Patent Publication Number: US-4147743-A

Title: Ampholytic, fluorine-containing esters of phosphorous acid

Description:
The invention relates to ampholytic, fluorine-containing esters of phosphorous acid of the general formula ##STR3## in which R f  represents a perfluoroalkyl radical having 3 to 16 C atoms, R 1  and R 2  which can be identical or different represent hydrogen atoms, short-chain alkyl radicals having 1 to 4 C atoms, cyclohexyl radicals, 2-hydroxyalkyl radicals or the radical R f  --(CF═CH) m  --(CH 2 ) p  and Q represents alkylene radicals --(CH 2 ) x  -- with x = 2 or 3 and alkylene radicals --CH 2  CHR-- or --CH 2  CRR&#39;--CH 2  -- with R and R&#39; being a short-chain alkyl radical or a phenyl radical, it also being possible for R&#39; to be H, and in which, furthermore, m is 0 or 1 and p is an integer from 1 to 4. 
     In the general formula indicated above, R f  preferably represents a perfluoroalkyl radical having 5 to 12 C atoms, and straight-chain perfluoroalkyl radicals are particularly preferred. R 1  and R 2  which can be identical or different are preferably straight-chain alkyl radicals having 1 to 4, in particular 1 to 2, C atoms, and also the 2-hydroxyethyl radical, one of the two radicals R 1  to R 2  being especially a 2-hydroxyethyl radical. R 1  or R 2  can also preferably denote a radical of the formula R f  (CF═CH) m  --(CH 2 ) p , and p here preferably is an integer from 1 to 3 and m can be 1 or preferably 0. For Q, in addition to radicals of the structure --(CH 2 ) x  -- with x = 2 or 3, those of the structure --CH 2  CHR-- and --CH 2  CRR&#39;--CH 2  -- are preferred in which R and R&#39; are an alkyl radical having 1 to 2 C atoms and, in particular, are a methyl radical. Preferably, R&#39; can also be a phenyl radical. The index p preferably assumes integral values from 1 to 3. 
     The invention also relates to a process for the manufacture of ampholytic, fluorine-containing esters of phosphorous acid of the abovementioned general formula I, in which R f , R 1 , R 2 , Q, m and p have the abovementioned meaning (also with respect to the preferred limits), in which process amines of the general formula 
     
         R.sub.f --(CF═CH).sub.m --(CH.sub.2).sub.p --NR.sub.1 R.sub.2 
    
     in which R f , R 1 , R 2 , m and p have the abovementioned meaning, are reacted with cyclic phosphites of the general formula ##STR4## in which Q has the abovementioned meaning, at temperatures between +20° C. and +140° C., in bulk or in the presence of polar solvents. In particular, this process according to the invention is carried out with amines of the abovementioned formula and cyclic phosphites of the abovementioned formula, in which R f , R 1 , R 2 , Q, m and p have the preferred meaning mentioned. 
     The said reaction is advantageously carried out at a temperature between +20° and +140° C., preferably between +60° and +140° C. It is appropriate here to initially introduce the fluorine-containing amine, warmed to the reaction temperature, and slowly to add the cyclic phosphorous acid ester, used as the alkylating agent, until the amounts are in an equimolar ratio. It is also advisable to blanket the reaction mixture with an inert gas, such as, for example, nitrogen. The reaction is preferably carried out under normal pressure, but it is also possible to operate under reduced pressure or, especially in the presence of solvents, under a slightly elevated pressure. In principle, the reaction does not require a solvent. However, for easier handling of the starting materials and end products, which are very viscous at room temperature, it is advantageous to add polar solvents which appropriately are capable of dissolving both the starting materials and the end products. Polar solvents, such as methanol, ethanol, isopropanol, methylene chloride, chloroform as well as glycol and dimethyl glycol are particularly suitable. At the reaction temperatures of +60° to +120° C., which are generally used, the reaction has ended after about 2 to 4 hours. To increase the conversion and the reaction rate, it has proved to be particularly advantageous to add a relatively small amount of water, preferably  1 to 10 mole %, to the reaction process. 
     The fluorinated amines employed as the starting compounds can be manufactured, for example, in accordance with U.S. Pat. No. 3,535,381, U.S. Pat. No. 3,257,407, DT-OS No. 2,141,542 or DT-OS No. 1,768,939. For the further reaction with the cyclic esters of phosphorous acid, it is also possible successfully to employ mixtures of saturated and unsaturated fluorinated amines of the abovementioned formula, that is to say those amines in which m is 0 or 1. The cyclic esters of phosphorous acid, used as the further reaction component, are readily accessible from the corresponding 1,2- or 1,3-glycols and phosphorus trichloride by methods which are generally known (compare Houben-Weyl, Methoden der organischen Chemie, [Methods of Organic Chemistry], 4th edition, volume 12; 2, page 25 to 26). They can also be obtained directly by transesterification of dialkyl phosphites with the corresponding glycols (ibid. page 35 to 36). 
     The resulting yields of ampholytic, fluorine-containing esters of phosphorous acid according to the invention, of the formula I, are virtually quantitative and most of these compounds are excellently soluble in water. The solvent which may have been added can be separated off by distillation, if necessary under reduced pressure. In many cases, however, this is unnecessary since the compounds according to the invention are employed in the dissolved form, if necessary with the addition of water. 
    
