RU2346926C1 - Method of obtaining simple polyfluoroalkyl ethers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining simple polyfluoroalkyl ethers of the formula H(CF₂)_nCH₂OR (n=2, 4, 6; R=n-Pr, n-Bu, iso-Bu, n-C₅H₁₁, iso-C₅H₁₁, n-C₆H₁₃, C₆H₁₁(cyclohexyl), R_F (where R_F=H(CF₂)_nCH₂, n=2, 4, 6, 8), Ph, ArCH₂ (where Ar=Ph, p-Cl-Ph, p-CH₃O-Ph, m-NO₂-Ph)) by reaction of respective alcohols or phenol with polyfluoroalkylchlorosulfites in the presence of solvent, the reagents mixed at - 10 - -5°C. Alcohols or phenol are added to polyfluoroalkylchlorosulfite solution in portions mixed with N,N-dimethylformamide catalyst at mol ratio of 1:(1-1.1):(0.005-0.1) respectively. Reaction is performed at 40-50°C for 4-6 hours, and exuded sulfur dioxide and hydrochloride are blown off by inert gas.

EFFECT: high output and simplified process of obtaining polyfluoroalkyl ethers.

1 tbl, 28 ex

Description

The invention relates to a method for the synthesis of polyfluoroalkyl ethers from alcohols and polyfluoroalkyl chlorosulfites.

Many methods for the synthesis of polyfluorinated ethers are known. The most common are two directions - this is fluorination with elemental fluorine, hydrogen fluoride and various fluorides. The second direction is the synthesis of esters based on polyfluorinated alcohols or alcoholates.

Fluorinated alcohols of the type R _f CH ₂ OH and (R _f ) ₂ CHOH are readily available, their interaction with various reagents has been widely studied [A. Krolevets Chemistry of aliphatic fluorinated alcohols // Itogi Nauki i Tekhniki. Ser. organic chemistry / VINITI. 1985.V.6. 150 s.].

The interaction of polyfluorinated alcohols with chlorine-containing polyfluoroalkoxyethanes is known, as a result of which the corresponding polyfluoroalkyl ethers of ethylene glycol were obtained [A.I. Krylov, L.Sh. Vakhlamova, T.N. Petrova, E.A. Ostapenko, A.P. Kharchenko. Ethylene glycol polyfluoroalkyl esters // ZhVHO im. D.I. Mendeleev. 1977.V.22. Issue 4. S.469-470]. An alkaline agent (KOH, Na) and dimethyl sulfoxide were added to the initial alcohol at 40-80 ° C, then polyfluoroalkoxyethyl chloride was pinned for 1.5 hours and stirred at 80-105 ° C for another 3-6 hours, and esters were obtained with a yield of 59-68%.

The disadvantage of this method is the low yield of esters. In addition, the initial polyfluoroalkoxyethyl chloride must first be obtained by the reaction of the corresponding alcohols with thionyl chloride, which greatly complicates the technology.

A known method of producing dipolyfluorinated esters [RU 2203881 C1, C07C 43/12, publ. 2003.05.10] by the interaction of polyfluorinated alcohol with tetrafluoroethylene in the presence of a catalyst - potassium hydroxide (1.2-2.0% by weight of polyfluorinated alcohol). The process is conducted in the presence of 2-10 wt.% Methanol, the process temperature is 50-110 ° C, the pressure is 9-16 kgf / cm ² .

The disadvantage of this method is the formation of by-products - alkyl esters of 2,3,3,3-tetrafluoropropionic acid and products of the substitution of fluorine for alkoxygroup.

A known method of producing symmetric trifluoroethyl ether with a yield of about 60% in one stage by reaction of 2, 2, 2-trifluoroethyl alcohol with arylsulfonates [Pat 1076113 Germany, publ. 1960] and perfluoromethanesulfonic acid fluoride [Burdon J., McLoughlin V.C.R. // Tetrahedron. 1965. Vol. 21. N.1. P. 1-4]. The process is carried out with a significant excess of alcohol (more than 3 times), boiling for 5-10 hours in the presence of NaOH or metallic Na. The reaction proceeds through the formation of an intermediate aryl sulfonic acid or trifluoromethyl sulfonic acid.

The disadvantage of this method is the low yield, the formation of a by-product of trifluoromethyl sulfonic acid or arylsulfonic acid and the use of a large excess of alcohol, which must be further cleaned and dried for repeated use after isolation of the products.

A known method of producing dipolyfluoroalkyl ethers from polyfluorinated alcohols and polyfluoroalkylchlorosulfites [Rakhimov A.I., Nalesnaya A.V., Vostrikova OV Synthesis of di (polyfluoroalkyl) ethers / HPLC. 2004.V.77. Issue 9. S.1573-1574]. Dipolyfluoroalkyl ethers are obtained by two methods - the catalytic interaction of polyfluoroalkyl chlorosulfites with polyfluorinated alcohols in the presence of N, N-dimethylformamide (DMF) and the non-catalytic interaction of polyfluoroalkyl chlorosulfites with polyfluorinated alcohols in the presence of triethylamine. According to the first method, a solution of chlorosulfite is added to a mixture of the corresponding alcohol with DMF in a molar ratio of chlorosulfite: polyfluorinated alcohol: DMF equal to 1: 1: (0.005-0.01) at -10 ° C, then the reaction mass is kept at 20 ° C for two hours, blowing off hydrogen chloride and sulfur dioxide released by dried air, and another 1 day at room temperature. After distillation of the solvent (chloroform, diethyl ether) and distillation of the product, the yield of ether is 59-98%. According to the second method, the chlorosulfite solution was dosed into a previously prepared complex of alcohol with triethylamine at -10 ° C, then the reaction mixture was kept at room temperature for a day; the solvent is pentane or hexane. The resulting triethylammonium chloride was filtered off, the resulting ether was purified by distillation, yield 52-85%.

