decomposition temperature within the temperature range mentioned, which applies to many of the customary free-radical initiators, which al60 have an acceptable half-life. The free-radical initiator will therefore be S advantageou~ly matched to the reaction temperature. Since the boiling point of isopropanol is 80C and that of secondary butanol is 100C, the reaction will be carried out under atmospheric or superatmo6pheric pressure, depending on the free-radical initiator employed. The reaction can also be carried out continuously or batch-wise. The end of the reaction has been reached when no more or virtually no more perfluoroalkylethylene is detected.
The preferred procedure for carrying out the process according to the invention will therefore be such that the secondary alcohol, isopropanol or sec.-butanol, the R~-CH=CH2 compound and the free-radical initiator are placed, in the amounts indicated, in a reaction vessel or autoclave, after which the reaction mixture i8 heated with stirring to the reaction temperature and i~ kept at this temperature until the end of the reaction. In another preferred embodiment of the process according to the invention the procedure will be to take only the secondary alcohol and the perfluoroalkylethylene product initially and to heat them to reaction temperature, i.e.
to at least the temperature at which the chosen initiator compound decomposes. When this temperature has been established the initiator compound, in the form of a solution of varying dilution in the secondary alcohol employed, i~ metered in in the amount in which it is consumed in the reaction mixture. This procedure will be preferred from considerations o safety in operation under certain circumstances, because it ensures a lower steady-state concentration of free radicals. The metering in of the solution of free-radical initiator is carried out continuously or in portions, for example by means of a metering pump. The reaction time of the reaction according to the invention depends above all on the - 6 - ;:0~77~L
free-radical initiator employed and on the reaction temperature, and is, as a rule, 3 to 15 hours.
The process according to the invention produces the desired tertiary fluoroalcohol in the form of a solution in the excess Recondary alcohol employed. Since the reaction to give the desired product takes place virtu-ally quantitatively and no appreciable byproducts are formed in the course of it, isolation of the tertiary fluoroalcohol from the solution mentioned is often not necessary at all; on the contrary, the tertiary fluoro-alcohol is already the desired product in this form. If its isolation is desired, the excess alcohol i6 simply removed by distillation. As a rule, any organic initiator compound still present will also be distilled off at the same time. The removal of initiator compound can also be achieved, for example, by wa~hing.
The process according to the invention has a number of advantages. The desired tertiary fluoroalcohol is obtained in a high yield and a high state of purity. ~he process i8 simple and economical. It thus represents an advantageous method for the conversion of perfluoroalkyl-ethylenes into tertiary fluoroalcohols. The tertiary fluoroalcohols obtained by the process according to the invention con titute novel, highly reactive fluorine compounds.
The invention will now be illustrated in greater detail by means of examples.
Example 1 Batch.
200.00 g (0.375 mol) of Rf-CH=CHz, Rf-= C6F13 to C12F25 338.00 g (5.630 mol) of isopropanol 3.60 g (0.015 mol) of benzoyl peroxide Molar rakio: 1 to 15 to G.04.
- 7 ~ 3~771 Procedure:
The R-CH=CHz product and the isopropanol were plac~d in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. After being flushed with nitrogen, the mixture was heated with stirring to 80C (boiling point of isopropanol). The benzoyl peroxide, dissolved in 100 g of isopropanol, was added dropwise with ~tirring to the mixture thus heated over a time of 7 hours. When the slow addition of benzoyl peroxide was complete, the mixture was kept for a further hour at 80C, with stirring, in order to complete the - reaction. Here, and in all the further examples, the isolation, for the purposes of determininq the yield, of the tertiary fluoroalcohol formed was effected by di~-tilling off the excess secondary alcohol and, if approp-riate, washing once or more often with water or with a slightly alkaline aqueou~ solution.
Result:
The tertiary fluoroalcohol obtained was, at room tempera-ture, a colorless, crystalline, waxy product. Yield: 94 of theory.
Example 2 Batch:
50.00 g (0.112 mol) of CaFl7-cH=cH2 134.70 g (2.240 mol) of isopropanol 0.25 g (0.0017 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 20 to 0.015.
Procedure:
The C8F17-CH-CH2 product, the isopropanol and the peroxide were placed in an autoclave equipped with a stirrer.