    
     The examples which follow illustrate the manufacture of the compounds according to the invention: 
     EXAMPLE 1 
     399.2 g = 1.0 mole of C 5  F 11  CF═CH--CH 2  --N(C 2  H 5 ) 2 , 500 ml of isopropanol and 5 ml of water are initially introduced into a glass flask which is equipped with a stirrer, reflux condenser, dropping funnel and thermometer, the mixture is heated up to the boiling point of isopropanol and 150.1 g (= 1.0 mole) of a cyclic phosphite of the formula ##STR5## are then added in the course of 20 minutes. The reaction mixture is then boiled under reflux for a further 4 hours. After the reaction has ended, the isopropanol is distilled off and even small residual amounts of the solvent are removed by applying a water pump vacuum. This gives a light brown oil which is highly viscous at room temperature and which is soluble in water giving a clear solution. 
     Yield: 545.6 g = 99.3% of theory. 
     The nuclear magnetic resonance spectra of the substance showed the following signals: 
       1  H nuclear magnetic resonance spectrum (measured here and in the further examples using a 60 MHz instrument from Messrs. Japan Electron Optics Co. Ltd. at 25° C., with tetramethylsilane as an internal standard; the signals are indicated in ppm in accordance with the δ scale) in d 4  -methanol: 
     
         ______________________________________                                    
 ##STR6##       doublet with a coupling constant  of ˜629 Hz        
5.7 to 6.8: CFCH                                                          
                triplettized doublet                                      
 ##STR7##        multiplet                                                
3.7 to 4.1: HO.sub.2 POCH.sub.2                                           
                multiplet                                                 
 ##STR8##       superimposing multiplets                                  
 ##STR9##       triplet                                                   
 ##STR10##      singlet                                                   
______________________________________                                    
 
    
       19  F nuclear magnetic resonance spectrum (measured here and in the further examples using a 56 MHz spectrometer from Messrs. Japan Electron Optics Lab. Co. Ltd. at 25° C. with trifluoroacetic acid as an external standard, data in ppm), in CHCl 3  : 
     
         ______________________________________                                    
2.6:             --CF.sub.3                                               
43.8 to 45.0:    =CF-13 CF.sub.2 --(CF.sub.2).sub.3 --                    
47.5:            CF.sub.3 --CF.sub.2 --                                   
39.0:            =CF--CF.sub.2 --                                         
______________________________________                                    
 
    
     EXAMPLE 2 
     5 g of water and 237.0 g of a mixture of fluorine-containing amines of the formula ##STR11## and of the following composition R f  = C 5  F 11  = 41.8% by weight, C 7  F 15  = 34.4% by weight, C 9  F 19  = 17.7% by weight and C 11  F 23  = 6.1% by weight are initially introduced into a glass flask which is equipped with a stirrer, reflux condenser, dropping funnel and thermometer, the mixture is heated to about 80° C. and blanketed with nitrogen and 75.06 g of ##STR12## are then added in the course of half an hour. 
     The reaction mixture which initially consists of two phases is then heated up to 120° C., whilst stirring well, and kept at this temperature for 2 hours. After cooling, this gives 314 g of a brown, clear, highly viscous oil, which is very readily soluble in water without a residue (yield: 99.8% of theory). The nuclear magnetic resonance spectra of the substance shows the following signals: 
       1  H spectrum in d 4  -methanol 
     
         ______________________________________                                    
 ##STR13##       Doublet with a coupling constant of ˜ 654 Hz       
7.6 to 7.9: CH.sub.2 OH                                                   
                 broad singlet                                            
5.7 to 6.7: CFCH triplettized doublet                                     
 ##STR14##       and HO.sub.2 POCH.sub.2multiplets                        
 ##STR15##       and CH.sub.2 OH multiplets                               
 ##STR16##       singlet                                                  
 ##STR17##       singlet                                                  
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
30:               --CF.sub.3                                              
39.0:             --CH=CF--CF.sub.2 --                                    
43.4 to 44.2      --(CF.sub.2).sub.n --                                   
45.0:             --CF.sub.2 --CF=CH--                                    
48.0:             CF.sub.3 --CF.sub.2 --                                  
______________________________________                                    
 
    
     The following further compounds of the general formula I were prepared in accordance with the methods described in Example 1 and 2 (with and without solvent). 
     
