FR2516920A1 - Fluorinated sulphide, sulphoxide and sulphone cpds. - useful as gas vehicles and blood substitutes - Google Patents

Abstract

Fluorinated cpds. of formula Rf-C2H4-S(O)x-R' (I) are new (where Rf is a perfluoroalkyl gp. with at least 2C atoms; x=0-2; R' is an alkyl, aryl, aralkyl or alkaryl gp. opt. substd. by OH, alkoxycarbonyl, aryloxycarbonyl, alkanoyl, aroyl, CN, SC2H4Rf or perfluoroalkyl, or R' may be SC2H4R'f when x=O, where R'f is perfluoralkyl). (I) are useful as industrial gas-transport media and/or blood substitutes. They are good solvents for gases and are auto-emulsifiable. (I;x=O) may be prepd. by metallating a thiol of formula RfC2H4SH or R'SH and reacting the resulting thiolate with R'X or RfC2H4I respectively (where X is halogen).

Description

 The present invention relates to novel perfluorinated ring compounds suitable especially as gas carriers useful in industrial applications and more particularly in the biological field as blood substitutes.

 The ability of perfluorinated compounds to dissolve gases is known. It has also been known since 1966, with the work of F. GOLLAN and LC CLARK (Science 152, 1755, 1966), that a perfluorinated derivative can be used instead of blood to ensure, apart from the various physiological functions, the transport and the exchange of oxygen and carbon dioxide within living tissues or organs that one wants to preserve, or even living bodies that one wants to maintain in survival.

 Since then, much work has been done to achieve a partial or complete substitution of blood in an animal or human titer by a composition containing perfluorinated products and many studies have been conducted on organ perfusions by fluorinated compounds. However, in the latter case, and with the compounds currently available, emulsions of a fluorocarbon (or a mixture of fluorocarbons with a surfactant) are generally used. The fluorocarbons are generally perfluorinated amines or cyclic compounds (perfluorodecalin and derivatives, perfluoromethylcyclohexane, perfluoro methyltetrahydrofuran) or F-alkylated alkenes or dienes and the surfactants are generally nonionic polyethers (of the tetronic type), polyoxyethylenes, polyoxypropylenes or phospholipids.

 Likewise, for the substitution of blood, fluorinated product emulsions with a surfactant are generally used. The fluorinated products then used are either amines (in particular perfluorobutylamines), or ethers (in particular perfluorobutyltetrahydrofuran, various "Freons" and various perfluorinated ethers with a linear or cyclic aliphatic chain), or F-alkylE alkenes or dienes, either straight-chain or branched-chain fluorocarbons (perfluoroalkane-like) or cyclic chain fluorocarbons (perfluorodecalin type and its derivatives, fluorinated cyclohexanes and their derivatives, perfluorinated aromatic derivatives) and mixtures of these various compounds. active it is generally chosen from polyols fluorinated nonionic surfactants or surfactants such as egg yolk lecithin, phospholipids, polyoxyethylene-polyoxypropylene mixtures (of the "Pluronic" type).

 Thus, all fluorinated products known and used until now for their application as blood substitutes, require as we see the use of a surfactant for their passage in the form of emulsion and the main problems that we encounter At the present time, it is precisely for each fluorinated compound involved, in terms of the choice of surfactant, and in terms of the emulsification mode to lead to a stable emulsion.

Moreover, it is found that according to the emulsification mode used (for example by sonication) there are significant risks of modification of the chemical structure that may lead to either a toxic product or a product no longer meets the desired characteristics.

On the other hand, milder processes allowing emulsification without excessive energy input, such as that described in French Patent No. 73 39 533, have the disadvantage of requiring the particular determination and choice of at least two surfactants such as those belonging to for example, to the family of polyethoxylated surfactants.

