Patent Publication Number: US-4482713-A

Title: Quaternary ammonium salts and their preparation

Description:
Among cationic surfactants, quaternary ammonium salts have achieved great importance, and are used, for example, as biocides, as cationic detergents, as emulsifiers in building protection and anti-corrosion technology and in ore dressing, and as dyeing assistants in the textile and leather industries. 
     The starting materials for quaternary ammonium salts are tertiary amines, which can be converted into the ammonium salts by alkylation. The availability of these salts thus depends on the accessibility of the corresponding tertiary amines. 
     Tertiary amines have hitherto essentially been prepared by catalytic hydrogenating alkylation of amine/alcohol or amine/aldehyde mixtures. Typical side reactions are trans-alkylations, which, especially in the case of unsymmetrically substituted amines, lead to product mixtures which can be worked up only with difficulty. In particular, product mixtures are obtained in the reaction of polyalkylene glycol ethers, as the alcohol component, with amines under alkylating hydrogenation conditions as a result of splitting of the ether. It is therefore very difficult to prepare, in good yield, tertiary alkyl- or aryl-polyether-amines having a particular structure, and consequently corresponding quaternary ammonium salts are also not readily accessible. 
     In contrast, (poly)alkanolamines having free hydroxyl groups and ammonium salts thereof are readily accessible, in particular by oxyalkylation of ammonia or a primary or secondary amine with an alkylene oxide, in which a quaternary ammonium salt, which, like the alkanolamine employed, still contains hydroxyl groups, is obtained with an alkylating agent in a conventional manner. In many fields of use, these quaternized alkanolamines are inferior to the simple polyalkylammonium salts. 
     There has as yet been no possibility of obtaining good yields of polyether-quaternary salts with blocked end groups by etherifying the hydroxyl groups of these alkanolammonium salts. When prepared from an alcoholate and an alkylating agent, eg. an alkyl halide, under Williamson ether synthesis conditions, the quaternary salts decompose by Hofmann degradation. 
    
    
     I have found that alkylation of an alkanolamine (I) or an alkanolammonium salt (II) with an alkylating agent R 3  X (III) or R 4  X (IV) in the presence of a phase transfer catalyst under mild conditions gives a quantitative yield of novel substances, namely polyether-quaternary salts (V) with blocked end groups, in accordance with the following equation: ##STR1## 
     The first reaction can evidently be regarded as N-alkylation and the second as O-alkylation. 
     R 1  and R 2  can be identical or different and each is alkyl, cycloalkyl, aryl, aralkyl, alkylaryl or alkoxyalkyl or a (poly)alkylene glycol radical, or R 1  and R 2 , together with the nitrogen atom, can also be a heterocyclic ring, which may contain further hetero-atoms, in which case R 1  and R 2  together are a divalent alkylene, oxaalkylene or azaalkylene radical, which, depending on availability, may also contain one or more, generally short-chain, alkyl substituents. 
     If a polyfunctional amine in which one or more substituents R 1  or R 2  are in turn substituted by a tertiary amino group --NR 1  R 2  is used as the starting material, the novel quaternary salt can likewise contain several ammonium groups. 
     In the above formulae, A furthermore is alkylene of 2 to 10 C atoms, X is a substituent of a conventional alkylating agent, in particular a halide, a (metho)sulfate or an (alkyl)aryl-sulfonate, and n is an integer, in particular an integer from 1 to 5. 
     R 1 , R 2  and R 3  can in themselves be any desired shape and size, for example straight-chain or branched. In general, compounds in which these substituents are alkyl of 1 to 20, in particular 2 to 20, carbon atoms, aryl of 6 or 10 carbon atoms, alkylaryl or aralkyl of 7 to 20 carbon atoms, alkoxy(polyoxy)alkyl of 3 to 100 or more carbon atoms or (poly)alkylene glycol groups of 2 to 100 or more carbon atoms are of particular industrial interest. 