         __________________________________________________________________________
                                                  Reaction                
                                                  tempera-                
Sub-                                              ture                    
stance                                                                    
    Starting                                  Reaction                    
No. Formula                    materials      Solvent                     
                                                  time Yield              
__________________________________________________________________________
 3                                                                        
     ##STR18##                                                            
                                ##STR19##     Iso- pro- panol             
                                                  3 hours/ 100° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.5%              
 4                                                                        
     ##STR20##                                                            
                                ##STR21##     Iso- pro- panol             
                                                  3 hours/ 100° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.3%              
 5                                                                        
     ##STR22##                                                            
                                ##STR23##     with- out solvent           
                                                  5 hours/ 100°    
                                                       98.8%              
 6                                                                        
     ##STR24##                                                            
                                ##STR25##     with- out solvent           
                                                  2 hours/ 140°    
                                                       98.8%              
 7                                                                        
     ##STR26##                                                            
                                ##STR27##     with- out solvent           
                                                  3 hours/ 140°    
                                                       98.2%              
 8                                                                        
     ##STR28##                                                            
                                ##STR29##     Iso- pro- panol             
                                                  2 hours/ 120° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.3%              
 9                                                                        
     ##STR30##                                                            
                                ##STR31##     Iso- pro- panol             
                                                  4 hours/ 100° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.6%              
10                                                                        
     ##STR32##                                                            
                                ##STR33##     Iso- pro- panol             
                                                  4 hours/ 100° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.0%              
11                                                                        
     ##STR34##                                                            
                                ##STR35##     Iso- pro- panol             
                                                  2 hours/ 120° C. 
                                                  nder auto- genous       
                                                  pressure                
                                                       97.8%              
12                                                                        
     ##STR36##                                                            
                                ##STR37##     with- out solvent           
                                                  4 hours/ 105°    
                                                       98.2%              
13                                                                        
     ##STR38##                                                            
                                ##STR39##     Iso- pro- panol             
                                                  5 hours/ 80°     
                                                       98.9%              
14                                                                        
     ##STR40##                                                            
                                ##STR41##     Iso- pro- panol             
                                                  5 hours/ 80°     
                                                       98.5%              
15                                                                        
     ##STR42##                                                            
                                ##STR43##     Iso- pro- panol             
                                                  5 hours/ 80°     
                                                       97.2%              
16                                                                        
     ##STR44##                                                            
                                ##STR45##     Iso- pro- panol             
                                                  5 hours/ 80°     
                                                       98.6%              
17                                                                        
     ##STR46##                                                            
                                ##STR47##     with- out solvent           
                                                  4 hours/ 120°    
                                                       92.0% (after       
                                                       recryst- allization
                                                       ) Elementary       
                                                       analysis: cal-     
                                                       found: culated:    
                                                       C26.3%  26.5% H    
                                                       1.7% 1.7% N 1.8%   
                                                       1.7% F60.4%60.4% P 
                                                       .7% 3.8%           
18                                                                        
     ##STR48##                                                            
                                ##STR49##     with- out solvent           
                                                  4 hours/ 120°    
                                                       94% (after         
                                                       recryst- allization
                                                       ) cal- found:      
                                                       culated: C28.9%    
                                                       28.3% H 2.3% 1.9%  
                                                       N 1.4% 1.3%        
                                                       F61.0%58.7% P 3.2% 
                                                       .9%                
19                                                                        
     ##STR50##                                                            
                                ##STR51##     with- out solvent           
                                                  4 hours/ 140°    
                                                       97.4%              
20                                                                        
     ##STR52##                                                            
                                ##STR53##     with- out solvent           
                                                  5 hours/ 140°    
                                                       99%                
21                                                                        
     ##STR54##                                                            
                                ##STR55##     with out solvent            
                                                  3 hours/ 120°    
                                                       98.2%              
__________________________________________________________________________
 
    
     nuclear magnetic resonance spectra for Examples 3 to 21: 
     EXAMPLE 3 
       1  h spectrum in CDCl 3   
     
         __________________________________________________________________________
 12.05 1.62                                                               
      ##STR56##            doublet with a coupling constant of ˜629 
                           Hz                                             
5.6  to      6.6: CFCH     triplettized doublet                           
3.7  to                                                                   
              ##STR57##    and HO.sub.2 POCH.sub.2 ; multiplets           
2.7  to                                                                   
              ##STR58##    quartet and broad singlet                      
1.0  to                                                                   
              ##STR59##    triplet                                        
0.9:                                                                      
              ##STR60##    singlet                                        
__________________________________________________________________________
 
    
       19  F spectrum in CDCl 3   
     
         ______________________________________                                    
2.9:               --CF.sub.3,                                            
38.5:              --CF.sub.2 --CF═                                   
42.0 to 44.5       --(CF.sub.2).sub.4 --                                  
45.5:              --CF.sub.2 --CF═                                   
47.2:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 4 
       1  h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane. 
     
         __________________________________________________________________________
 11.9 1.5                                                                 
      ##STR61##            doublet, coupling constant of ˜624 Hz    
6.8  to      7.1: CH.sub.2 OH                                             
                           broad singlet                                  
5.7  to      6.6: CFCH     triplettized doublet                           
3.8  to                                                                   
              ##STR62##    and HO.sub.2 POCH.sub.2 multiplets             
2.9  to                                                                   
              ##STR63##                                                   
                            ##STR64##                                     
2.6  to      2.7:                                                         
              ##STR65##                                                   
1.1  to      1.4:                                                         
              ##STR66##                                                   
__________________________________________________________________________
 
    
       19  f spectrum in CHCl 3   
     
         ______________________________________                                    
3.5:                --CF.sub.3                                            
39.5:               ═CF--CF.sub.2 --                                  
43.0 to 45.5:       --(CF.sub.2).sub.n --                                 
46.0:               --CF.sub.2 --CF═                                  
48.2:                CF.sub.3 --CF.sub.2 --                               
______________________________________                                    
 
    
     EXAMPLE 5 
       1  h spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane (1:1) 
     
         __________________________________________________________________________
 12.2 1.5                                                                 
      ##STR67##            doublet, coupling constant 642 Hz              
                            broad, indistinct singlet                     
5.6  to      6.7: CFCH     triplettized doublet                           
3.8  to                                                                   
              ##STR69##    multipet                                       
 3.2  to                                                                  
              ##STR70##     superimposing muliplets                       
2.5  to                                                                   
              ##STR71##    singlet                                        
0.87:                                                                     
              ##STR72##    singlet                                        
__________________________________________________________________________
 