After being flushed with nitrogen, the mixture was heated to 140C with stirring and was kept at this temperature for 5 hours, with stirring. The pressure in the autoclave was 0.8 MPa. After the reaction time mentioned, all the perfluoroalkylethylene had reacted.
- 8 - ~ ~ ~9~71 Result:
The tertiary fluoroalcohol obtained was, at room tempera-ture, a colorless, crystalline, waxy product. Yield: 96 of theory.
Example 3 Batch:
50.00 g ~0.094 mol) of Rf-CH=CH2, R = C6F~3 to C12F25 32.40 g (0.540 mol) of technical isopropanol 1.20 g (0.0086 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 5 to 0.08.
Procedure:
The Rf-CH=CH2 product, the isopropanol and the peroxide were placed in the autoclave of Ex~mple 2. After being flushed with nitrogen, the mixture was heated with stirring to 125C and was kept at this temperature for 10 hours, with stirring. The pres~ure in the autoclave was 0.5 MPa. Since the reaction was still not complete after this reaction time, the mixture was kept at the tempera-ture of 140C for a further 3 hours, with ~tirring.
Result:
As in Example 2, with a yield of 89% of theory.
Example 4 Batch:
200.00 g (O.375 mol) of Rf-CH=CH2, R~ = C6F~3 to C12F25 338.00 g (5.630 mol) of isopropanol 3.84 g (0.0168 mol) of ammonium peroxodisulfate Molar ratio: 1 to 15 to 0.045.
Procedure:
As in Example 1, with the difference that the ammonium peroxodisulfate, dissolved in 5 g of water and 5 g of isopropanol, was added dropwise over a tLme of 5 hours to the mixture, heated at 80C, and the mixture was then 9 20~97~1 kept at 80C for a further 2 hours in order to complete the reaction.
Result:
As in Example 1, with a yield of 90~ of theory.
Example 5 Batch:
200.00 g (0.375 mol) of Rf-CH=CH2, R~ = C6F13 to C12Fz5 338.00 g (5.630 mol) of isopropanol 1.08 g (0.0056 mol) of azobi~isobutyronitrile Molar ratio: 1 to 15 to 0.015.
Procedure:
As in Example 1, with the difference that the azobisiso-butyronitrile, dissolved in 80 g of isopropanol, was added dropwise over a time of 7 hours to the mixture, heated at 80C, and the mixture was then kept at 80DC for a further 5 hours in order to complete the reaction.
Result:
As in Example 1, with a yield of 93~ of theory.
Example 6 Batch:
200.00 g (0.375 mol) of Rf-CH=CH2, Rf = C6F13 to C~F25 338.00 g (5.630 mol) of isopropanol 0.27 g (0.0019 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 15 to 0.005.
Procedure:
The Rr-CH=CH2 product and the isopropanol were placed in the autoclave of Example 2. After being flushed with nitrogen, the mixture was heated with stirring to 135C.
The di-tert.-butyl peroxide, dissolved in 80 g of iso-propanol, was added dropwise, with stirring, over a time of 4 hours by means of a metering pump to the mixture ~ 49t~71 thus heated. The pressure in the au~oclave was 0.7 MPa.
When the 810w addition of peroxide was complete, the mixture was kept at 140C for a further 5 hours, with stirring, in order to complete the reaction.
Result:
As in Example 2, with a yield of 95% of theory.
US Patent 3,532,659 di~closes primary and secondary fluorine-containing alcohol~ of the following formula:
R'f-CH2-CH2-CH-OH
. R' in which R~ is a perfluoroalkyl radical having 5 to 13 carbon atoms and R' is an alkyl radical having 1 to 5 carbon atoms or is H; compare column 2, equation (c) in connection with column 1, lines 27 to 30 and Example 17.
The primary alcohols containing fluorine are prepared by reacting perfluoroalkylethylenes of the formula R'~-CH=CH2 in which R'~ has the meaning indicated above, with the primary alcohol methanol, and the secondary alcohols containing fluorine are prepared by reacting the said perfluoroalkylethylenes with an aliphatic, primary alcohol belonging to the group comprising ethanol, propanol, butanol or pentanol. The reaction is carried out in the presence of a free-radical initiator and using a varyingly large excess of primary alcohol. Particularly - 2 - ~049~771 in respect of yield, this process leaves something to be desired.
