CS238906B1 - Processing of fluorinated diaalcali - Google Patents

Description

From the addition of Ν, Ν, Ν *, N'-tetramethyl-1,6-hexanediamine (IV, n 6 6) to tetrafluoroethylene, 1,1,2,2-tetrafluoro-4,11-dimethyl-4,11- diazadecane (1, Ry x HCF 3 CF 3, n = 6), 3-dimethylamino-1,1,2,2-tetrafluoro-9-methyl-9-azadecane (XI, Ry 4 HCF 3 CF 3, n = 6) and 1,1, 2,2-Tetrafluoro-4, 11-dimethyl-5- [1,1,1,2-tetrafluoroethyl-4, U-diazadodecane (XXX, Ry-HCF3CF3, n6) from the addition to chlorotrifluoroethylene gave 1- chloro-1,2,2-trifluoro-4, 11-dimethyl-4,11-diazadodecane (1,1'-HCFCICF, n-6), 1-chloro-3-dimethylamino-1,2,2-trifluoro-9 -methyl-9-azadecane (II). Ry-HCFCICF, n-6) and 1-chloro-5- (2-chloro-1,1,2-trifluoroethyl) -1,2,2-trifluoro-4,11-dimethyl-4,11-diazadodecane / III , Ry HCFCICF, n »6 /.

The process according to the invention is described below with reference to several exemplary embodiments.

He did

To 78.6 g (0.677 mol) of Ν, Ν, Ν ', N'-tetramethyl-1,2-ethanediamine (IV, n = 2), tetrafluoroethylene was introduced at a rate of 0.75 liters under irradiation with a 125 M high pressure mercury vapor lamp. hour for 14 hours.

The weight gain of the reaction mixture was 2.4 g. Rectification of the reaction mixture yielded 1.5 g of a mixture of substances distilling between 62-65 ° C / 2.0 kPa and containing 1,1,2,2-tetrafluoro-4,7- dimethyl-4,7-diazaoctane (1, Ry χ HCF 3 CF 3, na 2) and 3-dimethylamino-1,1,2,2-tetrafluoro-5-methyl-5-azahexane (II, Ry with HCF 3 CF 3, ns 2) v ratio of 56: 44 and 1.4 g of a substance mixture distilling in the range from 50 to 58 ^O C / O, O3 psi and containing 58% of relative 3-dimethylamino-l, l, 2,2,7,7,8,8-octafluoro -5-methyl-5-azaoctane and 42% relative 1,1,2,2,9,9,10,10-octafluoro-4,7-dimethyl-4,7-diazadecane.

Example 2

116.5 g (0.896 mol) of Ν, Ν, Ν ', Ν'-tetramethyl-1,3-propandlamine (IV), on 3) and 11.9 g (0.119 mol) of tetrafluoroethylene were irradiated in a sealed glass ampoule with gamma- ^60. Co dose 5.10 ⁴ Gg.

Rectification of the reaction mixture obtained gave 21.7 g of a mixture of substances distilling between 80 and 89 ° C / 2.5 kPa and containing 45% relative 1,1,2,2-tetrafluoro-4,8-dimethyl-4,8- diazanonan (1, Ry and HCF ₃ CF ₃ , n 3) and 55% relative 3-dimethylamino-1,1,2,2-tetrafluoro-6-roethyl-6-azaheptane (II, Ry x HCF ₂ CF ₂ , n 3) and 3.6 g of a mixture of substances distilling between 63 and 80 ° C (0.1 kPa) and containing 3,5-bis- (dimethylamino) -1,2,2,2,6,6,7,7-octafluorobutane,

1,1 2,2-tetrafluoro-4,8-dimethyl-5- (1,1,2,2-tetrafluoroethyl) -4,8-diazanonane (III), Ry = HCF ₂ CF ₂ , n = 3 /, 3 -dimethylamino-1,1,2,2,8,9-octafluoro-6-methyl-6-azanonane and 1,1,2,2,10,10,11,11-octafluoro-4,8-dimethyl-4- , 8-diazaundecane.

Example 3

The glass ampoule containing 131.5 g / 0.844 mol / N _F N, N ', IJ'-tetramethyl-4-butanediamine / IV, n> 4 / was flushed with nitrogen and evacuated. After cooling in liquid nitrogen, 11.8 g (0.118 mol) of tetrafluoroethylene was uncondensed and sealed.