Now the present invention provides novel compounds having the general formula RF 2H 4ASOxR 'wherein is a perfluorinated chain of the form
CnF 2n + 1 with n>, 2
- x equals 0, 1 or 2
R 'is a monovalent organic group of the alkyl, aryl, aralkyl or alkylaryl type, substituted or unsubstituted, the substituents possibly being groups
- hydroxyls

<tb> CO (alkyl <SEP> or <SEP> aryl)
<tb><SEP> o
<tb> - <SEP> C- (alkyl <SEP> or <SEP> aryl)
<tb><SEP> o
<Tb>
- CN
- SC2H4RF (with RF having the meaning here
above)
or
- CmF2m + 1 with m equal to or different from n or else, when x = 0,
R 'can also represent a group -SC2H4R'F with R'F representing -CpF2p + 1 with E equal to or different from n.

 These compounds have the property of well dissolving the gases, in particular O2, CO, CO2, CH4, N2, which allows their application as industrial carriers of dissolved gases.

 They also have the property of being able to give stable emulsions without the need for additional surfactants, which represents a clear improvement over known gas transporters requiring such a supply of surfactants.

 Finally, some of them such as sulphides (x = O) and certain sulphoxides and sulphones (x = 1 or 2 and R '# CH2 linked to an attracting electron group) are chemically inert, which makes them particularly suitable as biological carriers of gas and, especially as substitutes for blood.

The compounds according to the invention also have the advantage that they can be obtained simply and economically with good yields. Thus
the sulphides (x = 0) are obtained in a synthesis proceeding in two stages from a thiol
. the first step consisting of thiol metallation
. the second in the alkylation of the thiolate formed by an alkyl halide
The starting thiol will be either RFC2H4SH, itself obtained simply from RFC2H4I which is commercially available, or R'SH, (RF and R 'having the meaning given above).

 When the starting thiol is flFC2K4 SH, the corresponding metal thiolate will be alkylated by R'X (X being a halogen).

If the starting thiol is R'SH, the corresponding thiolate will be alkylated by iodide
RFC2H4I
The metallization step of the thiol is carried out in the presence of polar solvent (for example HMPT, DMF or
THF) with a conventional metallation reagent such as, for example, sodium amide, sodium hydride or sodium alkoxide.

 The addition of the thiol to the metallation reagent is done under nitrogen at a temperature close to OOC. The mixture is then stirred at ambient temperature for a few hours.

 The alkylation step (II) is carried out by adding to the product of step (i) at OOC the alkylating halide, itself in solution in a polar solvent.

 The reaction is completed by stirring the mixture a few hours at room temperature.

 Then, after hydrolysis, the organic product is extracted, dried, filtered and evaporated (or distilled the solvents) and the product is recovered by distillation under reduced pressure.

 The sulphoxides tex = 1) and the sulphones (x = 2) are obtained from the corresponding sulphides by oxidation sevbre by hydrogen peroxide. To obtain the sulfoxide, it is carried out in acetone medium. To obtain the sulfone, the oxidation is carried out in the presence of acetic acid and a few drops of concentrated sulfuric acid.

 The following examples are given by way of non-limiting illustration.

Example 1
A.Synthesis of RFC2H4SH: (from RF C2 H4 I)
In a 250 ml flask, 0.086 mol of RF-C2H4-I, 0.086 mol of thiourea and 20 ml of absolute ethyl alcohol are placed. The whole is heated with stirring at 800C until complete dissolution of the thiourea. The ethanol is then removed; white crystals are obtained. 41 ml of NaOH (2N) and 7 g of glycine previously dissolved in 15 ml of hot water (approximately 800 ° C.) are added to the same flask.

The whole is then heated with magnetic stirring at 800C for two to three hours. It is distilled under normal pressure; a little water is drawn.

 The denser thiol is in the lower phase. Decant if necessary, dry over Na 2 SO 4 and filter.

 The thiol thus obtained is pure enough for later use. Yield: 85 to 90% of thiol.