It has now been found that the reaction of perfluoro-alkylethylenes with an aliphatic alcohol results in fluoroalcohols (tertiary fluoroalcohols) in a high yield if æecondaxy alcohols are employed as the aliphatic alcohol (in contrast with the known process, in which only primary aliphatic alcohols are employed, resulting in primary and secondary fluoroalcohols), specifically isopropyl alcohol or secondary butyl alcohol.
The process according to the invention for the preparation of the tertiary alcohols, containing fluor-ine, mentioned initially, therefore comprises reacting perfluoroalkylethylenes of the formula 2 below R~-CH=CH2 (2) in which Rf has the meaning indicated, with excess iso-propanol or excess sec.-butanol in the presence of free-radical initiators.
The process according to the invention is therefore based on equations 1 and 2 below, the secondary starting alcohol being isopropanol in equation 1 and secondary butanol in equation 2:
Equation 1:
R~-CH~CH2 + CH-OH -- > Rf-CH2-C~2-C-O~
Equation 2:
1 2CH3 CH2C~3 Rf-CH=CH2 + CH-OH - > Rf-CH2-CH2-C-OH
_ 3 _ Z04~
Surprisingly, the two reactions proceed virtually quanti-tatively, as a result of which the desired tertiary fluoroalcohol is obtained in a high yield. It could not have been expected that a perfluoroalkylethylene would react so smoothly with preci~ely the secondary alcohols in question.
Isopropanol and sec.-butyl alcohol thus constitute the first reactant, and perfluoroalkylethylenes of the formula Rs-CH=CH2 constitute the second reactant, of the process according to the invention.
The perfluoroalkyl group Rr having 4 to 20 carbon atoms, preferably 6 to 16 carbon atoms, can be linear or branched, saturated or unsaturated (preferably having 1 to 3 double bonds), saturated groups being preferred. In the case of a branched perfluoroalkyl group the termin-ally branched group iB preferred. ~he perfluoroalkyl radical is often a mixture of perfluoroalkyl having the said number of carbon atoms, namely 4 to 20 carbon atoms (C4F8 to C20F4l), preferably 6 to 16 carbon atoms (C6Fl3 to Cl6F33), or having 6 to 12 carbon atoms ~C6Fl3 to C12F25~.
The secondary alcohol reactant is employed in excess, i.e. in an amount of such an excess that the perfluoro-alkylethylene reactant i5 thoroughly dissolved. It has been found that, in the absence of excess ~econdary alcohol, side reactions take place and side products are thus formed. The excess amount of secondary alcohol in compari~on with the perfluoroalkylethylene is not criti-cal and is determined more by economic considerations. In general, at least 3 mol of secondary alcohol, preferably 5 to 20 mol of secondary alcohol, will be employed for 1 mol of perfluoroalkylethylene.
Furthermore the reaction according to the invention is carried out in the presence of an initiator which forms free radicals (free-radical initiator). The amount of free-radical initiator can be varied within wide limits.
- 4 - ~049~7~
It depends particularly on the capacity for decompogition by heat (half-life) of the initiator compound and on the ~tability ~lifetLme) of ~he free radicals formed, and i8, as a rule, O.0005 to 0.1 mol per mol of perfluoroalkyl-ethylene, preferably 0.001 to O.OS mol per mol of per-fluoroalkylethylene. The nature of the free-radical initiator is not critical. Thus it i8 possible to employ inorganic or organic initiators. As a rule, compounds which exhibit advantageouE decomposition phenomena under the action of heat and provide reactive free radicals will be selected. Peroxo-acids, peroxoborates, peroxo-carbonates, peroxophosphates and peroxodisulfates may be mentioned a6 representatives of inorganic free-radical initiators. The organic peroxides (for example dial~yl peroxides, diacyl peroxides, per-acids and per-esters) and the azo compounds may be mentioned as representatives of organic free-radical initiators. Organic free-radical initiators are preferred. The following organic peroxides may be mentioned individually: di-tert.-butyl peroxide, tert.-butyl hydroperoxide, tert.-butyl perbenzoate, benzoyl peroxide, diacetyl peroxide and lauroyl peroxide.