    
       19  F NMR spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane (1:1) 
     
         ______________________________________                                    
30:                 --CF.sub.3                                            
39.3:               --CF.sub.2 --CF═                                  
42.5 to 44.5:       --(CF.sub.2).sub.4 --                                 
45.0:               --CF.sub.2 --CF═                                  
47.8:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 6 
       1  h nmr spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane (1:1) 
     
         ______________________________________                                    
 12.17 1.55                                                               
      ##STR73##               doublet, coupling constant 637 Hz           
5.7  to 6.6:   CFCH           triplettized doublet                        
3.5  to 4.1:                                                              
                ##STR74##     and CH.sub.2OPO.sub.2 H multliplets         
3.2  to 3.5:                                                              
                ##STR75##     multiplet                                   
2.75:                                                                     
                ##STR76##     singlet                                     
0.86:                                                                     
      ##STR77##                                                           
               singlet                                                    
______________________________________                                    
 
    
       19  F spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane (1:1) 
     
         ______________________________________                                    
3.0:                 CF.sub.3 --                                          
39.4:               --CF.sub.2 --CF═                                  
42.5 to 45.0:       --(CF.sub.2).sub.6 --                                 
45.5:               --CF.sub.2 --CF═                                  
48.0:                CF.sub.3 --CF.sub.2 --                               
______________________________________                                    
 
    
     EXAMPLE 7 
       1  h nmr spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 12.2 1.6                                                                 
      ##STR78##              doublet, coupling constant 636 Hz            
6.8  to 7.4:    C.sub.6 H.sub.5                                           
                             multiplet                                    
5.4  to 6.4:    CFCH         triplettized doublet                         
3.5  to 4.4:                                                              
                 ##STR79##   CH.sub.2OP.sub.2 H multiplets                
2.8  to 3.2:                                                              
                 ##STR80##   multiplets                                   
1.1  to 1.4:                                                              
                 ##STR81##                                                
                              ##STR82##                                   
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
2.9:               CF.sub.3 --                                            
39.0:             --CF.sub.2 --CF═                                    
43.5 to 45.0:     --(CF.sub.2).sub.2 --CF--CF═                        
47.7:              CF.sub.3 --CF.sub.2 --                                 
______________________________________                                    
 
    
     EXAMPLE 8 
       1  h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 11.90 1.63                                                               
      ##STR83##              doublet, coupling constant 616 Hz            
7.4  to 7.9:    OH           broad singlet                                
5.7  to 6.7:    CFCH         triplettized doublet                         
3.5  to 4.5:                                                              
                 ##STR84##   CH.sub.2 OH and HO.sub.2 POCH.sub.2 superimpo
                             sed multiplets                               
2.7  to 2.8:                                                              
                 ##STR85##   singlet                                      
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
3.0:                --CF.sub.3                                            
39.0:               ═CF--CF.sub.2 --                                  
43.0 to 44.2:       --(CF.sub.2).sub.n --                                 
45.0:               ═CF--CF.sub.2 --                                  
48.0:                CF.sub.3 --CF.sub.2 --                               
______________________________________                                    
 
    
     EXAMPLE 9 
       1  h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 12.40 1.51                                                               
      ##STR86##               doublet, coupling constant 653 Hz           
5.5  to 6.3:   CFCH           triplettized doublet                        
3.4  to 4.4:                                                              
                ##STR87##     and CH.sub.2 OP.sub.2 H multiplets          
2.4  to 3.0:                                                              
                ##STR88##     quartet                                     
1.0  to 1.5:                                                              
                ##STR89##                                                 
                               ##STR90##                                  
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
3.4:                --CF.sub.3                                            
39.2:               ═CF--CF.sub.2 --                                  
43.0 to 45.0:       --(CF.sub.2).sub.4 --                                 
48.0:                CF.sub.3 --CF.sub.2 --                               
49.0:               ═CF--CF.sub.2                                     
______________________________________                                    
 
    
     EXAMPLE 10 
       1  h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 ##STR91##                                                                
      ##STR92##               doublet, coupling constant 618 Hz           
5.8  to 6.8:   CFCH           triplettized doublet                        
3.5  to 4.2:                                                              
                ##STR93##     and CH.sub.2 OP.sub.2 H multiplets          
2.8  to 3.3:                                                              
                ##STR94##     quartet                                     
1.0  to 1.6:                                                              
                ##STR95##                                                 
                               ##STR96##                                  
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
2.6:              --CF.sub.3                                              
38.9:             ═CF--CF.sub.2 --                                    
43.8 to 45.0:     ═CF--CF.sub.2 --(CF.sub.2).sub.2 --                 
47.5:              CF.sub.3 --CF.sub.2 --                                 
______________________________________                                    
 