The disadvantage of this method is the long reaction time (more than a day), as well as the use of large quantities of triethylamine (TEA) according to the second method.

Closest to the alleged invention is a method for producing simple polyfluorinated ethers by reacting saturated monohydric alcohols and phenol with polyfluoroalkylchlorosulfites in the presence of tertiary amines [A.I. Rakhimov, A.V. Nalesnaya, O.V. Vostrikova. A new method for the synthesis of polyfluorinated ethers // Journal of General Chemistry. 2004.V. 74 Issue 4. S.693-694] (prototype). Alcohols and phenol are introduced into the reaction in the form of a complex with an equimolar amount of triethylamine, a solution of polyfluoroalkylchlorosulfite is metered into a previously prepared alcohol (phenol) complex with TEA at -10 ÷ -5 ° C, then the reaction mixture is kept for 5-6 hours at room temperature. The solvent - pentane or hexane, the resulting salt - triethylammonium chloride, is not soluble in it, precipitates. The resulting ether was purified by distillation. The yield of ether is 39-51%.

The disadvantages of this method are not high yields of esters, as well as the use of large quantities of triethylamine and, as a result, the formation of a by-product of triethylammonium chloride. The formation of salt comes with the release of heat, which contributes to the occurrence of adverse reactions and a decrease in the yield of ether. In addition, triethylammonium chloride is an undesirable pollutant that is difficult to dispose of.

The technical result of the invention is the production of polyfluoroalkyl ethers in high yield (up to 90.2%), without the use of triethylamine, which greatly simplifies the method of obtaining the claimed compounds.

The technical result is achieved by the fact that the method of producing polyfluoroalkyl ethers of the formula H (CF ₂ ) _n CH ₂ OR (n = 2, 4, 6; R = n-Pr, n-Bu, ISO-Bu, nC ₅ H ₁₁ , iso-C ₅ H ₁₁ , nC ₆ H ₁₃ , C ₆ H ₁₁ (cyclohexyl), R _F (where R _F = H (CF ₂ ) _n CH ₂ , n = 2, 4, 6, 8), Ph , ArCH ₂ (where Ar = Ph, p-Cl-Ph, p-CH ₃ O-Ph, m-NO ₂ -Ph)) by the reaction of the corresponding alcohols or phenol with polyfluoroalkylchlorosulfites in the presence of a solvent, consists in mixing the reagents at a temperature of -10 ÷ -5 ° C, moreover, alcohols or phenol are dosed into a solution of polyfluoroalkylchlorosulfite in a mixture with a catalyst - N, N-dimethylformamide in their molar ratio equal to 1: (1-1.1) :( 0.005-0.1), respectively, the reaction is carried out at 40-50 ° C for 4-6 hours, the released sulfur dioxide and hydrogen chloride are blown off with an inert gas.

The essence of the proposed method lies in the fact that alcohols and phenol, having acidic properties, form a donor-acceptor complex with DMF, as with a weak base, which leads to an increase in the reactivity of alcohol (phenol) in a specific interaction with polyfluoroalkylchlorosulfite (PFAHS), resulting to ether formation.

The catalytic effect of DMF was studied in detail in the reaction of polyfluorinated alcohols with thionyl chloride [Nalesnaya A.V. Catalytic synthesis and reactions of polyfluoroalkylchlorosulfites: Abstract of Ph.D. diss. Cand. Chem. sciences. 02.00.03 Organic chemistry, Volgograd, 2004, 20 pp.], It was found that the molecule of the amide catalyst, being associated with a carbonyl group on the hydroxyl alcohol, is involved in the polarization of the starting reagents and intermediate structures. It is known that associates are more stable at low temperature, that is, for the formation and stability of associates when mixing reagents, cooling to -10 ÷ -5 ° C is necessary.

PFAHS, as the most reactive reagent, prone to decomposition (hydrolysis), should be in excess, therefore, it is necessary to take 1-1.1 mol of PFAHS for 1 mol of alcohol and at the same time the alcohol solution should be metered in PFAHS.

It is known that to obtain dipolyfluoroalkyl ethers from polyfluorinated alcohols and polyfluoroalkylchlorosulfites [Rakhimov AI, Nalesnaya AV, Vostrikova OV Synthesis of di (polyfluoroalkyl) ethers / HPLC. 2004.V.77. Issue 9. S.1573-1574.] Use the molar ratio of alcohol: DMF equal to 1: (0.005-0.01). We found that non-fluorinated alcohols are less reactive when interacting with PFAHS, in addition, an increase in the molecular weight of polyfluorinated alcohol also reduces its reactivity, which requires an increase in the amount of catalyst, therefore we increased the amount of DMF in these cases to (0.01-0.1) mol per 1 mol of the corresponding alcohol.