The compounds are thus obtained
C2F5-C2H4-SH Eb = 77-780C Rt = 88% C4F9-C2H4-SH Eb = 108-1120C Rt = 80-85%
C6F13-C2H4-SH Eb = 1200C Rt = 88%
C8F17-C2H4-SH F = 400C R t = 86%
The thiols were characterized by elemental analysis, mass spectrometry, proton and fluorine NMR.

B. Synthesis of C6F13-C2H4-S-CH3
In a flask surmounted by a condenser and a dropping funnel, cooled in an ice bath and placed under a nitrogen atmosphere, 1 g of NaH (50% in dispersion in oil), suspended in 20 ml of freshly distilled anhydrous THF. With the dropping funnel, 0.0237 moles of C6F13-C2H4-SH (9 g) in 20 ml of anhydrous THF are added dropwise. The solution becomes red.

After adding the thiol, the bath is removed and the magnetic stirring is continued for one hour at room temperature. The flask is again cooled in an ice bath. With the addition funnel, 3.5 g of
CH3I (- 0.0237 mol) in 20 ml of THF. The mixture becomes light yellow. The reaction mixture is allowed to warm to room temperature and stirring is continued for 3 to 4 hours. It is thrown on ice, extracted with dichloromethane (or ether), dried over Na2SO4. Then the solvents are evaporated in a rotavapor.

 It is distilled under reduced pressure.

 C6F13-C2H4SCH3-Eb / 120 mm = 530C was obtained in 70% yield.

 This product is characterized by infrared, proton NMR and fluorine, mass spectrometry.

We also collect 30% of a heavy product which is sulphide
RF C2H4 SS C2H4 RF
Example 2
Preparation of RFC2H4SC6H5
a) Metallization by NaNH2 (method A)
In a 100 ml Erlenmeyer flask, surmounted by a condenser and a dropping funnel, placed under nitrogen, 0.02 mol of NaNH 2 is placed in 10 ml of HMPT. case, then 10 ml of anhydrous THF and 10 ml of HMPT to dissolve the precipitate which appears.

The temperature is brought to 350.degree.-400.degree. C. and 0.01 mol of RF-C2H4-I is added in one go and NaNH.sub.2 (0.02 mol) is added little by little.

It is then stirred for 20 hours at 35-400C.

It is hydrolyzed with water and extracted with ether. The ether phase is washed 3 times with portions of 50 ml of dilute HCl. Then, wash 3 times with water. We then dry on
Na2SO4, filter, evaporates the solvents.

 The yield varies between 30 and 60%.

The following compounds are obtained: C2F5-C2H4-S-Eb / 30 mm = 450C Rt = 30%
C4F9-C2H4-S Eb / 20 mm = 35 C Rt = 55% C6F13-C2H4-S- Eb / 20 mm = 400C Rt = 55%
C8F17-C2H4-S-Eb / 27 mm = 650C Rt = 50%
b) Metallation for NaH (method B)
In a flask surmounted by a condenser and a dropping funnel, placed under nitrogen, 0.015 mol (2.9 g) of NaH are introduced in suspension in 45 ml of anhydrous DMF. The flask is cooled and the dropping funnel is added dropwise 0.01 mol of -SH in solution in 45 ml of DMF for 45 minutes. The mixture turns red. The bath is removed once the addition of the thiol is complete, and magnetic stirring is continued for 2 hours. The flask is again cooled in an ice bath and the dropping funnel is added dropwise. mole of iodide (RF-C2H4-I), previously dissolved in 30 ml of anhydrous DMF, for one hour.

When the addition is complete, the bath is removed and the magnetic stirring is continued for two hours at 30-350 ° C. The mixture is poured into ice, extracted with dichloromethane, dried over Na 2 SO 4, filtered and the solvents evaporated with a rotavapor. It is distilled under reduced pressure.