~he following azo compounds may be mentioned individu-ally:azobisisobutyronitrile,2,2'-azobis(2-methylbutyro-nitrile),2,2'-azobis(2,4-dimethylvaleronitrile),azobis-isobutyramidine and 4,4'-azobis(4-cyanopentanoic acid~.
The reaction according to the invention i8 carried out without using a separate solvent and in an essentially anhydrous medium. The presence of a small amount of water, i.e. water up to about 5% by weight, relative to the total weight of R~-CH=CH~ product, secondary alcohol and free-radical initiator does not, in general, cause problems, 80 that, for example, it is also pos6ible to emplby technical isopropanol. The reaction temperature is advantageously within the range from 50 to 160C, prefer-ably sa to 14Q~C. At a temperature below 50C th~ reac-tion only takes place very slowly, and at over 160C very high pressures build up. It is self-explanatory that the free-radical initiator employed is one having a - 5 ~ 771.
decomposition temperature within the temperature range mentioned, which applies to many of the customary free-radical initiators, which al60 have an acceptable half-life. The free-radical initiator will therefore be S advantageou~ly matched to the reaction temperature. Since the boiling point of isopropanol is 80C and that of secondary butanol is 100C, the reaction will be carried out under atmospheric or superatmo6pheric pressure, depending on the free-radical initiator employed. The reaction can also be carried out continuously or batch-wise. The end of the reaction has been reached when no more or virtually no more perfluoroalkylethylene is detected.
The preferred procedure for carrying out the process according to the invention will therefore be such that the secondary alcohol, isopropanol or sec.-butanol, the R~-CH=CH2 compound and the free-radical initiator are placed, in the amounts indicated, in a reaction vessel or autoclave, after which the reaction mixture i8 heated with stirring to the reaction temperature and i~ kept at this temperature until the end of the reaction. In another preferred embodiment of the process according to the invention the procedure will be to take only the secondary alcohol and the perfluoroalkylethylene product initially and to heat them to reaction temperature, i.e.
to at least the temperature at which the chosen initiator compound decomposes. When this temperature has been established the initiator compound, in the form of a solution of varying dilution in the secondary alcohol employed, i~ metered in in the amount in which it is consumed in the reaction mixture. This procedure will be preferred from considerations o safety in operation under certain circumstances, because it ensures a lower steady-state concentration of free radicals. The metering in of the solution of free-radical initiator is carried out continuously or in portions, for example by means of a metering pump. The reaction time of the reaction according to the invention depends above all on the - 6 - ;:0~77~L
free-radical initiator employed and on the reaction temperature, and is, as a rule, 3 to 15 hours.
The process according to the invention produces the desired tertiary fluoroalcohol in the form of a solution in the excess Recondary alcohol employed. Since the reaction to give the desired product takes place virtu-ally quantitatively and no appreciable byproducts are formed in the course of it, isolation of the tertiary fluoroalcohol from the solution mentioned is often not necessary at all; on the contrary, the tertiary fluoro-alcohol is already the desired product in this form. If its isolation is desired, the excess alcohol i6 simply removed by distillation. As a rule, any organic initiator compound still present will also be distilled off at the same time. The removal of initiator compound can also be achieved, for example, by wa~hing.
The process according to the invention has a number of advantages. The desired tertiary fluoroalcohol is obtained in a high yield and a high state of purity. ~he process i8 simple and economical. It thus represents an advantageous method for the conversion of perfluoroalkyl-ethylenes into tertiary fluoroalcohols. The tertiary fluoroalcohols obtained by the process according to the invention con titute novel, highly reactive fluorine compounds.
The invention will now be illustrated in greater detail by means of examples.
Example 1 Batch.
200.00 g (0.375 mol) of Rf-CH=CHz, Rf-= C6F13 to C12F25 338.00 g (5.630 mol) of isopropanol 3.60 g (0.015 mol) of benzoyl peroxide Molar rakio: 1 to 15 to G.04.