     The alkanolamines can accordingly be reaction products of ammonia, a primary or secondary alkylamine, a polybasic amine or a polyamine and an alkylene oxide, eg. dimethylethanolamine, triethanolamine, triisopropanolamine, butyldiethanolamine, diethylethanolamine, tetrahydroxyethylhexamethylenediamine and (poly)oxyalkylates thereof, and also alkanolamines of a different origin, eg. 3-dimethylaminopropanol, dimethylneopentenolamine, N,N&#39;-dimethylneopentanediamine and oxyalkylates thereof. Suitable alkylene oxides include ethylene oxide, propylene oxide and butylene oxide. Most of the above alkanolamines, and many other such compounds, are commercially available. 
     Conventional alkylating agents R 3  X (III) and R 4  X (IV) which can be used are alkyl, (alkyl)aryl, benzyl or 2-alkylene halides, methosulfates, and arylsulfonates, for example benzyl chloride, methyl chloride, cyclohexyl bromide, dimethyl sulfate and methyl p-toluenesulfonate. 
     In principle, any alkali metal hydroxide or alkaline earth metal hydroxide may be used as the base, but sodium hydroxide solution is preferred, for economic reasons. 
     Suitable phase transfer catalysts are quaternary ammonium salts, such as are described in the relevant literature (cf. E. V. Dehmlow, Angew. Chem. 86, (1974), 187-196), eg. trialkylbenzylammonium salts and tetraalkylammonium salts. These ammonium salts can be added as catalysts before the reaction, or they can be prepared in situ from a tertiary amine in the course of the alkylation reaction (for example, triethylbenzylammonium chloride can be prepared from triethylamine and benzyl chloride). 
     The reaction according to the invention sometimes proceeds autocatalytically, ie. the quaternary salt formed catalyzes its own etherification, so that separate addition of a phase transfer catalyst would be superfluous. This situation can always be achieved by a procedure in which part of the reacted mixture is recycled or used as the solvent, especially in the case of continuous operation. 
     The reaction can be carried out as a one-stage process, but is preferably carried out as a two-stage process. In this case, the first step is quaternization (N-alkylation) of the initially introduced alkanolamine to the alkanolammonium salt with an alkylating agent at from 20° to 160° C., preferably at from 40° to 120° C. The etherification (O-alkylation) under phase transfer catalysis does not take place until the second step, after addition of an alkali (preferably as an aqueous alkali metal hydroxide solution in a concentration of from 10 to 60%), at from 20° to 90° C., in particular from 30° to 60° C. The alkylating agent (R 3  X) in the first step may in each case differ from that in the second step (R 4  X). If the same alkylating agent is used in the quaternizing stage as in the etherification stage, a one-stage reaction is also possible, in which case the alkanolamine and the alkali metal hydroxide solution and, where relevant, the foreign phase transfer catalyst are introduced jointly and the above alkylating agent can then be added in one step or at the rate at which it reacts. The quaternizing step can be monitored with the aid of the amine number and, where relevant, the etherification step can be monitored by the liberation of halide, but also by the OH number of a sample of the reaction mixture. 
     The reaction can be carried out in the mixture per se, or in the presence of a suitable solvent, eg. benzene, toluene, chlorobenzene, carbon tetrachloride, methylene chloride and the like, but preferably in water. It usually proceeds under atmospheric pressure. 
     The anion X of the alkylating agent can be replaced by any other desired inorganic or organic anion, and halides, sulfates, phosphates, nitrates and carboxylates are preferred. 
     The reaction mixture is worked up by separating off the alkali metal hydroxide solution, where relevant after dilution with a solvent, eg. isobutanol, isopropanol or another solvent which is immiscible or only slightly miscible with the alkali metal hydroxide solution. Evaporation of the solvent under reduced pressure first gives a crude product which in most cases is pasty. This can be purified further; for example, recrystallization from ethyl acetate or toluene has proved suitable for a large number of products, white, crystalline products of definite melting point being obtained. 