Method B gives better yields than method A. Thus, we obtain
RF Efficiency boiling temperature
% (Eb)
C2F5 80 Eb / 30 mm = 450C
C4F9 80 Eb / 30 mm = 43 "C
C6F13 80 Eb / 20 mm = 400
C8F17 75 Eb / 27 mm = 650C
The different products were characterized and identified by elemental analysis, infrared spectrometer, proton and fluorine NMR, mass spectrometry.

Example 3
Preparation of RFC2H4SCH2C6H5
The procedure is as above, replacing thiolphenol SH with thiol CH2SH in the preparations according to methods A and B.

 In method B, C6F13C2H4SCH2 was collected in 85% yield with Eb / 20 mm = 950C.

Example 4 Preparation of sulphides of the form
-C02Et RF-C2H4-S-CH2 Y

CN
-COCH3 CH2OH
General method

 In a flask surmounted by a condenser, a dropping funnel and placed under a nitrogen atmosphere, sodium hydride (0.026 mol) is introduced in suspension in anhydrous THF. The flask is cooled in an ice bath, and the dropping funnel is added dropwise thiol (0.025 mol) dissolved in anhydrous THF. After the addition, the bath is removed and stirring continued for two to three hours.

 The flask is then cooled and the halogenated reagent (0.026 mol) in THF is added dropwise to the dropping funnel. When all the reagent is added, the bath is removed and stirring continued overnight. It is hydrolyzed with water, extracted with ether, dried over Na 2 SO 4, filtered and the solvents evaporated.

 The characteristic of the different products is made by infrared, mass spectrometry, proton NMR and fluorine.

Example 4a
Preparation of RF-C2H4-S-CH2-CO2Et -
a) From 7 g of C2F5-C2H4-SH and 3.5 g of Cl-CH2-CO2Et, 3.6 g of a clear liquid are collected after distillation under reduced pressure. By this method a) C2F5-C2H4-S-CH2-Co2Et is obtained: Eb / 40 mu = 60 CR t = 40%
The percentage of product recovered is low because the product distills with unreacted ethyl chloroacetate.

b) C4F9-C2H4-S-CH2-CO2Et: Eb / 30 1n1n = 97-980C Rt = 75% c) C6F13-C2H4-S-CH2-CO2Et: Eb / 20 nm = 820C R = 80% d) C8F17 -C2H4-S-CH2-CO2Et: Eb / 20 = 90-910C R t = 80%
Example 4b
Preparation of

By proceeding in a similar manner with the appropriate corresponding reagents, the compounds of the above formula are obtained with RF = C2F5 Eb / 0.8 mm = 99-1040C R t = 60%
C4F9 Eb / 0.7 mm = 105-1080C Rt = 70%
C6F13 Eb / o mm = 111-115 CR t = 68%
Example 4c: RF-C2H4-S-CH2-CN - as
C4F9-C2H4-S-CH2-CN: Eb / 20 mm = 1100C
Example 4d: RF-C2H4-S-CH2-C-CH3 - as
O C4F9-C2H4-SC-CH3: Eb / 20 mm = 114-118 C Rt = 56%
O
Example 4e: RFC2H4-S-CH3-CH2OH
Starting from 9 g of C2F5C2H4SH (0.05 mol), 9.5 g of a product which has risen to 85-880 ° C. at 20 mmHg are collected by distillation under reduced pressure.

Yield 78%.

 NMR and mass spectrometry are in agreement with the structure; in IR, #OH is observed around 3500 cm -1.

Example 5
Preparation of di- (F-alkyl-2-ethyl) sulfides (RFC2H4SC2H4R ')
a) Metallation with sodium hydride
In a 100 ml flask equipped with a condenser, a magnetic stirrer and a dropping funnel, cooled in an ice bath, 1 g of NaH and a minimum of
Anhydrous THF for sodium hydride to bath.

 0.02 mol of RF-C2H4-SH previously dissolved in 20 ml of anhydrous THF are added dropwise under a nitrogen atmosphere. After addition of thiol complete, the bath is removed and stirring is continued for 2 to 3 hours at room temperature. The flask is then cooled in an ice bath and the dropping funnel is added with the stoichiometric amount of iodide RF-C2H4-I (or R'F-C2H4I).