The following optimal ratios of alcohol (phenol) and DMF were established:

- for polyfluorinated alcohols H (CF ₂ ) _n CH ₂ OH

cn = 2, 4, 6 1: (0.005-0.01) cn = 8 1: 0.1;

- for non-fluorinated alcohols 1: 0.01;

- for phenols 1: (0.005-0.01).

According to the prototype, the reaction of alcohols with PFAHS takes 5-6 hours at room temperature (20 ° C), while the yield of esters is 39-51%. It is known that increasing the temperature increases the reaction rate, therefore, we increased the temperature to 40-50 ° C (depending on the reactivity of the starting alcohols and PFAHS), while the reaction time decreased to 4-6 hours and the yield of esters increased to 60.5-89.9% . Obviously, with a decrease in the reaction temperature, it is necessary to increase the reaction time to obtain esters in high yield.

Gases released during the reaction — hydrogen chloride and sulfur dioxide — must be removed from the reaction mixture to prevent side reactions, as well as to shift the equilibrium towards ether formation. For this, purge (sparging) with an inert gas, such as nitrogen, is used.

Example 1. Obtaining 1- (2,2,3,3,4,4,5,5-octafluoro) pentoxypropane

1.3705,

1.4234. ИК-спектр, v, см^-1:1154 (С-О-С), 1180 (CF₂), 2892 (CH₂-O), 2980 (CH₂, СН₃).1.4 g (0.023 mol) of propyl alcohol was mixed with 0.018 ml (0.00023 mol) of DMF in 20 ml of hexane, cooled to -5 ° C and, with vigorous stirring, 7.7 g (0.024 mol) of 1, 1, 5-trihydroperfluoropentylchlorosulfite in 15 ml of hexane, maintaining a temperature of -5 ° C. The molar ratio of the reagents alcohol: PFAHS: DMF (hereinafter simply the molar ratio) is 1: 1.04: 0.01. After mixing the reagents, the temperature of the reaction mixture was raised to 45-50 ° C and held for 6 hours under continuous purging with an inert gas (nitrogen). Hexane was distilled off, the product was distilled in vacuo. The yield of 1- (2,2,3,3,4,4,5,5-octafluoro) pentoxypropane 5.54 g (87.9%), mp 104 ° C (13 mmHg),

1.3705,

1.4234. IR spectrum, v, cm ^-1 : 1154 (С-О-С), 1180 (CF ₂ ), 2892 (CH ₂ -O), 2980 (CH ₂ , CH ₃ ).

Example 2. Obtaining 1- (2, 2, 3, 3-tetrafluoro) propoxybutane

1.4180,

1.2770. ИК-спектр, ν, см^-1:1171 (С-О-С), 1206 (CF₂), 2912 (O-CH₂), 2963 (СН₂), 2997 (СН₃).1.6 g (0.022 mol) of 1-butanol was mixed with 0.017 ml (0.00022 mol) of DMF in 20 ml of hexane, cooled to -10 ° C, and 4.7 g (0.022 mol) of 1,1,3-trihydroperfluoropropylchlorosulfite were added in portions to the solution with vigorous stirring. in 10 ml of hexane, maintaining a temperature of -10 ° C. The molar ratio of 1: 1: 0.01. After mixing the reagents, the temperature of the reaction mixture was increased to 40-45 ° C and kept for 5 hours under continuous purging with an inert gas (nitrogen). Hexane was distilled off, the product was distilled in vacuo. The yield of 1- (2,2,3,3-tetrafluoro) propoxybutane 3.72 g (89.9%), mp 95 ° C (4 mmHg),

1.4180,

1.2770. IR spectrum, ν, cm ^-1 : 1171 (С-О-С), 1206 (CF ₂ ), 2912 (O-CH ₂ ), 2963 (СН ₂ ), 2997 (СН ₃ ).

Example 3. Obtaining 1- (2,2,3,3,4,4,5,5-octafluoro) pentoxybutane

1.3700,

1.4165.Received analogously to example 1. The yield of 85.0%, so Kip 102 ° C (4 mm RT. Art.),

1.3700,

1.4165.

Example 4. Obtaining 1- (2,2,3,3-tetrafluoro) propyloxypentane

1.3996,

1.0371. ИК-спектр, v, см^-1: 1137 (С-О-С), 1214 (CF₂), 2885 (O-CH₂), 2963 (CH₂, СН₃).Received analogously to example 2. Yield 80%, so Kip. 88 ° C (2 mmHg),

1.3996,

1.0371. IR spectrum, v, cm ^-1 : 1137 (С-О-С), 1214 (CF ₂ ), 2885 (O-CH ₂ ), 2963 (CH ₂ , СН ₃ ).

Example 5. Obtaining 1- (2,2,3,3-tetrafluoropropoxy) -2-methylpropane

1.3450,

1.1020.Received analogously to example 2. The yield of 60.0%, so Kip. 95 ° C (3 mmHg),

1.3450,

1.1020.

Example 6. Obtaining 1- (2,2,3,3,4,4,5,5-octafluoropentoxy) -2-methylpropane

1.3520,

1.3040.Received analogously to example 1. The yield of 56.0%, so Kip 106 ° C (3 mm RT. Art.),

1.3520,

1.3040.

Example 7. Obtaining 1- (2,2,3,3-tetrafluoropropoxy) -3-methylbutane

1.3550,

1.0990.Received analogously to example 2. The yield of 70.0%, so Kip 100 ° C (3 mm RT. Art.),

1.3550,

1.0990.

