GB1583363A

GB1583363A - Amphoteric fluorinated sulphonamides

Info

Publication number: GB1583363A
Application number: GB3572977A
Authority: GB
Original assignee: Produits Chimiques Ugine Kuhlmann; Ugine Kuhlmann SA
Current assignee: Produits Chimiques Ugine Kuhlmann; Ugine Kuhlmann SA
Priority date: 1977-05-12
Filing date: 1977-08-25
Publication date: 1981-01-28
Also published as: CH599142A5; FR2390426B2; IT1117098B; BR7703531A; BE855791R; FR2390426A2; NL7706475A

Description

(54) AMPHOTERIC FLUORINATED SULPHONAMIDES (71) We, PRODUITS CHIMIQUES UGINE KUHLMANN, a French Body Corporate, of 25 boulevard de l'Amiral Bruix, 75116 Paris, France, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to amphoteric fluorinated sulphonamides.

In our British Patent Specification No. 1343990, we describe a class of particularly surface active amphoteric fluorinated sulphonamide compounds corresponding to the general formula:

in which CnF2n+l represents a straight or branched perfluorinated alkyl chain in which n is an integer from 1 to 20, a is an integer from 2 to 10, R1 is a hydrogen atom, an alkyl radical containing 1 to 6 carbon atoms, or the radical CF2+1 - (CH2)a - SO2-, R2 and R3 are alkyl radicals containing 1 to 3 carbon atoms, and at least one of these radicals must be methyl, p is 0 or an integer from 1 to 10 and q is an integer from 2 to 10.

In our British Patent Specification No. 1343990 there is also described a method of preparing the amphoteric fluorinated sulphonamides of general formula (I) which comprises reacting with a polyfluoroamine compound of general formula (II)

either with a saturated aliphatic lactone of general formula:

or an a-ethylenic acid of the general formula: H (CH2)q2 - CH = CH - COOH (IV) The sulphonamides of general formula (II), and their preparation are described and claimed, inter alia, in our British Patent Specification No. 1304135.

We have now found that certain N-alkylated derivatives have an advantage that they have an improved solubility in organic solvents.

According to one aspect of the present invention there is provided amphoteric fluorinated sulphonamides of the general formula:

wherein CnF2n+l represents a straight or branched perfluorinated alkyl chain in which n is an integer from 1 to 20, preferably from 6 to 10, a is an integer from 2 to 10, R2 and R3 are alkyl radicals containing 1 to 3 carbon atoms, and at least one of these radicals must be methyl, p is 0 or an integer from 1 to 10, R; is an alkyl radical containing from 1 to 6 carbon atoms and b is 1.

The present invention also provides a process for the preparation of the fluorinated sulphonamides of general formula (V) which comprises (i) reacting an acid chloride of the general formula: CnF2n+l - (CH2)a - SO2 Cl (VI) wherein n and a are as defined above, with an amine of the general formula:

wherein p, R;, R2 and R3 are as defined above to give a product of the general formula:

and (ii) reacting the product of formula (VIII) with a carboxylic acid salt of the general formula X - CH2 - COOM (X) wherein X is a halogen atom, and M is an alkali metal or alkaline earth metal atom.

In order to prepare a compound of general formula (V) in which b is greater than or equal to 2, a compound of formula (VIII) is reacted at ambient temperature with an a-ethylenic acid of formula: H-(CH2) b-2 - CII = CH - COOH (IX) wherein b' is an integer of 2 or more.

Preferably, the a-ethylenic acid of formula (IX) is acrylic acid.

The N-alkylated sulphonamide products of the present invention are of particular interest because they have greater solubility in organic media than analogous sulphonamides in which the R; group is replaced by a hydrogen atom.