A change of color is observed. After addition of the iodide, the bath is removed and allowed to stir at room temperature overnight.

 It is hydrolyzed with water, extracted with ether and dried over Na 2 SO 4. After filtration, the solvents are evaporated in a rotary evaporator. It is distilled under reduced pressure and the sulphide is obtained.

C6F13-C2H4-S-C2H4-C6F13: Eb / 20 mm - 117-1200C Rt = 74%
C6F13-C2H4-S-C2H4-C4F9: Eb / 20 mm = 114-1150C Rt = 76% C6F13-C2H4-S-C2H4-C2F5: bp = 96-990C Rt = 75%
C4F9-C2H4-S-C2H4-C2F5 Eb / 20 mm 86 86-870C Rt = 76%
The products obtained were characterized and identified by elemental analysis, mass spectrometry, infrared spectrometry, proton and fluorine NMR, as an example for RF = R 'F = C6F13, elemental analysis gives
Calculated Found
% C 26.46 26.36
% H 1,11 1,01
% S 4.41 4.59
% F 68.02 68.04
The NMR results added to those of the elemental analysis indicate the presence of two RF = C6F13 chains.

Mass spectrometry confirms the presence of these chains by their characteristic fragmentations. Proton NMR shows two multiplets attributable to both CH2 (between 2.5-3 ppm and 2.6-3 ppm). The mass spectrum shows a base peak at m / e 393 attributable to C6F13CH2CH2S = CH2.

b) Metallation with sodium alkoxide
{sodium ethoxide)
In a 500 ml flask equipped with a condenser, a magnetic stirrer and a dropping funnel cooled in an ice bath, 5.06 g of sodium and 108 ml of absolute ethanol are added. 76 g (0.2 moles) of thiol C6F13C2H4SH are added dropwise under a nitrogen atmosphere in 200 ml of
Anhydrous THF.

 After addition of the complete thiol, the ice bath is removed and stirred at room temperature for two to three hours.

 It is cooled again to 0-5 ° C. and 94.8 g (0.2 mol) of C6F13C2H4I iodide are added. There is a change in color from brown red to light red. The bath is removed and stirred for 2 to 3 hours at room temperature.

 It is hydrolyzed with water, extracted with ether and dried over Na 2 SO 4. The mixture is filtered and the THF-distilled and then distilled under reduced pressure to recover the sulfide.

 Eb / 0.05 mm = 78-880C Yield 75%.

 purity 96%.

Elemental analysis gives
theoretical found
C% 26.46 26.28
H% 1.11 1.31
S% 4.41 4.22
68.04%
Example 6
A. Synthesis of sulfones
In a flask equipped with a condenser and a dropping funnel, 1 ml of H 2 O 2 (110 volumes), 2.5 ml of CH 3 COOH and a few drops of concentrated H 2 SO 4 are placed. 0.003 moles of sulfide in 1.5 ml of CH 3 COOH are added dropwise to the dropping funnel. The addition is made by cooling the balloon or not in a water bath.

 Once the addition is complete, the mixture is heated at 80 850C for three hours. It is poured on ice, extracted with dichloromethane or with chloroform or even with ethyl ether. The organic phase is washed two to three times until the neutral pH. It is dried over Na 2 SO 4, filtered and the rotavapor solvents are removed. -We recover white crystals.

1) C8F17-C2H4-SO2--
From 1.6 g of C8F17-C2H4-S-O (0.0029 mol), 1.5 g of sulfone are recovered after recrystallization from petroleum ether.

F = 1230C R t = 90%
2) C6F13C2H4-SO2- # -
From 12.1 g of C6F13-C2H4-S- (0.0029 mol), 10.2 g are recovered.