Example 8. Obtaining 1- (2,2,3,3,4,4,5,5-octafluoropentoxy) -3-methylbutane

1.3600,

1.2990.Received analogously to example 1. Yield 71.0%, so Kip. 113 ° C (3 mmHg),

1.3600,

1.2990.

Example 9. Obtaining 1 - (2,2,3,3-tetrafluoro) propoxyhexane

1.3650,

1.0870.Received analogously to example 2. The yield of 60.0%, so Kip. 100 ° C (2 mm Hg),

1.3650,

1.0870.

Example 10. Obtaining 1 - (2,2,3,3,4,4,5,5-octafluoro) pentoxyhexane

1.3480,

1.2130.Received analogously to example 1. Yield 55.0%, so Kip. 120 ° C (2 mmHg),

1.3480,

1.2130.

Example 11. Obtaining 2, 2, 3, 3-tetrafluoropropoxycyclohexane

1,3798,

1,1005. ИК-спектр, ν, см^-l: 1170 ср (νC-O-C); 1170c (ν CF₂); 2878 cp, 2965 cp (ν CH₂); 3005 сл (CHF₂), 714 cp, 760 cp, 800 cp, 1000 cp (колебания кольца). ПМР-спектр, δ, м.д.: 5.95 т.т. (1Н, HCF₂); 3.86 т (2Н, О-СН₂-СР₂), 2.85 с (CH кольца), 1.74 и 1.32 (мультиплет кольца).Received analogously to example 2. Yield 82.3%, so Kip. 95 ° C (3 mmHg),

1,3798,

1,1005. IR spectrum, ν, cm ^-1 : 1170 sr (νC-OC); 1170c (ν CF ₂ ); 2878 cp, 2965 cp (ν CH ₂ ); 3005 cl (CHF ₂ ), 714 cp, 760 cp, 800 cp, 1000 cp (ring vibrations). PMR spectrum, δ, ppm: 5.95 t.p. (1H, HCF ₂ ); 3.86 t (2H, O-CH ₂ -CP ₂ ), 2.85 s (CH rings), 1.74 and 1.32 (multiplet of the ring).

Example 12. Obtaining 2,2,3,3,4,4,5,5-octafluoropentoxycyclohexane

1,3865,

1,3733. ИК-спектр, ν, см^-1: 1165 ср (νC-O-C); 1185 с (νCF₂); 2870, 2960 (ν CH₂); 3005 сл (CHF₂), 716 cp, 763 cp, 810 cp, 960 cp (колебания кольца). ПМР-спектр, δ, м.д.: 5.99 т.т. (1Н, HCF₂); 3.95 т (2Н, O-CH₂-CF₂), 2.89 с (СН кольца), 1.75 и 1.31 (мультиплет кольца).Received analogously to example 1. The yield of 75.5%, so Kip. 105 ° C (3 mmHg),

1.3865,

1.3733. IR spectrum, ν, cm ^-1 : 1165 sr (νC-OC); 1185 s (νCF ₂ ); 2870, 2960 (ν CH ₂ ); 3005 cl (CHF ₂ ), 716 cp, 763 cp, 810 cp, 960 cp (ring vibrations). PMR spectrum, δ, ppm: 5.99 t.p. (1H, HCF ₂ ); 3.95 t (2H, O-CH ₂ -CF ₂ ), 2.89 s (CH rings), 1.75 and 1.31 (multiplet of the ring).

Example 13. Obtaining 1, 1, 7-trihydroperfluoroheptyloxycyclohexane

1.3891,

1.4067. ИК-спектр, ν, см^-1: 1165 ср (νC-O-C); 1185 с (νCF₂); 2870, 2960 (ν CH₂); 3005 сл (CHF₂), 716 cp, 763 cp, 810 cp, 960 cp (колебания кольца).Received analogously to example 1. The yield of 65.2%, so Kip.123 ° C (3 mm RT. Art.),

1.3891,

1.4067. IR spectrum, ν, cm ^-1 : 1165 sr (νC-OC); 1185 s (νCF ₂ ); 2870, 2960 (ν CH ₂ ); 3005 cl (CHF ₂ ), 716 cp, 763 cp, 810 cp, 960 cp (ring vibrations).

Example 14. Obtaining 2,2,3,3-tetrafluoro-1- (2,2,3,3,4,4,5,5-octafluoropentoxy) propane

1.3500,

1.6790. ИК-спектр, ν, см^-1: 1116 с (νC-O-C); 1242 с (νCF₂); 1300 с; 1416 с, 1464 с (C-F); 1530 сл; 1575 сл; 1667 ср; 2860 сл (ν^S CH₂); 2934 сл (ν^as CH₂); 2980 ср; 3017 сл (CHF₂). ПМР-спектр, δ, м.д.: 5.966 т.т. (1Н,

(CF₂)₄CH₂OCH₂(CF₂)₂H); 5.823 т.т. (1Н, H(CF₂)₄CH₂OCH₂(CF₂)₂

); 4.321 д.кв. (4Н,-СН₂-).4.4 g (0.019 mol) of 1, 1, 5-trihydroperfluoro-1-pentanol was mixed with 0.007 ml (0.0001 mol) of DMF in 15 ml of chloroform, cooled to -10 ° C and dosed with vigorous stirring into a solution of 4.48 g (0.02 mol) 1,1,3-trihydroperfluoropropylchlorosulfite in 10 ml of chloroform, maintaining a temperature of -10 ° C. The molar ratio of 1: 1.05: 0.005. Then, the temperature of the reaction mixture was raised to 40 ° C and held for 4 hours under continuous purging with an inert gas (nitrogen). The solvent was distilled off, the product was distilled in vacuo. Yield 5.56 g (84.6%), mp. 83 ° C (2 mmHg),