- 7 ~ 3~771 Procedure:
The R-CH=CHz product and the isopropanol were plac~d in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. After being flushed with nitrogen, the mixture was heated with stirring to 80C (boiling point of isopropanol). The benzoyl peroxide, dissolved in 100 g of isopropanol, was added dropwise with ~tirring to the mixture thus heated over a time of 7 hours. When the slow addition of benzoyl peroxide was complete, the mixture was kept for a further hour at 80C, with stirring, in order to complete the - reaction. Here, and in all the further examples, the isolation, for the purposes of determininq the yield, of the tertiary fluoroalcohol formed was effected by di~-tilling off the excess secondary alcohol and, if approp-riate, washing once or more often with water or with a slightly alkaline aqueou~ solution.
Result:
The tertiary fluoroalcohol obtained was, at room tempera-ture, a colorless, crystalline, waxy product. Yield: 94 of theory.
Example 2 Batch:
50.00 g (0.112 mol) of CaFl7-cH=cH2 134.70 g (2.240 mol) of isopropanol 0.25 g (0.0017 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 20 to 0.015.
Procedure:
The C8F17-CH-CH2 product, the isopropanol and the peroxide were placed in an autoclave equipped with a stirrer.
After being flushed with nitrogen, the mixture was heated to 140C with stirring and was kept at this temperature for 5 hours, with stirring. The pressure in the autoclave was 0.8 MPa. After the reaction time mentioned, all the perfluoroalkylethylene had reacted.
- 8 - ~ ~ ~9~71 Result:
The tertiary fluoroalcohol obtained was, at room tempera-ture, a colorless, crystalline, waxy product. Yield: 96 of theory.
Example 3 Batch:
50.00 g ~0.094 mol) of Rf-CH=CH2, R = C6F~3 to C12F25 32.40 g (0.540 mol) of technical isopropanol 1.20 g (0.0086 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 5 to 0.08.
Procedure:
The Rf-CH=CH2 product, the isopropanol and the peroxide were placed in the autoclave of Ex~mple 2. After being flushed with nitrogen, the mixture was heated with stirring to 125C and was kept at this temperature for 10 hours, with stirring. The pres~ure in the autoclave was 0.5 MPa. Since the reaction was still not complete after this reaction time, the mixture was kept at the tempera-ture of 140C for a further 3 hours, with ~tirring.
Result:
As in Example 2, with a yield of 89% of theory.
Example 4 Batch:
200.00 g (O.375 mol) of Rf-CH=CH2, R~ = C6F~3 to C12F25 338.00 g (5.630 mol) of isopropanol 3.84 g (0.0168 mol) of ammonium peroxodisulfate Molar ratio: 1 to 15 to 0.045.
Procedure:
As in Example 1, with the difference that the ammonium peroxodisulfate, dissolved in 5 g of water and 5 g of isopropanol, was added dropwise over a tLme of 5 hours to the mixture, heated at 80C, and the mixture was then 9 20~97~1 kept at 80C for a further 2 hours in order to complete the reaction.
Result:
As in Example 1, with a yield of 90~ of theory.
Example 5 Batch:
200.00 g (0.375 mol) of Rf-CH=CH2, R~ = C6F13 to C12Fz5 338.00 g (5.630 mol) of isopropanol 1.08 g (0.0056 mol) of azobi~isobutyronitrile Molar ratio: 1 to 15 to 0.015.
Procedure:
As in Example 1, with the difference that the azobisiso-butyronitrile, dissolved in 80 g of isopropanol, was added dropwise over a time of 7 hours to the mixture, heated at 80C, and the mixture was then kept at 80DC for a further 5 hours in order to complete the reaction.
Result:
As in Example 1, with a yield of 93~ of theory.
Example 6 Batch:
200.00 g (0.375 mol) of Rf-CH=CH2, Rf = C6F13 to C~F25 338.00 g (5.630 mol) of isopropanol 0.27 g (0.0019 mol) of di-tert.-butyl peroxide Molar ratio: 1 to 15 to 0.005.
Procedure:
The Rr-CH=CH2 product and the isopropanol were placed in the autoclave of Example 2. After being flushed with nitrogen, the mixture was heated with stirring to 135C.
The di-tert.-butyl peroxide, dissolved in 80 g of iso-propanol, was added dropwise, with stirring, over a time of 4 hours by means of a metering pump to the mixture ~ 49t~71 thus heated. The pressure in the au~oclave was 0.7 MPa.