    
     EXAMPLE 11 
       1  h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 11.85  1.61                                                              
      ##STR97##               doublet, coupling constant 614 Hz           
7.8  to 8.3:   OH             broad singlet                               
5.70 to 6.70:  CFCH           triplettized doublet                        
3.5  to 4.4:                                                              
                ##STR98##     CH.sub.2 OH and CH.sub.2 OPO.sub.2 H        
                              superimposing multiplets                    
2.7  to 2.8:                                                              
                ##STR99##     singlet                                     
1.3  to 1.5    CH.sub.2CH.sub.2CH.sub.2                                   
                              multiplet                                   
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
3.0:             --CF.sub.3                                               
39.0:            ═CF--CF.sub.2 --                                     
42.5 to 45.5:    --(CF.sub.2).sub.n --CF.sub.2 --CF═                  
47.8:             CF.sub.3 --CF.sub.2 --                                  
______________________________________                                    
 
    
     EXAMPLE 12 
       1  h spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 ##STR100##                                                               
          doublet with a coupling constant of 636 Hz                      
7.8 to 8.2:                                                               
          CH.sub.2 OH broad singlet                                       
5.7 to 6.8:                                                               
          CFCHtriplettized doublet                                        
3.8 to 4.4:                                                               
           ##STR101##                                                     
          HO.sub.2 POCH.sub.2multiplets                                   
2.8 to 3.4:                                                               
           ##STR102##                                                     
2.82:                                                                     
           ##STR103##                                                     
0.82:                                                                     
           ##STR104##                                                     
______________________________________                                    
 
    
       19  F spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 3.3:            CF.sub.3 --                                              
38.3:            --CF.sub.2 --CF═                                     
42.5 to 45.0:    --(CF.sub.2).sub.4 --CF.sub.2 --CF═                  
48.0:            CF.sub.3 --CF.sub.2 --                                   
______________________________________                                    
 
    
     EXAMPLE 13 
       1  h spectrum in CDCl 3   
     
         ______________________________________                                    
 ##STR105##                                                               
          doublet with a coupling constant of 635 Hz                      
8.1 to 8.3:                                                               
           ##STR106##                                                     
3.6 to 4.2:                                                               
          CH.sub.2OPO.sub.2 Hmultiplet                                    
2.9 to 3.3:                                                               
           ##STR107##                                                     
2.0 to 3.3:                                                               
          CF.sub.2CH.sub.2CH.sub.2unresolved multiplet                    
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
 3.1:               --CF.sub.3                                            
35.2:               --CF.sub.2 --CH.sub.2 --                              
42.0 to 45.0:       --(CF.sub.2).sub.5 --                                 
47.7:               CP.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 14 
       1  h spectrum in CDCl 3   
     
         ______________________________________                                    
 ##STR108##                                                               
          doublet with a coupling constant of 632 Hz                      
8.3 to 9.2:                                                               
           ##STR109##                                                     
3.8 to 4.2:                                                               
          CH.sub.2OPO.sub.2 H multiplet                                   
2.7 to 3.3:                                                               
           ##STR110##                                                     
2.0 to ˜3.3:                                                        
          CF.sub.2CH.sub.2CH.sub.2unresolved multiplet                    
1.2 to 1.5:                                                               
          CH.sub.2CH.sub.2CH.sub.2multiplet                               
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
 3.4:               CF.sub.3 --                                           
35.3:               --CF.sub.2 --CH.sub.2 --                              
42.0 to 45.5:       --(CF.sub.2).sub.5 --                                 
47.8:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 15 
       1  h spectrum in CDCl 3   
     
         ______________________________________                                    
 ##STR111##                                                               
          doublet with a coupling constant of 633 Hz                      
8.8 to 9.4:                                                               
           ##STR112##                                                     
3.8 to 4.2:                                                               
          CH.sub.2OPO.sub.2 H multiplet                                   
2.8 to 3.3:                                                               
           ##STR113##                                                     
2.6 to 2.7:                                                               
           ##STR114##                                                     
2.1 to 3.2:                                                               
          CF.sub.2CH.sub.2broad, unresolved multiplet                     
______________________________________                                    
 
    
       19  F spectrum in CDCl 3   
     
         ______________________________________                                    
 2.6:                CF.sub.3 --                                          
34.6:                --CF.sub.2 --CH.sub.2                                
42.0 to 45.0:        --(CF.sub.2).sub.5 --                                
47.2:                CF.sub.3 --CF.sub.2 --                               
______________________________________                                    
 
    
     EXAMPLE 16 
     
         ______________________________________                                    
 ##STR115##                                                               
          doublet                                                         
6.5 to 7.0:                                                               
           ##STR116##                                                     
3.8 to 4.2:                                                               
          CH.sub.2OPO.sub.2 H multiplet                                   
2.9 to 3.4:                                                               
           ##STR117##                                                     
2.1 to 3.2:                                                               
          CF.sub.2CH.sub.3broad, unresolved multiplet                     
0.9 to 1.1:                                                               
           ##STR118##                                                     
______________________________________                                    
 
    
       19  F spectrum in CDCl 3   
     
         ______________________________________                                    
 2.6:               CF.sub.3 --                                           
35.0:               --CF.sub.2 --CH.sub.2 --                              
42.5 to 45.0:       --(CF.sub.2).sub.3 --                                 
47.5:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 19 
       1  h spectrum in CDCl 3   
     