This feature is illustrated by the experimental results shown in the Table which sets out the + solubility in certain organic solvents of C6F1.7 - C2H4 - SO2N'H-(CH2) - N (CH3)2-CH2CH2 - COO (FOR 1116) and of its N' - methylated derivative (FOR 1116A), and of C6F13-C2H4 - SO2N'H - (CH2) - N (cm3)2 - CH2 - COO (FOR 1157) and of its N' - methylated derivative (FOR 1157A) TABLE Solubility in g of dry product/100 g of solution Solvent FOR 1116 FOR 1116A FOR 1157 FOR 1157 A Ethyl O.QS 0.65% 0.08% 0.12% acetate Toluene 0.007% 0.015% 0.001% 0.003% Cyclo- 0.004% 0.005% 0.001% 0.002% hexane The process of preparation of the N-alkylated sulphonamides in which b is an integer of two or more by the action of an a-ethylenic acid (IX) on the polyfluoroamine compounds of general formula (VIII) is particularly interesting because it provides a chemical process for the preparation of the said products which can be performed with complete safety.The process for preparing such N-alkylated sulphonamides which comprises reacting a polyfluoroamine (VIII) with a saturated aliphatic lactone (HI) is unsafe because it is now known that the said lactones have carcinogenic properties.

The following Examples illustrate the present invention.

Examole 1

446.5 g (1 mole) of C6Fl3C2H4SO2Cl are introduced over one hour into- a reactor containing 348 g (3 moles) of trimethyl N,N,N' diamino-1,3 propane CI-E3NH-CH2-CH2CH,N (CH3)2 dissolved in 400 cc of chloroform. In the course of this addition the temperature rises to 65at. The mixture is then heated under reflux for two hours and the chloroform solution is then washed three times with 500 cc of water. By evaporation of the chloroform 500 g of C6F13 C2H4S02N(CH3)CH2CH2CH2N(CH3)2 are obtained.

This product is in the form of a white powder, melting point 50"C. The yield of the reaction is 95 %.

105 g (0.21 mole) of C6F > 3C2H4SO2N(CH3)CH2CH2CH2N(CH3)2 prepared as described above, 200 cc of carbon tetrachloride, and 22 g (0.39 mole) of acrylic acid are introduced into a reactor. The solution is agitated at ambient temperature for 36 hours. The precipitate formed is collected by filtration and then dried in vacuo. 115 g (yield 96%) of a yellow pasty solid are thus obtained, which is identified as being

Example 2

A solution of 54.6 g (0.1 mole) of C8Ffi7C2H4SO2Cl dissolved in 40 cc of ethyl acetate are introduced over one hour into a reactor containing 35 g (0.30 mole) of CH3NH-CH2CH2CH,N (cho)2 dissolved in 60 cc of ethyl acetate. During the addition the temperature is kept at 25"C by cooling. At the end of the addition the reaction mixture is kept at 25"C for 3 more hours and then heated under reflux for one hour. The reaction mixture is then washed three times with 60 cc of water and the organic phase is evaporated.

After drying in vacuo there are thus obtained 49 g of a white solid product which was identified as being C8F17C2H4SO2N(CH3) CH2 CH2 CH2 N (cur3)2 (yield 78 %). 31.3 g 51 millimoles) of this product are then dissolved in 100 cc of carbon tetrachloride and 7.2 g 100 millimoles) of acrylic acid are added. The mixture is kept under agitation for 36 hours and then 34 g of a pasty solid are collected by filtration, this solid being identified as:

Example 3 446.5 g of C6F13C2H4SO2Cl are introduced over a period of one hour into a reactor containing 290 g of N,N' trimethylpropanediamine-1,3 dissolved in 400 cc of chloroform. In the course of this addition the temperature rises to 650C. The mixture is then heated under reflux for two hours, and then the chloroform solution is washed four times with 300 cc of water.By evaporation of the chloroform, 495 g of

are obtained in the form of a yellowish powder, melting point 49"C.