1.3500,

1.6790. IR spectrum, ν, cm ^-1 : 1116 s (νC-OC); 1242 s (νCF ₂ ); 1300 s; 1416 s, 1464 s (CF); 1530 cl; 1575 cl; 1667 cf. 2860 cl (ν ^S CH ₂ ); 2934 cl (ν ^as CH ₂ ); 2980 Wed; 3017 ct (CHF ₂ ). PMR spectrum, δ, ppm: 5.966 t.p. (1H,

(CF ₂ ) ₄ CH ₂ OCH ₂ (CF ₂ ) ₂ H); 5.823 t.t. (1H, H (CF ₂ ) ₄ CH ₂ OCH ₂ (CF ₂ ) ₂

); 4.321 sq. (4H, -CH ₂ -).

Example 15. Obtaining 2,2,3,3-tetrafluoro-1- (1,1,7-trihydroperfluoroheptyloxy) propane

1.3450,

1.7310. ИК-спектр, ν, см^-1: 1116 с (νC-O-С); 1223 с (νCF₂); 1300 ср; 1412 ср, 1464 ср (C-F); 1530 сл; 1566 сл; 1669 ср; 2868 сл (ν^s CH₂); 2937 сл (ν^as СН₂); 2968 ср; 3014 сл (CHF₂).Obtained analogously to example 14, using 1,1,7-trihydroperfluoro-1-heptanol and 1,1,3-trihydroperfluoropropylchlorosulfite. Yield 71.6%, bp 95 ° C (1 mmHg),

1.3450,

1.7310. IR spectrum, ν, cm ^-1 : 1116 s (νC-O-C); 1223 s (νCF ₂ ); 1300 cf. 1412 cf., 1464 cf (CF); 1530 cl; 1566 cl; 1669 cf. 2868 cl (ν ^s CH ₂ ); 2937 cl (ν ^as CH ₂ ); 2968 Wed; 3014 ct (CHF ₂ ).

Example 16. Obtaining 2,2,3,3,4,4,5,5-octafluoro-1- (1,1,7-trihydroperfluoroheptyloxy) pentane

1.3380,

1.7647. ИК-спектр, ν, см^-1: 1120 с (νC-O-С); 1220 с (νCF₂); 1300 сл; 1412 ср, 1468 ср (C-F); 1556 сл; 1658 ср; 2864 сл (ν^s СН₂); 2932 ср (ν^as CH₂); 2961 ср; 3009 сл (CHF₂).Received analogously to example 14, using 1,1,7-trihydroperfluoro-1-heptanol and 1,1,5-trihydroperfluoropentylchlorosulfite. Yield 61.5%, bp 110 ° C (1 mmHg),

1.3380,

1.7647. IR spectrum, ν, cm ^-1 : 1120 s (νC-O-C); 1220 s (νCF ₂ ); 1300 cl; 1412 cf., 1468 cf (CF); 1556 cl; 1658 cf. 2864 cl (ν ^s CH ₂ ); 2932 cf (ν ^as CH ₂ ); 2961 cf. 3009 ct (CHF ₂ ).

Example 17. Obtaining 2,2,3,3-tetrafluoro-1- (1,1,9-trihydroperfluorononyloxy) propane

(CF₂)₈CH₂OCH₂(CF₂)₂

); 4.358 д.т. (4Н,-СН₂-).3.96 g (0.0091 mol) of 1,1,9-trihydroperfluoro-1-nonanol was mixed with 0.07 ml (0.0009 mol) of DMF in 20 ml of chloroform, cooled to -5 ° C and dosed with vigorous stirring into a solution of 2.15 g (0.01 mol) 1, 1, 3-trihydroperfluoropropylchlorosulfite in 10 ml of chloroform, maintaining a temperature of -5 ° C. The molar ratio of 1: 1.1: 0.1. Then the temperature of the reaction mixture was raised to 50 ° C and held for 6 hours with constant purging with an inert gas (nitrogen). The solvent, unreacted alcohol and chlorosulfite were distilled off; non-vacuum distillable residue was recrystallized from chloroform. Received 1.72 g (34.5%) of ether, so pl. 49 ° C. IR spectrum, ν, cm ^-1 : 1120 s (νC-OC); 1216 s (νCF ₂ ); 1277cp; 1394 cl, 1421 cl (CF); 1505 sl; 1540 cl; 1728 Wed; 2856 cf (ν ^s CH ₂ ); 2894 (ν ^as CH ₂ ); 2932 cf. 2954 ct (CHF ₂ ). PMR spectrum, δ, ppm: 5.975 t.p. (2H,

(CF ₂ ) ₈ CH ₂ OCH ₂ (CF ₂ ) ₂

); 4.358 d.t. (4H, -CH ₂ -).