When the 810w addition of peroxide was complete, the mixture was kept at 140C for a further 5 hours, with stirring, in order to complete the reaction.
Result:
As in Example 2, with a yield of 95% of theory.
Claims (8)
1. A process for the preparation of tertiary alcohols, containing fluorine, of formula 1 below (1) in which Rf is a perfluoroalkyl radical having 4 to 20 carbon atoms, R1 is CH3 and R2 is CH3 or C2H5, which com-prises reacting perfluoroalkylethylenes of formula 2 below Rf-CH=CH2 (2) in which Rf has the meaning indicated, with excess isopropenyl or excess sec.-butanol in the presence of free-radical initiators.
2. The process as claimed in claim 1, wherein at least 3 mol of isopropanol or sec.-butanol are employed per mol of perfluoroalkylethylene.
3. The process as claimed in claim 1, wherein 5 to 20 mol of isopropanol or sec.-butanol are employed per mol of perfluoroalkylethylene.
4. The process as claimed in any one of claims 1 to 3, wherein the reaction is carried out at a temperature of 50 to 160°C.
5. The process as claimed in any one of claims 1 to 3, wherein the reaction is carried out at a temperature of 80 to 140°C.
6. The process as claimed in one or more of claims 1 to 5, wherein the free-radical initiators are employed in an amount of 0.001 to 0.05 mol per mol of perfluoro-alkylethylene.
7. The process as claimed in one or more of claims 1 to 6, wherein an organic free-radical initiator belonging to the group comprising dialkyl peroxides, diacyl peroxides, per-acids, per-esters and azo compounds is employed.
8. The process as claimed in one or more of claims 1 to 7, wherein the perfluoroalkyl group of the perfluoro-alkylethylene compounds employed has 6 to 16 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4026712A DE4026712A1 (en) | 1990-08-24 | 1990-08-24 | METHOD FOR PRODUCING TERTIARY FLUORINE ALCOHOLS |
| DEP4026712.1 | 1990-08-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2049771A1 true CA2049771A1 (en) | 1992-02-25 |
Family
ID=6412783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002049771A Abandoned CA2049771A1 (en) | 1990-08-24 | 1991-08-23 | Process for the preparation of tertiary alcohols containing fluorine |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0473053A1 (en) |
| JP (1) | JPH04244038A (en) |
| KR (1) | KR920004320A (en) |
| CA (1) | CA2049771A1 (en) |
| DE (1) | DE4026712A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4124807A1 (en) * | 1991-07-26 | 1993-01-28 | Hoechst Ag | METHOD FOR PRODUCING PRIMARY AND SECOND FLUORINE ALCOHOLS |
| ES2157497T3 (en) * | 1996-06-06 | 2001-08-16 | Asahi Glass Co Ltd | PRODUCTION PROCEDURE CARRIED OUT IN A DISTILLATION COLUMN. |
| US6673976B1 (en) * | 2002-09-19 | 2004-01-06 | Honeywell International, Inc | Process of making fluorinated alcohols |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1065347A (en) * | 1952-07-07 | 1954-05-24 | Standard Oil Dev Co | Manufacture of alcohols and olefins |
| US3532659A (en) * | 1967-04-26 | 1970-10-06 | Pennsalt Chemicals Corp | Fluorinated organic compounds and polymers thereof |
| IT1176233B (en) * | 1984-06-01 | 1987-08-18 | Montefluos Spa | PROCEDURE FOR THE PREPARATION OF ALCOHOL, ETHER AND ESTER ADDUCTS WITH 1,2-DICHLORODIFLUOROETILENE |
-
1990
- 1990-08-24 DE DE4026712A patent/DE4026712A1/en not_active Withdrawn
-
1991
- 1991-08-21 EP EP91114005A patent/EP0473053A1/en not_active Withdrawn
- 1991-08-22 KR KR1019910014484A patent/KR920004320A/en not_active Application Discontinuation
- 1991-08-22 JP JP3211135A patent/JPH04244038A/en not_active Withdrawn
- 1991-08-23 CA CA002049771A patent/CA2049771A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04244038A (en) | 1992-09-01 |
| DE4026712A1 (en) | 1992-02-27 |
| KR920004320A (en) | 1992-03-27 |
| EP0473053A1 (en) | 1992-03-04 |
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