     The particular advantages of the process described are that the quaternary ammonium salts can be synthesized, starting from an amine or ammonia, in a single reaction chamber, eg. a stirred kettle or a cascade of stirred kettles, under mild reaction conditions, working up of the mixtures is simple, without a distillation step for separating mixtures of the desired products, the synthesis is controlled and gives defined products and not isomer mixtures, and quaternary ammonium salts can be synthesized without the use of trisalkylamines which are not readily accessible. 
     The resulting polyether-quaternary salts can be used for the purposes conventional for quaternary ammonium salts, for example as textile assistants, cationic surfactants and the like. 
     The individual substances listed as examples in the Table which follows can all be obtained in accordance with the instructions below. 
     1.1 equivalents of the alkylating agent are added a little at a time to 1 equivalent of a tertiary alkanolamine and 0.03 equivalent of benzyltriethylammonium chloride at the required quaternization temperature (see Table), and the mixture is stirred until the amine titer is less than 0.1 m equivalent/g. The mixture is then left to cool, (n+1) moles of NaOH, in the form of a 50% strength aqueous solution, are added, with further cooling to 40° C., for n moles of hydroxyl groups to be etherified, and a further n moles of alkylating agent are then added, with vigorous stirring. Stirring is continued at 40° C. for some hours, and if necessary the mixture can be diluted with water for easier stirring. Isobutanol and a sufficient amount of water to dissolve all the solids are then added, with stirring, stirring is continued for half an hour, and the aqueous alkali metal hydroxide solution is decanted off. The remaining mixture is washed with water and, finally, the solvent is distilled off under reduced pressure. If necessary, the resulting pasty crude product can be precipitated by being poured into from 250 to 500 ml of ethyl acetate and, finally, can be filtered off. 
     
           Reaction   conditions  Melt- Ex-  Quatern- Subs. Product ing am-
 ization stir- Elementary analysis  point ple Starting Temper- ring
 Empirical C H N Cl.sup.⊖ OHZ (EA) .sup.1 HNMR No. materials
 ature time Yield Structural formula formula % % % % no. °C.
 (starter in ppm)
                 1 89.1 g (1mole) ofdimethyl-ethanol-amine 100° C. 1
 2hours 281 g
  ##STR2##
  C.sub.18 H.sub.24 NOCl 70.1(70.7) 7.8(7.8) 4.2(4.6) 11.8(11.6) 13(O)
 180 in CDCl.sub.3 δ=3.3(s,6H,N(CH.sub. 3).sub. 2)δ=3.9(s,4H,C
 H.sub. 2CH.sub.2)δ=4.5(s,2H,φCH.sub.2
  O)δ=5.1(s,2H,φCH.sub.2H)  265.9 g            δ=7.2-7.8(m
 ,10Hφ)  (2.1  mole) of  benzyl  chloride  80 g of  NaOH  2 117.2 g   m
 (1ole) ofdiethyl-ethanol-amine 100°
  C. 12hours 265 g
 ##STR3##
  C.sub.20 H.sub.28 NOCl 71.9(72.0) 8.5(8.4) 4.2(4.2) 10.1(10.6) 24(0)
 116 in CDCl.sub.3δ=1.4(t,6H,2CH.sub. 3) δ3.2-4.1(m,8H,4CH.sub
 .2)δ=4.6(s,2H,φ-CH.sub.2 O)δ=4.9(s,2H,φOH.sub.2 N)
 265.9 g            δ=7.2-7.7(m,10H,φ)  (2.1  mole) of  benzyl
 chloride  80 g of  NaOH  3 131.2 g (1mole) of4-(2-hy-droxy-ethyl)morpho-
 100°
  C. 12hours 196 g
 ##STR4##
  C.sub.20 H.sub.26 NO.sub.2 Cl 68.7(69.1) 7.3(7.5) 4.2(4.0) 10.1(10.2)
 8(0) 152 in CDCl.sub.3δ=3.3-4.5(m,12H,6CH.sub.3)δ=4.6(s,2H,.p
 hi.CH.sub.2 O) δ=5.2(s,2H,φCH.sub.2
  N)δ=7.1-7.8(m,10H,φ )  line 265.9  g of ben-  zyl  chloride
 80 g of  NaOH  4 119.2 g (1mole) ofNmethyl-diethan- 100° C.