Example 18. Obtaining 2,2,3,3,4,4,5,5-octafluoro-1- (1,1,9-trihydroperfluorononyloxy) pentane

(CF₂)₈CH₂OCH₂(CF₂)₄

); 4.354 д.т. (4Н,-СН₂-).Obtained analogously to example 17, using 1,1,9-trihydroperfluoro-1-nonanol and 1,1,5-trihydroperfluoropropylchlorosulfite. Yield 32.1%, mp 53 ° C. PMR spectrum, δ, ppm: 5.973 tp (2H,

(CF ₂ ) ₈ CH ₂ OCH ₂ (CF ₂ ) ₄

); 4.354 d.t. (4H, -CH ₂ -).

Example 19. Obtaining 1-phenoxy-2,2,3,3-tetrafluoropropane

1.4508,

1.4378. ИК-спектр, ν, см^-1: 2932 (CH₂), 1604, 1504 (Ph), 1239, 1032 (C-O-C), 1192 (CF₂).Received analogously to example 2. The yield of 61.5%, so Kip. 53 ° C (3 mmHg),

1.4508,

1.4378. IR spectrum, ν, cm ^-1 : 2932 (CH ₂ ), 1604, 1504 (Ph), 1239, 1032 (COC), 1192 (CF ₂ ).

Example 20. Obtaining 1-phenoxy-2,2,3,3,4,4,5,5-octafluoropentane

1.3980,

1.5760. ПМР-спектр, δ, м.д.: 6.05 т.т. (1Н, HCF₂); 4.47 т (2Н, O-CH₂-CF₂), 6.84 и 7.16 (мультиплет Ph).Received analogously to example 1. Yield 81.3%, so Kip. 68 ° C (3 mmHg),

1.3980,

1.5760. PMR spectrum, δ, ppm: 6.05 t.t. (1H, HCF ₂ ); 4.47 t (2H, O-CH ₂ -CF ₂ ), 6.84 and 7.16 (multiplet Ph).

Example 21. Obtaining [(2,2,3,3-tetrafluoropropoxy) methyl] benzene

1.3580,

1.5065. ИК-спектр, ν, см^-1: 1160 ср (νC-O-C); 1200 с (νCF₂); 3050 (ν СН₂); 1456 ср, 1500 ср (Ph). ПМР-спектр, δ, м.д.: 5.96 т.т. (1Н, HCF₂); 4.37 т (2Н, O-CH-CF₂), 7.39 мультиплет (Ph) 4.32 с (Ph-CH₂).3.25 g (0.03 mol) of benzyl alcohol was mixed with 0.02 ml (0.0003 mol) of DMF in 20 ml of benzene, cooled to -10 ° C and dosed with vigorous stirring into a solution of 6.44 g (0.03 mol) of 1, 1, 3-trihydroperfluoropropylchlorosulfite in 10 ml of benzene, maintaining a temperature of -10 ° C. The molar ratio of 1: 1: 0.01. Then the temperature of the reaction mixture was raised to 45-50 ° C and held for 6 hours with constant purging with an inert gas (nitrogen). After distillation of the solvent and distillation in vacuo, 5.69 g (85.4%) of ether were obtained, b.p. 120 ° C (3 mmHg),

1.3580,

1.5065. IR spectrum, ν, cm ^-1 : 1160 sr (νC-OC); 1200 s (νCF ₂ ); 3050 (ν CH ₂ ); 1456 cf., 1500 cf. (Ph). PMR spectrum, δ, ppm: 5.96 t.p. (1H, HCF ₂ ); 4.37 t (2H, O-CH-CF ₂ ), 7.39 multiplet (Ph) 4.32 s (Ph-CH ₂ ).

Example 22. Obtaining [(2,2,3,3,4,4,5,5-octafluoropentoxy) methyl] benzene

1.3730,

1.6382. ИК-спектр, ν, см^-1: 1163 ср (νC-O-C); 1210 с (νCF₂); 3051 (ν СН₂); 1460 ср, 1500 ср (Ph).Received analogously to example 21. The yield of 83.1%, so Kip. 125 ° C (3 mmHg),

1.3730,

1.6382. IR spectrum, ν, cm ^-1 : 1163 sr (νC-OC); 1210 s (νCF ₂ ); 3051 (ν CH ₂ ); 1460 sr, 1500 sr (Ph).

Example 23. Obtaining 1-chloro-4 - [(2,2,3,3-tetrafluoropropoxy) methyl] benzene

1.4580,

1.4025. ИК-спектр, ν, см^-1: 1168 ср (νC-O-C); 1195 с (νCF₂); 3050 (ν СН₂); 1470 ср, 1550 ср (Ph), 810cp (Cl). ПМР-спектр, δ, м.д.: 5.97 т.т. (1Н, HCF₂); 3.34 т (2Н, O-CH₂-CF₂), 7.21 мультиплет (Ph) 4.42 с (Ph-СН₂).Received analogously to example 21. The yield of 90.2%, so Kip. 130 ° C (3 mmHg),

1.4580,

1.4025. IR spectrum, ν, cm ^-1 : 1168 sr (νC-OC); 1195 s (νCF ₂ ); 3050 (ν CH ₂ ); 1470 sr, 1550 sr (Ph), 810cp (Cl). PMR spectrum, δ, ppm: 5.97 t.t. (1H, HCF ₂ ); 3.34 t (2H, O-CH ₂ -CF ₂ ), 7.21 multiplet (Ph) 4.42 s (Ph-CH ₂ ).