It was then irradiated with 5 ° Mrad gamma irradiation, opened and rectified to give 20.3 g of a b.p. 87-97 ° C / 2000 Pa containing 1,1,2,2-tetrafluoro, 4. 9-dimethyl-4,9-diazadecane (1'-HCF ₂ CF ₃ , 4 ') and 3 * dimethylamino-1,1,2,2-tetrafluoro-7-methyl-7-azaoctane (II), Ry-HCF ₂ CF ₂ , η χ 4 / at a ratio of 45 to 55 and 3.1 g of a fraction with a boiling point of 50 to 83 ° C / 1,33 Pa which was a mixture of 1,1,2,2-tetrafluoro-4,9-dimethyl-5 - (1,2,2,2-Tetrafluoroethyl) -4,9-palzadecane (III, Ry x HCF 3 CF 3, n 4), 3-dimethylamino-1,1,2,2,9,9,10,10- octafluoro-7-methyl-7-azadecane, 1,1,2,2,11,11,12,12-octafluoro-4,9-dimethyl-4,9-diazadodocane and 3,6-bis (dimethylamino) -1 1,2,2,7,7,8,8-octafluorooctane.

The invention relates to a process for the preparation of fluorinated diazaalkanes of the general formula I and / or II and / or III

Rp-CH ₂ N ₂ / CH / _{N-CH 3} -N

CH.

CH.

/ 1 / Rp-CHn / CH _3/2

- ^ 2 ^ -1 ^ 3

CH, / 11 /,

Rp-CH ₂ -N-CH- / _CH2 / _{N-1 N-CH3}

CH ₃ R p CH ₃ wherein R p is a fluoroalkyl or chlorofluoroalkyl group having a carbon number by radical addition of N, N, N *, N'-tetramethyl-1, omega-alkanediamines (111),

Iku 2-4, n = 2-10, Joint IV / CH _3/2 N / CH ₂ / _N N / _CH3 / ₂ / IV / n 2-10 fluorinated or chlorofluorinated alkenes of the number 2 up to 4 carbon atoms.

Fluorinated diazaalkanes of formulas I, II and III have not been previously described in the literature and can serve as starting compounds for the preparation of fluorinated cationic surfactants.

The invention relates to a process for the preparation of fluorinated diazaalkanes of formulas I, II and III by radically initiated addition of 1, omega-alkanediamines of formula IV to fluorinated or chlorofluorinated alkenes having 2 to 4 carbon atoms.

The reaction is carried out by subjecting a mixture of N, N, N *, N ' -tetraalkyl-1, omega-alkandlamine of the formula IV and a fluorinated alkene to ultraviolet or gamma-ZO Co radiation at temperatures of 10-30 [deg.] C, or is heated in the presence of organic initiators such as di-tert-butyl peroxide, azo-bis-iso-butyronitrile at temperatures of 80-160 ° C, depending on the type of initiator used. The reaction mixture after addition is worked up by distillation, rectification or steam distillation.

The advantage of the process according to the invention is that it is simple to carry out the reaction and the relatively high yields of the addition products of formulas I, II and III, which are otherwise difficult to obtain.

The effect of the process according to the invention is that, under radical conditions, selective fluoroalkylation occurs in the alpha- and / or alpha * - and / or alpha, alpha'- position of the starting amines of the formula IV.

From the addition of N, N, N *, N * -tetramethyl-1,2-ethanediamine (IV, n = 2) to tetrafluoroethylene, 1,1,2,2-tetrafluoro-4,7-dimethyl-4,7- diazaoctane-I, _Rp = HCF ₂ CF ₂ , n · 2 / and 3-dimethylamino-1,1,2,2-tetrafluoro-5-methyl-5-azahexane / II, Rp = HCF ₂ CF ₂ , n 2 /.

Addition of Ν, Ν, Ν *, N'-tetramethyl-1,3-propanediamine (IV, n = 3) to tetrafluoroethylene gives 1,1,2,2-tetrafluoro-4,8-dimethyl-4,8-diazanonan (1, Rp = HCF ₂ CF ₂ , n 2), 3-dimethyl * amino-1,1,2,2-tetrafluoro-6-methyl-6-azaheptane (II) = HCF ₂ CF ₂ , n »2 and 1,1,2,2-tetrafluoro

-4,8-dimethyl-5- (1,1,2,2-tetrafluoroethyl) -4,8-aziazanamine (III, R p = HCF 4 CF 3, n = 3).

From the addition of Ν,-, Ν *, N'-tetramethyl-1,4-butanediamine (IV, n-4) to tetrafluoroethylene, 1,1,2,2-tetrafluoro-4,9-dimethyl-4,9- diazadecane (1, Rp HCF ₂ CF ,, to 4), 3-dimethylamino-1,1,2,2-tetrafluoro-7-methyl-7-azaoctane / II, Rp · HCF ₂ CF ₂ , n · 4 / a 1,1,2,2-tetrafluoro-4,9-dimethyl-5- (1,1,2,2-tetrafluoroethyl) -4,9-diazadecane (III, R _p = HCF ₂ CF ₂ , n = 4) .

Example 4

Tetrafluoroethylene was introduced at an average rate of 0.4 liters per hour to 20 g (0.174 mol) of Ν, Ν, Ν ', N' -tetramethyl-1,4-butanediamine (IV, n = 4) at 20-30 ° C. for 7 hours while irradiating with a high pressure mercury vapor lamp immersed in the reaction mixture.