 12hours 360 g
  ##STR5##
  C.sub.26 H.sub.32 NO.sub.2 Cl 72.7(73.3) 7.4(7.5) 3.3(3.3) 8.5(8.3)
 4(0) 107 in CDCl.sub.3δ=3.2(s,3H,CH.sub.3)δ=3.9(s,8H,2C.sub.2
  H.sub.4)δ=4.5(s,4H,2φCH.sub.2
  O)δ=5.1(s,2H,φCH.sub.2
  N)  olamine            δ=7.2-7.5(m,15H,φ)  392.5 g  (3.1
 mole) of  benzyl  chloride  120 g of  NaOH
  5 287.6 g (1mole) ofNtri-decyldi-ethan- 100° C. 12hours 340 g
  ##STR6##
  C.sub.38 H.sub.56 NO.sub.2 Cl 76.9(76.8) 9.2(9.4) 2.3(2.4) 5.2(6.0)
 34(0)  ol-  amine  392.5 g  (3.1  mole) of  benzyl  chloride  120 g of
 NaOH  6 161.3 g (1mole) ofNn-butyldi-ethanol- 100° C. 24hours 450
 g
  ##STR7##
  C.sub.29 H.sub.38 NO.sub.2 Cl 73.8(74.4) 8.4(8.1) 2.7(3.0) 7.3(7.6)
 14(0)  amine  392.5 g  (3.1  mole) of  benzyl  chloride  120 g of  NaOH
 7 149.2 g (1mole) of 110°
  C. 20hours 364 g
 ##STR8##
  C.sub.34 H.sub.40 NO.sub.3 Cl 74.5(74.8) 7.3(7.3) 2.8(2.6) 6.6(6.5)
 1(0) 109 in CDCl.sub.3δ=3.6-4.1(m,12H,3C.sub.2 H.sub.4)  triethan-
            δ=4.5(s,6H,3φCH.sub.2 O)  olamine
 δ=5.1(s,2H,φCH.sub.2
  N)  519.0 g            δ=7.2-7.4(m,20H,φ)  (4.1  mole) of
 benzyl  chloride  160 g of  NaOH  8 236 g (1mole) oftetrahy-droxy-ethyl-
 110°
  C. 20hours 712 g
 ##STR9##
  C.sub.52 H.sub.62 N.sub.2 O.sub.4 Cl.sub.2 74.0(73.5) 7.1(7.3) 3.3(3.3)
  14(O) 129 in CDCl.sub.3δ=3.5-4.3(m,2OH,10CH.sub.2)δ=4.4(m,2H
 ,4φCH.sub.2 O)δ=5.3(s,4H,2φCH.sub.2
  N)δ=72-7.8(m,30H,φ  )  ethylene-  diamine  784.9 g  (6.2
 mole) of  benzyl  chloride  240 g of  NaOH
  9 131.1 g ofdimethyl-neopenta-nolamine265.9 g(2.1 110° C.
 12hours 188 g
  ##STR10##
  C.sub.21 H.sub.30 NOCl 75.5(75.6) 8.9(9.0) 4.0(4.2) 10.0(10.6) 20(O) 94 i
 n CDCl.sub.3δ=1.3(s,6H,2CH.sub.3)δ=3.3(s,6H,2NCH.sub.3).delta
 .3.4(s,2H,OCH.sub.2)δ=3.8(s,2H,NCH.sub.2)δ=4.5(s,2H,φ-CH.