F = 1190C Rt = 85% 3) C4F9-C2H4-SO2- #: F = 1100C Rt = 95% 4) C2F5-C2H4-SO2-: F = 96C Rt = 95% 5) C6F13-C2H4-SO2-C2H4 -C6F13: F = 110-1130C
Rt = 98% 6) C6F13-C2H4-SO2-CH2- #: F = 1190C
Rt = 90% 3) Other sulfones
Functionalized sulfones RF-C2H4-SO2-CH2-X

la réaction a lieu à température ambiante.<tb><SEP> -Co2And, <SEP> CO # <SEP>
<tb> avex <SEP> X <SEP> =
<tb><SEP> -CN, <SEP> COCH3
<tb> were synthesized by this method.
Only to

the reaction takes place at room temperature.

: F = 95-980C R t = 90 % : F = 104-1060C R t = 85 % : F = 108-111 C R t = 90 % C6F13-C2H4-S02-CH2-CN : F = 95-980C R t = 90 % C6F13-C2H4-S02-CH2-COCH3 F = 111-112 C R t = 87 %
B. Caractérisation des sulfones
Les produits ont été caractérisés par spectroscopie infrarouge (produit en solution dans le chloroforme), par
RMN du proton dans le chloroforme deutéré CDCl3, RMN du fluor dans CFCl3,spectromérie de masse. These sulfones were recrystallized from carbon tetrachloride C2F5-C2H4-SO2-CH2-CO2Et: F = 38-390C Rt = 70% C4F9-C2H4-SO2-CH2-CO2Et: F = 48-500C Rt = 74% C6F13- C2H4-SO2-CH2-CO2Et: F = 63-660C R t = 70%
C8F17-C2H4-SO2-CH2-CO2Et: F = 79-800C R t = 73%

: F = 95-980C R t = 90%: F = 104-1060C R t = 85%: F = 108-111 CR t = 90% C6F13-C2H4-SO2-CH2-CN: F = 95-980C R t = 90% C6F13-C2H4-SO2-CH2-COCH3 F = 111-112 CR t = 87%
B. Characterization of sulfones
The products were characterized by infrared spectroscopy (product in solution in chloroform), by
Proton NMR in deuterated chloroform CDCl3, fluorine NMR in CFCl3, mass spectrometry.

Example 7
Formation of sulfoxides by oxidation of the corresponding sulphides

In this example, 1.5 g of
C6F13-C2H4-S-, 10 ml acetone and 15 ml H2O2.

After heating for 3 hours at 500 ° C. (conditions under which no reaction is observed), the reaction medium was left for 2 days at room temperature. The resulting crystals were collected
PF: 1250C
They are not soluble in CC14, but soluble in ether. The NMR spectrum confirmed the presence of phenyl groups and C2H4. The mass spectrometry is in agreement with the proposed structure as well as the elemental analysis.

Quantitative yield.

 By analogously proceeding from 1 g of C4F9-C2H4-S-a quantitative yield of sulfoxide of the above formula was obtained in the form of white crystals melting at 1100C.

 The compounds according to the invention, some examples of which have been given above, have the characteristic of well dissolving the gases. This characteristic has been demonstrated by the method of determining the gas solubility by gas chromatography consisting in making a chromatographic column packed with a support impregnated with the product to be tested and injecting on this column the gas of which it is desired to study solubility.

By way of example, the results obtained by this method for the solubility in
C6 F13 C2 H4 SC2 H4 C6 F13 (A) of different gases
SOLUBILITY K EXPRESSED IN THE FORM OF THE COEFFICIENT OF HENRY
+
at # 10 z IN THE SOLUÑT A

<tb> Gas <SEP> 23 <SEP> 35
<tb> 02 <SEP> 0.28 <SEP> 0.215
<tb> N2 <SEP> 0.24 <SEP> 0.16
<tb> H2 <SEP> 0.17 <SEP> 0.12
<tb> CO <SEP> 0.24 <SEP> 0.16
<tb> CH4 <SEP> 0.33 <SEP> 0.25
<tb> C02 <SEP> 1.30 <SEP> 1.04
<Tb>
These results were obtained by GPC on a copper column = 6.35 mm and 3 m long lined with teflon powder impregnated with 40 g of A per 100 g of Teflon.