         ______________________________________                                    
 ##STR119##                                                               
          doublet, coupling constant 638 Hz                               
7.0 to 7.5:                                                               
          C.sub.6 H.sub.5 unstructured multiplet                          
6.6 to 7.0:                                                               
          OHbroad singlet                                                 
5.4 to 6.5:                                                               
          CFCHtriplettized doublet                                        
3.5 to 4.4:                                                               
           ##STR120##                                                     
          CH.sub.2OPO.sub.2 H multiplets                                  
2.8 to 3.4:                                                               
           ##STR121##                                                     
2.5:                                                                      
           ##STR122##                                                     
1.1 to 1.3:                                                               
           ##STR123##                                                     
______________________________________                                    
 
    
       19  F spectrum 
     
         ______________________________________                                    
 2.7:               CF.sub.3 --                                           
38.8:               --CF.sub.2 --CF═                                  
42.5 to 45.0:       --(CF.sub.2).sub.n --                                 
45.5:               ═CF--CF.sub.2 --                                  
47.7:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 20 
       1  h spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 ##STR124##                                                               
          doublet with coupling constant of 636 Hz                        
3.8 to 4.2:                                                               
          CH.sub.2OPO.sub.2 H unresolved multiplet                        
2.8 to 3.4:                                                               
           ##STR125##                                                     
          CH.sub.2 OH unresolved multiplets                               
2.9:                                                                      
           ##STR126##                                                     
1.1 to 2.5:                                                               
          CF.sub.2CH.sub.2CH.sub.2broad, unresolved multi-                
          plet, partially super-                                          
           ##STR127##                                                     
0.8 to 0.9:                                                               
           ##STR128##                                                     
______________________________________                                    
 
    
       19  F spectrum in CDCl 3  /1,1,2-trichloro-1,2,2-trifluoroethane 
     
         ______________________________________                                    
 3.2:               CF.sub.3 --                                           
35.5:               --CF.sub.2 --CH.sub.2 --                              
42.5 to 45.5:       --(CF.sub.2).sub.4 --                                 
48.0:               CF.sub.3 --CF.sub.2 --                                
______________________________________                                    
 
    
     EXAMPLE 21 
       1  h spectrum in CDCl 3   
     
         ______________________________________                                    
 ##STR129##                                                               
          doublet with coupling constant of 632 Hz                        
5.5 to 6.6:                                                               
          CFCHtriplettized doublet                                        
3.6 to 4.3:                                                               
           ##STR130##                                                     
2.6 to 3.4:                                                               
           ##STR131##                                                     
1.1 to 1.5:                                                               
           ##STR132##                                                     
0.9                                                                       
           ##STR133##                                                     
______________________________________                                    
 
    
       19  F spectrum in CHCl 3   
     
         ______________________________________                                    
 3.0:            CF.sub.3 --                                              
38.4:            --CF.sub.2 --CF═                                     
42.0 to 45.5:    --(CF.sub.2).sub.n --CF.sub.2 --CF═                  
47.3:            CF.sub.3 --CF.sub.2 --                                   
______________________________________                                    
 
    
     Amongst the fluorinated surface-active agents hitherto known, the ampholytic, fluorine-containing esters of phosphorous acid of the formula I, according to the invention, are distinguished by a high surface-active effectiveness. This is shown by the measured surface tension values determined in water (see Table No. 1). Here and in the following text, the compounds are compared with the following 6 fluorine-containing surface-active agents of the state of the art, which contain ester groups of acids of phosphorus and/or quaternary nitrogen: 
     V1: Ammonium bis-(N-ethyl-2-perfluoro-octyl-sulfonamidoethyl) phosphate with at most 15% of ammonium mono-(N-ethyl-2-perfluorooctyl-sulfonamidoethyl) phosphate (compare U.S. Pat. No. 2,803,656). 
     
         ______________________________________                                    
 ##STR134##          (compare DT-OS 1,922,277)                            
 ##STR135##          (compare U.S. Pat. Specification 2,759,019)          
 ##STR136##          (compare U.S. Pat. Specification 3,083,224)          
 ##STR137##          (compare DT-OS 2,405,042)                            
V6: C.sub.6 F.sub.13 C.sub.2 H.sub.4 OPO.sub.3 H.sub.2                    
                     (compare U.S. Pat.                                   
                     Specification 3,083,224)                             
______________________________________                                    
 
    
     