 sub.2 O)  mole) of            δ=5.1(s,2H,φ-CH.sub.2 N)  benzyl
            δ=7.1-7.7(m,10H,φ)  chloride  80 g of  NaOH  10 133
 g ofN,Ndi- methyl-Ohy-droxy- 100°
  C. 12hours 347 g
 ##STR11##
  C.sub.20 H.sub.28 NO.sub.2 Cl 68.5(68.6) 8.1(8.0) 3.6(4.0) 8.4(10.1)
 4(0)  in CDCl.sub.3δ=3.3(s,6H,2CH.sub.3)δ=3.7(Cl,8H,4CH.sub.2
 )δ=4.5(s,2H,φ-CH.sub.2O)δ=5.0(s,2H,φ-CH.sub.2N)
 ethyl-            δ=7.2-7.7(m,10H,φ)  ethanol-  amine  265.9 g
 of  benzyl  chloride  80 g of  NaOH  11 147 g ofN,Ndi-methyl-Ohy-droxy-
 100°
  C. 12hours 319 g
 ##STR12##
  C.sub.21 H.sub.30 NO.sub.2 Cl 69.7(69.3) 8.4(8.3) 3.6(3.9) 7.8(9.8)
 22(0)  ethyliso-  propanol-  amine  20 g of  NaOH
  12 115.2 g of1-(2-hy-droxy-ethyl)-pyrroli-dine 100° C. 12hours
 235 g
  ##STR13##
  C.sub.20 H.sub.26 NOCl 71.9(72.4) 7.9(7.8) 3.9(4.2) 10.4(10.7) 12(0)
 114 in CDCl.sub.3δ=2.2(m,4H,2CH.sub.2)δ=3.8(m,8H,4CH.sub.2).d
 elta.=4.6(s,2H,φ-CH.sub.2
  O)δ=4.9(s,2H,φCH.sub.2N)δ=7.2-7.7(m,10H,φ)  265.9 g
 of  benzyl  chloride  80 g of  NaOH
  13 129.2 g of1-(2-hy-droxy-ethyl)-piperi-dine 100° C. 12hours
 389 g
  ##STR14##
  C.sub.21 H.sub.28 NOCl 72.5(72.9) 8.1(8.1) 3.9(4.1) 10.1(10.2) 18(0)
 162 in CDCl.sub.3δ=1.8(m,6H,3CH.sub.2)δ=3.8(m,8H,4CH.sub.2).d
 elta.=4.6(s,2H,φ-CH.sub.2O)δ=5.1(s,2H,φ-CH.sub.2           7
  N)δ=.2-7.8(m,10H,φ)  265.9 g of  benzyl  chloride  80 g of
 NaOH  14 270.3 g ofN,Ndi-butyl-N(tri-ethylene 100° C. 12hours 464
 g
  ##STR15##
  C.sub.28 H.sub.42 NO.sub.3 Cl 70.3(70.7) 9.1(8.8) 2.5(2.9) 6.4(7.5)
 15(0)  in CDCl.sub. 3δ=0.8-2.1(m,14H,2C.sub.3
  H.sub.7)δ=3.2(m,4H,2CH.sub.2)δ=3.9(m,12H,6CH.sub.2)δ=4
 .5(s,2H,φCH.sub.2
  O)  glycol)-            δ=4.9(s,2H,φCH.sub.2 N)  amine
     δ=7.2-7.7(m,10H,φ)  265.9 g of  benzyl  chloride  80 g of
 NaOH  15 175.9 g ofpentahy-droxy-ethyldi-propy- 100° C. 20hours
 571 g
  ##STR16##
  C.sub.72 H.sub.88 N.sub.3/5 Cl.sub.3 73.1(73.2) 7.9(7.5) 3.5(3.6)
 6.4(0) 19  lenetri-  amine  525.4 g  (4.15  mole) of  benzyl  chloride
 120 g of  NaOH  16 103.2 g of3-di-methyl-amino- 100° C. 12hours
 252 g
  ##STR17##
  C.sub.19 H.sub.26 NOCl 70.9(71.4) 8.1(8.1) 4.0(4.4) 11.4(11.1) 19(0)
 112 in CDCl.sub.3δ=2.2(m,2H,CH.sub.2)δ=3.3(s,6H,2CH.sub.3).de
 lta.=3.6(m,4H,2CH.sub.2)  propan-            δ=4.4(s,2H,φCH.sub
 .2 O)  ol 265 g of            δ=4.9(s,2H,φCH.sub.2 H)  benzyl
           δ=7.1-7.7(m,10H,φ)  chloride  80 g of  NaOH  17
 146.3 g oftetrahy- droxy-ethyl-hexa- 110° C. 24hours 412 g
  ##STR18##
  C.sub.56 H.sub.70 N.sub.2 O.sub.4 Cl.sub.2 75.2(75.4) 8.0(7.9) 3.0(3.1) 7
 .8(8.0) 18(0) 129 in CDClδ=1.2(m,4H,2CH.sub.2)δ=1.9(m,4H,2CH.