 For comparison, the solubility of oxygen in the blood at 37 C is 20% under 1 bar.

 Similarly, it turns out that in the presence of water they easily form emulsions without requiring the addition of a surfactant.

 By way of illustration of the surfactant character, it should be noted that the surface tension measured with the CAHN electro balance of C6 F13 C2 H4 SC2 4 C6 F13 is 21.2 dynes / cm at ambient temperature and 20, 3 dynes / cm at 370C.

Finally, all sulphides (x = O) are chemically inert: only oxidation under severe conditions (see examples above) leads to sulfones and sul oxides
Not only compounds of the form RFC2H4SC2H4RF or RFC2H4SC2H4R 'F' RFCZHqS-alkyl, RFC2HqS-alkylary] RFC2H4S-aryl, AFC2H4S-aralkyl do not alkylate on hydrogen carried by carbon to alpha sulfur and this even in the Hardest alkylation conditions (different metallizing media having been tested such as, for example, NaH / THF, nBuLi / THF, nBuLi / HMPT, nBuLi and the like at different temperatures and up to reflux of the solvents as well as different alkylating reagents as for example, RFC2H4f, CH3I, C2H5I, C6H5CH2Br and the like) but even sulfides in which this alpha to sulfur hydrogen is activated by the presence of a substituent
R 'of the form -CH2- linked to an electron-withdrawing group, prove to be equally inert with respect to these alkylation reagents.

The same inertness is observed for all the sulphides of the invention with respect to aromatic, homo- or heterocyclic aldehydes with which they have been tried to condense them.

The same inertia is observed for sulphoxides and sulphones when the hydrogens on the alpha carbon with respect to the sulfur atom is not activated by a group R 'of the form -CH2- linked to an electron-withdrawing group .

 Because of these characteristics and their combinations these products can be chosen for the intended purpose and applied in industrial chemistry as self-emulsifiable gas carriers and / or biological chemistry as blood substitutes.

 It goes without saying that the invention has been described as purely explanatory and not limiting and that any useful modification can be made without departing from its scope.

Claims (3)

 1. New perfluorinated chain compounds having the characteristic of being both good gas dissolvents, and of being self-emulsifiable, characterized in that they meet the general formula C2H4tS x + R in which :  - RF is a perfluorinated chain of the form  CF2n + i with na 2  - x equals 0, 1 or 2  - R 'is a monovalent organic group of the alkyl, aryl, aralkyl, alkylaryl, non-substituted, the substituents may be groups  - hydroxyls

 SC2H4R'F with R'F representing -CpF2p + 1 with E equal to or different from n.  R 'can also represent a group  - C F2m + l with m equal to or different from n or else, when x = 0,  or  above)  - SC2H4RF (with RF having the meaning here  - CN <Tb> <tb> <SEP> O <tb> - <SEP> C- (alkyl <SEP> or <SEP> aryl) <tb> <SEP> O <tb> - <SEP> C <SEP> -O (alkyl <SEP> or <SEP> aryl)  2. Application of the compounds according to claim as gas carriers in industrial chemistry and / or as blood substitutes in biological chemistry.  3. Process for the manufacture of the compounds according to claim 1, characterized in that it consists in the metallation of a thiol RFC2H4SH or R'SH (R and R 'having the meaning given to this claim) followed by an alkylation thiolate formed by means of a corresponding alkyl halide of the R'X or RCvH4I type to obtain the desired sulphide compounds (where x = 0), the sulphoxides (x = 1) and the sulphones (x = 2) which can then be be obtained from the corresponding sulphides by oxidation with hydrogen peroxide.