Example 24. Obtaining 1-chloro-4 - [(2,2,3,3,4,4,5,5-octafluoropentoxy) methyl] benzene

1.4100,

1.5002. ИК-спектр, ν, см^-1: 1167 ср (νC-O-C); 1190 с (νCF₂); 3055 (ν CH₂); 1475 ср, 1552 ср (Ph), 808 cp (Cl).Received analogously to example 21. The yield of 85.3%, so Kip. 135 ° C (3 mmHg),

1.4100,

1.5002. IR spectrum, ν, cm ^-1 : 1167 sr (νC-OC); 1190 s (νCF ₂ ); 3055 (ν CH ₂ ); 1475 sr, 1552 sr (Ph), 808 cp (Cl).

Example 25. Obtaining 1-methoxy-4 - [(2,2,3,3-tetrafluoropropoxy) methyl] benzene

1.4440,

1.2856. ИК-спектр, ν, см^-1: 1200 ср (νC-O-C); 1200 с (vCF₂); 3025 (ν CH₂); 1600 ср, 1516 ср (Ph). ПМР-спектр, δ, м.д.: 5.94 т.т. (1Н, HCF₂); 4.41 т (2Н, O-CH₂-CF₂), 6.73 и 7.14 д (Ph), 4.41 с (Ph-CH₂), 3.69 с (ОСН₃).Received analogously to example 21. The yield of 70.4%, so Kip 110 ° C (3 mm RT. Art.),

1.4440,

1.2856. IR spectrum, ν, cm ^-1 : 1200 sr (νC-OC); 1200 s (vCF ₂ ); 3025 (ν CH ₂ ); 1600 Wed, 1516 Wed (Ph). PMR spectrum, δ, ppm: 5.94 t.p. (1H, HCF ₂ ); 4.41 t (2H, O-CH ₂ -CF ₂ ), 6.73 and 7.14 d (Ph), 4.41 s (Ph-CH ₂ ), 3.69 s (OCH ₃ ).

Example 26. Preparation of 1-methoxy-4 - [(2,2,3,3,4,4,5,5-octafluoropentoxy) methyl] benzene

1.3995,

1.3643. ИК-спектр, ν, см^-1: 1205 ср (νC-O-C); 1200 с (νCF₂); 3030 (ν СН₂); 1610 ср, 1510 ср (Ph).Received analogously to example 21. The yield of 63.7%, so Kip. 116 ° C (3 mmHg),

1.3995,

1.3643. IR spectrum, ν, cm ^-1 : 1205 sr (νC-OC); 1200 s (νCF ₂ ); 3030 (ν CH ₂ ); 1610 Wed, 1510 Wed (Ph).

Example 27. Obtaining 1-nitro-3 - [(2,2,3,3-tetrafluoropropoxy) methyl] benzene

1.4760,

1.3570. ИК-спектр, ν, см^-1: 1170 ср (νC-O-C); 1850 с (νCF₂); 3025 (ν СН₂); 1450 ср, 1510 ср (Ph), 1320 (NO₂)cp. ПМР-спектр, δ, м.д.: 5.93 т.т. (1Н, HCF₂); 4.40 т (2Н, O-CH₂-CF₂), 7.45 мультиплет (Ph) 4.42 с (Ph-СН₂).Received analogously to example 21. The yield of 90.0%, so Kip. 130 ° C (3 mmHg),

1.4760,

1.3570. IR spectrum, ν, cm ^-1 : 1170 sr (νC-OC); 1850 s (νCF ₂ ); 3025 (ν CH ₂ ); 1450 sr, 1510 sr (Ph), 1320 (NO ₂ ) cp. PMR spectrum, δ, ppm: 5.93 t.p. (1H, HCF ₂ ); 4.40 t (2H, O-CH ₂ -CF ₂ ), 7.45 multiplet (Ph) 4.42 s (Ph-CH ₂ ).

Example 28. Obtaining 1-nitro-3 - [(2,2,3,3,4,4,5,5-octafluoropentoxy) methyl] benzene

1.4310,

1.5002. ИК-спектр, ν, см^-1: 1175 ср (νC-O-C); 1850 с (νCF₂); 3030 (ν СН₂); 1455 ср, 1511 ср (Ph), 1324 (NO₂)cp.Received analogously to example 21. The yield of 84.1%, so Kip. 140 ° C (3 mmHg),

1.4310,

1.5002. IR spectrum, ν, cm ^-1 : 1175 sr (νC-OC); 1850 s (νCF ₂ ); 3030 (ν CH ₂ ); 1455 sr, 1511 sr (Ph), 1324 (NO ₂ ) cp.

The yield and properties of the obtained esters are presented in the table. We found that the larger the molecular weight of the starting polyfluoroalkylchlorosulfite H (CF ₂ ) _n CH ₂ OS (O) Cl, the less reactive it is, therefore, it is necessary to increase the temperature and reaction time when passing from n = 2 to n = 6 (examples 1 and 2). The increase in molecular weight of polyfluorinated alcohol also reduces its reactivity, which requires an increase in the amount of catalyst, temperature and reaction time and reduces the yield of esters (examples 17, 18).