 sub.2)δ=3.2-4.2(m,20H,10CH.sub.2)δ=4.5(s,8H,4φCH.sub.2
 O)  methyl-            δ=4.9(s,4H,2φCH.sub.2 N)  enedi-
     δ=7.0-7.8(m,30H,φ)  amine  392.5 g of  benzyl  chloride
 120 g of  NaOH   18 138.4 g ofheptahy-droxy-ethyl-tetra- 110° C.
 24hours 399 g
  ##STR19##
  C.sub.110 H.sub.36 N.sub.5 O.sub.7 Cl.sub.5 72.6(72.7) 7.7(7.5)
 4.0(3.9) 5.4(5.4) 16(0)  propyl-  enepent-  amine  395.6 g of  benzyl
 chloride  120 g of  NaOH  19 191.3 g oftriisopro-anol-amine 120°
 C. 24hours 555 g
  ##STR20##
  C.sub.37 H.sub.46 NO.sub.3 Cl 75.2(75.6) 7.9(7.8) 2.3(2.4) 6.2(6.0)
 10(0) 143 in CDCl.sub.3δ=1.0(m,9H,3CH.sub.3)δ=3.4(m,6H,3CH.su
 b.2)δ=4.5(m,6H,3φCH.sub.2
  O)  519.0 g of            δ=4.6(s,2H,φCH.sub.2 N)  benzyl
        δ=5.1(q,3H,3CH)  chloride            δ=6.9-7.8(m,20H,.
 phi.)  160.0 g of  NaOH  20 119.2 g ofmethyldi-ethanol-amine265.9 g
 ofbenzyl 100°
  C. 12hours 222 g
 ##STR21##
  C.sub.15 H.sub.26 NO.sub.2 Cl 68.5(68.0) 7.9(7.7) 4.4(4.2) 10.8(10.6)
 176(167)  in CDCl.sub.3δ=1.9(s,1H,OH)δ=3.2(s,3H,1CH.sub.3).de
 lta.=3.4-4.2(m,8H,4CH.sub.2)δ=4.5(s,2H,φ-CH.sub.2
  O)δ=4.9(s,2H,φ-CH.sub.2
  N)  chloride            δ=7.1-7.7(m,10H,φ)  80 g of  NaOH  21 1
 03.2 g ofdimethyl-isopro-panol-amine 100° C. 12hours 317 g
  ##STR22##
  C.sub.19 H.sub.26 NOCl 70.9(71.4) 8.0(8.1) 4.1(4.4) 10.6(11.1) 12(0)
 80 g of  NaOH  22 187.9 g ofNtri-decylNNbis-(O 110° C. 24hours
 313 g
  ##STR23##
  C.sub.42 H.sub.64 NO.sub.4 Cl 74.5(74.0) 9.4(9.4) 2.0(2.1) 4.8(5.2)
 13(0)  hydroxy-  ethyl-  ethanol-  amine)  196.2 g of  benzyl  chloride
 60 g of  NaOH  23 89.1 g ofdimethyl-ethanol- 60° C. 12hours 288 g
  ##STR24##
  C.sub.13 H.sub.23 NSO.sub.5 51.3(51.1) 7.8(7.5) 4.5(4.6) 0.2(0) 10(0)
 amine  126.1 g of  dimethyl-  sulfate  126.6 g of  benzyl  chloride  80
 g of  NaOH  24 149.2 g (1mole) oftri- 50° C. 12hours 211 g
  ##STR25##
  C.sub.18 H.sub.32 NO.sub.3 Cl 61.9(62.5) 9.5(9.3) 3.8(4.0) 10.6(10.3)
 5(0) 80 in CDCl.sub.3δ=3.7-4.2(m,12H,6CH.sub.2)δ=4.3(d,2H,CH.