                                           Table No. 1                             
__________________________________________________________________________
Measured surface tension values at 20° C. in mN/m, measured by     
the `du Nouy tensiometer method` (draft DIN 53,914)                       
in aqueous solution                                                       
                  F content in                                            
Ex- Concentration (g/l)                                                   
                  the active                                              
ample                                                                     
    5 1 0.3                                                               
          0.1                                                             
            0.03                                                          
               0.01                                                       
                  substance                                               
                          The product was present as                      
__________________________________________________________________________
1   20                                                                    
      22                                                                  
        27                                                                
          37                                                              
            47 60 41.5%   Oil with 100% of active substance               
2   19                                                                    
      19                                                                  
        20                                                                
          23                                                              
            29 45 44.0%   Oil with 100% of active substance               
2a  19                                                                    
      20                                                                  
        22                                                                
          23                                                              
            30 43 44.0%   2 as a solution in isopropanol with             
                          50% by weight of active substance               
3   20                                                                    
      20                                                                  
        23                                                                
          35                                                              
            46 53 46.8%   Oil with 100% of active substance               
4   18                                                                    
      19                                                                  
        20                                                                
          23                                                              
            28 34 47.5%   Oil with 100% of active substance               
5   17                                                                    
      18                                                                  
        22                                                                
          33                                                              
            48 59 50.1%   Oil with 100% of active substance               
6   19                                                                    
      20                                                                  
        25                                                                
          35                                                              
            55 56 52.7%   Oil with 100% of active substance               
7   21                                                                    
      24                                                                  
        28                                                                
          32                                                              
            37 46 37.3%   Oil with 100% of active substance               
8   18                                                                    
      18                                                                  
        20                                                                
          22                                                              
            33 47 48.7%   Oil with 100% of active substance               
11  16                                                                    
      17                                                                  
        19                                                                
          21                                                              
            29 37 47.5%   Oil with 100% of active substance               
19  18                                                                    
      19                                                                  
        21                                                                
          23                                                              
            30 44 41.3%   Oil with 100% of active substance               
20  --                                                                    
      20                                                                  
        22                                                                
          24                                                              
            29 43 44.8%   Oil with 100% of active substance               
V1  22                                                                    
      --                                                                  
        47                                                                
          48                                                              
            62 63 21%, relative                                           
                          36% strength by weight solution in              
                  to the solution                                         
                          isopropanol/water                               
V2  22                                                                    
      23                                                                  
        35                                                                
          46                                                              
            56 57 49.8%   100% of active substance                        
V3  18                                                                    
      18                                                                  
        19                                                                
          21                                                              
            25 33 41.1%   100% of active substance                        
V4  27                                                                    
      31                                                                  
        43                                                                
          54                                                              
            66 -- 22.4%, relative                                         
                          34.5% by weight in 1:1 isopropanol/water        
                  to the solution                                         
V5  20                                                                    
      21                                                                  
        24                                                                
          35                                                              
            42 46 11.6%, relative                                         
                          19.9% by weight in isopropanol/water            
                  to the solution                                         
__________________________________________________________________________
 
    
     A further interesting property of the compounds according to the invention is their foaming behaviour (Table No. 2). The foam formation test according to Ross-Miles shows that, in the compounds according to the invention, the foaming power can be controlled by the chain length of the perfluoroalkyl radical. In addition to the weak foamers No. 1 and No. 7 having C 5  F 11  radicals, there are the strongly foaming products No. 3 and No. 4 having C 7  F 15  radicals. The product No. 2 or 2a with mixtures of perfluoroalkyl chains of C 5  -C 11  shows a medium foaming behaviour. The foaming power can be increased by omitting branches at the methyl groups adjacent to the phosphite group (comparison between compounds No. 8 and No. 2). As a result of their different foaming behaviour, the fluorinated surface-active agents according to the invention are available as tailor-made products for various applications. Thus, strongly foaming surface-active agents are employed for cleaning agents, whilst weak foamers having good values for lowering the surface tension are employed in aqueous phase for degreasing metal parts in electroplating lines. 
     
         ______________________________________                                    
Foam height (mm) at                                                       
25° C.         70° C.                                       
Example 0 minutes  5 minutes  0 minutes                                   
                                      5 minutes                           
______________________________________                                    
1       10         0          10      0                                   
2       75         70         30      25                                  
2a      65         65         85      85                                  
3       150        140        80      30                                  
4       50         50         35      35                                  
5       190        190        240     240                                 
6       90         90         160     160                                 
7       10         0          10      0                                   
8       150        140        160     160                                 
11      180        180        220     220                                 
V1      0          0          5       0                                   
V2      240        240        200     190                                 
V3      100        100        260     260                                 
______________________________________                                    
 
    
     Due to their surface properties, the ampholytic fluorinated phosphites according to the invention are widely used as surface-active agents in the textile industry for wetting and cleaning. Table No. 3 describes the wetting power of the products according to the invention towards cotton and wool in an aqueous system. The determination was carried out in accordance with an immersion wetting test in the following manner: 
     Determination of the immersion wetting power: 
     A disc (about 35 mm φ) of the test fabric is introduced into the test solution (600 ml beaker, tall type) by means of an immersion clamp in such a way that it is held about 30 mm above the bottom and 40 mm below the surface of the liquid. The disc sinks to the bottom when the air has been displaced from the fabric. The time from the immersion to the start of sinking is measured by means of light beams which are connected to a switch box (Viscomatik instrument). The pair of light beams is arranged in such a way that the determination of time corresponds to the DIN 53,901 method. 
     
         ______________________________________                                    
Sinking time (seconds)                                                    
Cotton                     Wool                                           
Example 25° C.                                                     
                  50° C.                                           
                             70° C.                                
                                     25° C.                        
______________________________________                                    
1       175       165        75      13                                   
2       145       100        60      18                                   
3       180       130        80      17                                   
4       &gt;300      235        95      8                                    
5       105       90         65      18                                   
6       &gt;300      155        75      6                                    
7       &gt;300      &gt;300       180     25                                   
8       135       165        95      14                                   
9       115       75         50      17                                   
11      45        30         25      7                                    
19      50        40         12      6                                    
V1      &gt;300      &gt;300       &gt;300    &gt;300                                 
V2      270       135        65      7                                    
V3      300       165        45      13                                   
______________________________________                                    
 