Rectification of the reaction mixture yielded 2.1 g of a fraction having a boiling point of 85 DEG-96 DEG C./1866 Pa containing 1,1,2,2-tetrafluoro-4,9-dimethyl-4,9-diazadecane / 1, Rp with HCF3 CF3, n = 4 / a 3-dimethylamino-1,1,2,2-tetrafluoro-7-methyl-7-azaoctane (II, Rp b HCF 3 CF 3), n »4 / and 0.4 g of bp 45-80 ° C (10.7 Pa) which contained 1,1,2,2-tetrafluoro-4,9-dimethyl-5- (1,1,2,2-tetrafluoroethyl) -4,9-diazadecane (III), Rp * HCF 3 CF 3 , n = 4, 3-dimethylamino-1,1,2,2,9,9,10,10-octafluoro-7-methyl-7-azadecane, 1,1,2,2,11,11,12, 12-octafluoro-4,9-diethyl-4,9-diazadodecane and 3,6-bis (dimethylamino) -1,1,2,2,7,7,8,8-octafluorooctane.

Example 5

The reaction mixture containing 105.6 g (0.613 mol) of Ν, Ν, Ν ', N'-tetramethyl-1,6-hexanedlamine (IV, n 6 6) and 11.5 g (0.199 mol) of chlorotrifluoroethylene was in a sealed glass arapule irradiated with 5 Mrad gamma radiation - ⁶⁰ co.

Rectification of the resulting reaction mixture yielded 16.2 g of a boiling point of 87-95 ° C (8 Pa) which was a mixture of 1-chloro-1,2,2-trifluoro-4, 11-dimethyl-4,1-diazadodecane / 1, Rp = HCFCICF, n6 and 1-chloro-3-dimethylamino-1,2,2-trifluoro-9-methyl-9-azadecane (II),

Rp b HCFC1CF ₂ , n - 6 / and 2.1 g of a bp 110-112 ⁰ C / 8 Pa containing 1-chloro-5/2-chloro-1,1,2-trifluoroethyl / 1,2,2, 2-Trifluoro-4,11-dimethyl-4,11-diazadodecane (III, Rp b HCFCICF, η b 6) and 1,12-dichloro-10-dimethylamino-1,2,2,11,11,12-hexa Fluoro-4-methyl-4-azadodecane.

Example

The reaction mixture containing 119.8 g (0.695 mol) of N, N, N ', N'-tetramethyl-1,6-hexanediamine (IV, η b 6) and 14.9 g (0.149 mol) of tetrafluoroethylene was in a sealed glass vial irradiated with a total dose of 5 Mrad with gamma radiation - ^6O Co.

Rectification of the reaction mixture after irradiation yielded 19.7 g of a boiling point fraction of 75-80 ° C / 10.7 Pa containing 1,1,2,2-tetrafluoro4,11-dimethyl-4,11-diazadodecane / 1, Rp b HCF 3 CF 3, η b 6) and 3-dimethylamino-1,1,2,2-tetrafluoro-9-methyl-9-azadecane (II, Rp HCF 3 CF 3, n = 6) and 2.7 g of the boiling point 101-110 ° C / 12 Pa containing 1,1,2,2-tetrafluoro-4, H-dimathyl-5- (1,1,2,2-tetrafluoroethyl) -4,11-diazadodecane (III), Rp = HCF 3 CF 3, n 6 / a 10-dimethylamino-1,1,2,2,11,11,12,12-octafluoro-4-methyl-4-azadodecane.

The fluorinated diazaalkanes of the present invention serve as starting materials for the preparation of catalyzed fluorinated surfactants.

Claims (2)

SUBJECT OF THE INVENTION A process for the preparation of fluorinated diazaalkanes of the general formula I and / or XI and / or III Rp - CH ₂ - N - / CH ₂ / _N - N - CH ₃ CH ₃ CH _3/1 /, R _p - CH - / CH ₂ / _n _ ₃ - N - CH ₃ N / CH _3/2 CH / 11 /, R _F - CH ₂ - N - CH - / CH ₂ / _n - ₁ - N - CH ₃ CH ₃ R p CH ₃ (111), wherein R p is a fluoroalkyl or chlorofluoroalkyl group having 2 to 4 carbons, ns 2 to 4 10, wherein the Ν, Ν, Ν ', Ν' tetramethyl-1, omega-alkanediamines general pattern IV / CH _3/2 N / CH ₂ / _N N / _CH3 / ₂ / IV /. wherein n »2 to 10 add under radical conditions to fluorinated or chlorofluorinated alkenes having a carbon number of 2 to 4 and the resulting mixture of products of formula I, II, III is separated by rectification. 2. The method of claim 1, wherein the initiation of the radical addition is effected by ultraviolet radiation in the wavelength range 200 to 600 nm. preferably mercury vapor lamps or γ gamma-radiation, or organic initiators, preferably peroxides and azo compounds.