 sub.2N)  ethanol-            δ=4.9-6.2(m,12H,CHCH.sub.2)  amine
         .sup.13
  CNMR-Spectrum(CDCl.sub. 3)  313.6 g            δ=60 ppm(3NCH.sub.2
 )  (4.1            δ=64 ppm(3OCH.sub.2)  mole)            δ=6
 5 ppm(1NCH.sub.2)  of allyl            δ=72 ppm(3OCH.sub.2)
 chloride            δ=118 ppm(3CH.sub.2)  160 g of
 δ=125 ppm(1CH)  NaOH            δ=130 ppm(1CH.sub.2)
      δ=134 ppm(3CH)  25 89.1 g (1mole)of dimeth- 45° C.
 12hours 142 g
  ##STR26##
  C.sub.6 H.sub.16 NOJ 29.2(29.4) 6.2(6.5) 5.7(5.7) 51.8(51.8) 12 235 in
 CDCl.sub.3δ=3.2(m,9H,NCH.sub.3)δ=3.5(s,3H,OCH.sub.3)
 ylethan-            δ=3.5-4.2(m,4H,C.sub.2 H.sub.4)  olamine  284
 g (2  mole)  of methyl-  iodide  80 g of  NaOH  26 89.1 g (1mole)of
 di-ethyleth-anol- 40°
  C. 12hours 185 g
 ##STR27##
  C.sub.8 H.sub.20 NOBr 42.0(42.5) 8.9(8.8) 5.9(6.2) 34.9(35.3) 7  amine
 218 g (2  mole)  of ethyl-  bromide  80 g of  NaOH  27 89.1 g (1mole)of
 di-methyl-ethanol- amine 90°
  C. 40hours 158 g
 ##STR28##
  C.sub.12 H.sub.28 NOCl 60.1(60.6) 11.5(11.8) 6.0(5.9) 14.9(14.9) 16 112 i
 n CDCl.sub.3δ=1.0(t,6H,CCH.sub.3)δ=1.2-22(m,8H,C.sub.2
 H.sub.4)δ=3.4(s,6H,NCH.sub.3)δ=3.6-39(m,2H,CH.sub.2O)δ=3
 .9(s,4H,NC.sub.2 H.sub.4 O)  185.2 g (2  mole)  of n-  butyl  chloride
 80 g of  NaOH  28 287.6 g (1mole)of tri-decyl-dieth- 110° C.
 24hours 564 g
  ##STR29##
  C.sub.32 H.sub.52 NO.sub.2 ClC.sub.35 H.sub.55 NO.sub. 6 S 66.7 8.7 2.4
 1.4 22  anol-  amine  126 g (1  mole)  of di-  methyl-  sulfate  253 g
 (2  mole) of  benzyl  chloride  120 g of  NaOH  29 187.2 g (1mole)of
 phenyl-dieth-anol-amine 110°
  C. 24hours 445 g
 ##STR30##
  C.sub.31 H.sub.33 NO.sub.2 Cl 76.3(76.3) 7.2(7.0) 3.0(2.9) 7.3(7.3) 25  i
 n CDCl.sub.3δ=3.6(s,8H,2C.sub.2
  H.sub.4)δ=4.5(s,4H2φCH.sub.2
  O)δ=4.55(s,2H,1φCH.sub.2 N)δ=6.5-7.5(m,15H,φ)
 392.5 g  (3.1  mole) of  benzyl  chloride  120 g of  NaOH