Table. Polyfluoroalkyl ethers Example No. Formula Exit, % T. bale., ° C / mmHg. Art. d ₂₀ ⁴ n _D ²⁰ one 2 3 four 5 6 one nC ₃ H ₇ OCH ₂ (CF ₂ CF ₂ ) ₂ N 87.9 (42 *) 104/13 1.4234 1.3705 2 nC ₄ H ₉ OCH ₂ CF ₂ CF ₂ H 89.9 (45 *) 95/4 1.2770 1.4180 3 nC ₄ H ₉ OCH ₂ (CF ₂ CF ₂ ) ₂ H 85.0 102/4 1.4165 1.3700 four nC ₅ H ₁₁ OCH ₂ CF ₂ CF ₂ H 80.0 (49 *) 88/2 1.2371 1.3996 5 iso-C ₄ H ₉ OCH ₂ CF ₂ CF ₂ N 60.0 95/3 1.102 1.345 6 iso-C ₄ H ₉ OCH ₂ (CF ₂ CF ₂ ) ₂ N 56.0 106/3 1.304 1.352 7 iso-C ₅ H ₁₁ OCH ₂ CF ₂ CF ₂ H 70.0 100/3 1.098 1.355 8 iso-C ₅ H ₁₁ OCH ₂ (CF ₂ CF ₂ ) ₂ N 71.0 113/3 1.299 1.360 9 nC ₆ H ₁₃ OCH ₂ CF ₂ CF ₂ N 60.0 100/2 1.087 1.365 10 nC ₆ H ₁₃ OCH ₂ (CF ₂ CF ₂ ) ₂ N 55.0 120/2 1.213 1.348 eleven C ₆ H ₁₁ OCH ₂ CF ₂ CF ₂ H 75.5 105/3 1.3733 1.3865 12 C ₆ H ₁₁ OCH ₂ (CF ₂ CF ₂ ) ₂ N 82.3 95/3 1.1005 1.3798 13 C ₆ H ₁₁ OCH ₂ (CF ₂ CF ₂ ) ₃ N 65.2 123/3 1.4067 1.3891 fourteen H (CF ₂ ) ₄ CH ₂ OCH ₂ (CF ₂ ) ₂ H 84.6 83/2 1.6790 1.3500 fifteen N (CF ₂ ) ₆ CH ₂ OCH ₂ (CF ₂ ) ₂ N 71.6 95/1 1.7310 1.3450 16 N (CF ₂ ) ₄ CH ₂ OCH ₂ (CF ₂ ) ₆ N 61.5 110/1 1.7647 1.3380 17 H (CF ₂ ) ₈ CH ₂ OCH ₂ (CF ₂ ) ₂ H 34.5 - so pl. 49 ° C eighteen H (CF ₂ ) ₈ CH ₂ OCH ₂ (CF ₂ ) ₄ H 32.1 - mp 53 ° C 19 PhOCH ₂ CF ₂ CF ₂ H 60.5 (43 *) 53/3 1.4378 1.4508 twenty PhOCH ₂ (CF ₂ CF ₂ ) ₂ H 81.3 (51 *) 110/4 1.5760 1.4050 21 PhCH ₂ OCH ₂ CF ₂ CF ₂ H 85.4 120/3 1.5065 1.3580 22 PhCH ₂ OCH ₂ (CF ₂ CF ₂ ) ₂ H 83.1 125/3 1.6382 1.3730 23 p-Cl-PhCH ₂ OCH ₂ (CF ₂ ) ₂ H 90.2 130/3 1.4025 1.4580 24 p-Cl-PhCH ₂ OCH ₂ (CF ₂ ) ₄ H 85.3 135/3 1.5002 1.4100 25 p-CH ₃ O-PhCH ₂ OCH ₂ (CF ₂ ) ₂ H 70.4 110/3 1.2856 1.4440 26 p-CH ₃ O-PhCH ₂ OCH ₂ (CF ₂ ) ₄ H 63.7 116/3 1.3643 1.3995 27 m-NO ₂ PhCH ₂ OCH ₂ (CF ₂ ) ₂ H 90.0 130/3 1.3570 1.4760 28 m-NO ₂ PhCH ₂ OCH ₂ (CF ₂ ) ₄ H 84.1 140/3 1.5002 1.4310 * - According to the prototype.

Thus, a method for producing polyfluoroalkyl ethers from alcohols (phenol) and polyfluoroalkyl chlorosulfites using N, N-dimethylformamide as a catalyst with the ratio of reagents alcohol (phenol): polyfluoroalkyl chlorosulfite: DMF equal to 1: (1-1.1) :( 0.005-0.1 ) a mole allowing to obtain esters with a yield of up to 90.2%.

Claims (1)

The method of producing polyfluoroalkyl ethers of the formula H (CF ₂ ) _n CH ₂ OR (n = 2, 4, 6; R = n-Pr, n-Bu, iso-Bu, n-C ₅ H ₁₁ , iso-C ₅ N ₁₁ , nC ₆ H ₁₃ , C ₆ H ₁₁ (cyclohexyl), R _F (where R _F = H (CF ₂ ) nCH ₂ , n = 2, 4, 6, 8), Ph, ArCH ₂ (where Ar = Ph, p-Cl-Ph, p-CH ₃ O-Ph, m-NO ₂ -Ph)) by the reaction of the corresponding alcohols or phenol with polyfluoroalkylchlorosulfites in the presence of a solvent, which consists in mixing the reagents at a temperature of -10 ÷ -5 ° С, characterized in that alcohols or phenol are metered into a solution of polyfluoroalkylchlorosulfite in a mixture with a catalyst N, N-dimethylformamide at a molar ratio of 1: (1-1.1) :( 0.005-0.1 ) accordingly, the reaction is carried out at 40-50 ° C for 4-6 hours, the released sulfur dioxide and hydrogen chloride are blown off with an inert gas.