    
     Due to their good wetting power, the compounds according to the invention can be used as dry-cleaning detergents. Dry-cleaning detergents are interface-active substances which enhance the cleaning action of organic solvents and broaden this action since hydrophilic soilings are also dealt with as the result of incorporating water into the organic medium. Table No. 4 shows the results of cleaning experiments in perchloroethylene. The cleaning experiments were carried out in the following manner: 
     Description of the procedure in the cleaning experiments: 
     Four series of artificially soiled standard test fabrics, in each case cotton, wool, polyester fabric and polyacrylonitrile fabric, manufactured by Testfabrics Inc. Middlesex, Ill. (USA) (soiling: iron oxide, carbon black, starch and oil) are successively cleaned in the same cleaning liquor in the laboratory. Cleaning is carried out in 400 ml of perchloroethylene liquors on fabrics which were conditioned beforehand under the action of atmospheric humidity in order to produce comparable conditions, corresponding to the so-called Lini test (in analogy to DIN Standard 54,024). The concentration of the fluorinated surface-active agents is 0.5 g/l and the temperature is 30° C. 
     The cleaning action is determined as % brightening in accordance with the formula 
     
         A = 100 · (Wg - Wa)/(Wo - Wa) 
    
     Wo = reflectance of the unsoiled original fabric 
     Wg = reflectance of the soiled fabric 
     Wa = reflectance of the soiled fabric after cleaning 
     The graying of the unsoiled original fabric, also treated, is determined in accordance with the formula 
     
         V = 100 · (Wo - Wv)/Wo 
    
     Wo = reflectance of the unsoiled original fabric 
     Wv = reflectance of the cleaned sample 
     On the basis of the brightening and graying values obtained, the products according to the invention are superior to the comparative products V2 and V6. 
     The compounds of the formula I, according to the invention, are also suitable for use as additives to fire-fighting agents based on synthetic foam, in particular in combination with other fluorine-containing surface-active agents. 
     
                                           Table 4                                 
__________________________________________________________________________
Results of the cleaning experiments in perchloroethylene with various     
fluorinated surface-active agents (test fabrics conditioned, before       
cleaning, for 24 hours at 80% relative atmospheric humidity and           
20° C.). B = Brightening, G = Graying                              
          Perchloro-                                                      
                  Product                                                 
                        Product                                           
          ethylene                                                        
                  from  from  Product                                     
                                    Product                               
          without additive                                                
                  Example 1                                               
                        Example 2                                         
                              V2    V6                                    
          % B % G % B                                                     
                     % G                                                  
                        % B                                               
                           % G                                            
                              % B                                         
                                 % G                                      
                                    % B                                   
                                       % G                                
__________________________________________________________________________
Series I.                                                                 
Cotton    2   1.9 3  2.3                                                  
                        4.7                                               
                           1.2                                            
                              6.5                                         
                                 7  0.4                                   
                                       10.9                               
Wool      5.8 0.0 10.8                                                    
                     0.8                                                  
                        15.8                                              
                           0.4                                            
                              0  18 10.5                                  
                                       5.3                                
Polyester fabric                                                          
          5.5 0.7 4.4                                                     
                     1.9                                                  
                        6.4                                               
                           1.1      5  2.0                                
Polyacrylonitrile                                                         
fabric    5.0 3.3 6.5                                                     
                     5.2                                                  
                        8.1                                               
                           3.4      4.2                                   
                                       7.7                                
Series II.                                                                
Cotton    3   4.7 2.6                                                     
                     3.7                                                  
                        4.5                                               
                           1.3                                            
                              1.0                                         
                                 16 0.4                                   
                                       11                                 
Wool      5   2   10 3  15.2                                              
                           0.6                                            
                              3.0                                         
                                 12 10 10.8                               
Polyester fabric                                                          
          6   1.5 3  2.6                                                  
                        5.9                                               
                           1.7      4.8                                   
                                       3.8                                
Polyacrylonitrile                                                         
fabric    6.1 2.9 5.5                                                     
                     3.2                                                  
                        7.7                                               
                           3.5      4.1                                   
                                       8.3                                
Series III.                                                               
Cotton    3.1 5.5 2.7                                                     
                     5.4                                                  
                        4.8                                               
                           1.7                                            
                              2.5                                         
                                 12 1.8                                   
                                       13.8                               
Wool      5.8 0   11.7                                                    
                     3.3                                                  
                        15.6                                              
                           0.7                                            
                              10.0                                        
                                 12.2                                     
                                    11.1                                  
                                       12.2                               
Polyester fabric                                                          
          5   4.1 3.5                                                     
                     5.1                                                  
                        5.7                                               
                           2.0      3.4                                   
                                       3.7                                
Polyacrylonitrile                                                         
fabric    5.3 4.8 5  6.1                                                  
                        7.5                                               
                           3.9      5  9.7                                
Series IV.                                                                
Cotton    3   7.1 2.6                                                     
                     8  4.2                                               
                           2.3                                            
                              1  13 0.8                                   
                                       13.4                               
Wool      5.9 1.1 10.6                                                    
                     2.7                                                  
                        15.1                                              
                           1.0                                            
                              9.0                                         
                                 1.5                                      
                                    13.1                                  
                                       11.8                               
Polyester fabric                                                          
          5.6 4.8 3.5                                                     
                     6.7                                                  
                        5.5                                               
                           2.8      4.5                                   
                                       8.8                                
Polyacrylonitrile                                                         
fabric    5.0 5.7 5  5.4                                                  
                        7.8                                               
                           3.6      4.5                                   
                                       10.1                               
__________________________________________________________________________