49.6 g of chloracetic acid, 21 g of sodium hydroxide, and 500 cc of 95% ethanol are introduced into a reactor. This mixture is heated under reflux for one hour, whereupon the pH is adjusted to 7 by adding either sodium hydroxide or chloroacetic acid. 263 g (0.5 mole) of

are then added and the mixture heated under reflux while verifying from time to time the content of unconverted amine. At the end of 4 hours there remained 11% of unconverted sulfamidamine, while at the end of 8 hours only 3% remained. The reaction mixture was then freed of sodium chloride by filtration and by evaporation of the solvent 290 g of a solid of yellow colour was obtained, which was identified as being:

WHAT WE CLAIM IS:1. Amphoteric fluorinated sulphonamides of the general formula

wherein CnF2n+, represents a straight or branched perfluorinated alkyl chain in which n is an integer from 1 to 20, a is an integer from 2 to 10, R2 and R3 are alkyl radicals containing 1 to 3 carbon atoms, and at least one of these radicals must be methyl, p is 0 or an integer from 1 to 10, R; is an alkyl radical containing from 1 to 6 carbon atoms and b is 1.

2. A fluorinated sulphonamide according to Claim 1, in which n is an integer from 6 to 10.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

After drying in vacuo there are thus obtained 49 g of a white solid product which was identified as being C8F17C2H4SO2N(CH3) CH2 CH2 CH2 N (cur3)2 (yield 78 %). 31.3 g

51 millimoles) of this product are then dissolved in 100 cc of carbon tetrachloride and 7.2 g

100 millimoles) of acrylic acid are added. The mixture is kept under agitation for 36 hours and then 34 g of a pasty solid are collected by filtration, this solid being identified as:

Example 3 446.5 g of C6F13C2H4SO2Cl are introduced over a period of one hour into a reactor containing 290 g of N,N' trimethylpropanediamine-1,3 dissolved in 400 cc of chloroform. In the course of this addition the temperature rises to 650C. The mixture is then heated under reflux for two hours, and then the chloroform solution is washed four times with 300 cc of water.By evaporation of the chloroform, 495 g of

are obtained in the form of a yellowish powder, melting point 49"C.

49.6 g of chloracetic acid, 21 g of sodium hydroxide, and 500 cc of 95% ethanol are introduced into a reactor. This mixture is heated under reflux for one hour, whereupon the pH is adjusted to 7 by adding either sodium hydroxide or chloroacetic acid. 263 g (0.5 mole) of

are then added and the mixture heated under reflux while verifying from time to time the content of unconverted amine. At the end of 4 hours there remained 11% of unconverted sulfamidamine, while at the end of 8 hours only 3% remained. The reaction mixture was then freed of sodium chloride by filtration and by evaporation of the solvent 290 g of a solid of yellow colour was obtained, which was identified as being:

WHAT WE CLAIM IS:1.Amphoteric fluorinated sulphonamides of the general formula

wherein CnF2n+, represents a straight or branched perfluorinated alkyl chain in which n is an integer from 1 to 20, a is an integer from 2 to 10, R2 and R3 are alkyl radicals containing 1 to 3 carbon atoms, and at least one of these radicals must be methyl, p is 0 or an integer from 1 to 10, R; is an alkyl radical containing from 1 to 6 carbon atoms and b is 1.
2. A fluorinated sulphonamide according to Claim 1, in which n is an integer from 6 to 10.
3. A fluorinated sulphonamide of formula
4. A fluorinated sulphonamide of formula:
5. A fluorinated sulphonamide of formula:
6. A process for the preparation of fluorinated sulphonamides according to Claim 1 which comprises (i) reacting an acid chloride of the general formula: CnF2n+l - (CH2)a - SO2 Cl (VI) wherein n and a are as defined in Claim 1, with an amine of the general formula:

wherein, R" R2 and R3 are as defined in Claim 1, to give a product of the general formula

and (ii) reacting the product of formula (VIII) with a carboxylic acid salt of the general formula: X - CH2 - COOM (X) wherein X is a halogen atom, and M is an alkali metal or alkaline earth metal atom.
7. A process according to Claim 6, substantially as described in Example 3.
8. A fluorinated sulphonamide according to any one of Claims 1, 2 or 5 when prepared by a process as claimed in Claim 6 or 7.