CA1126750A

CA1126750A - Phosphoric acid triesters

Info

Publication number: CA1126750A
Application number: CA356,655A
Authority: CA
Inventors: Martin K. O. Lindemann; Elvin R. Lukenbach; Robert J. Verdicchio
Original assignee: Johnson and Johnson Baby Products Co
Current assignee: Johnson and Johnson Professional Inc
Priority date: 1979-07-23
Filing date: 1980-07-21
Publication date: 1982-06-29
Also published as: PT71585A; JPS5622791A; ZW16980A1; KR830003506A; IN153525B; PT71585B; PH17453A; FR2461715A1; MX5854E; IT8049277A0; AU5976280A; BR8004564A; ES493597A0; AU536481B2; DE3027943A1; JPS648634B2; ES8105740A1; ZA804419B; AR228431A1; GR70013B

Abstract

PHOSPHORIC ACID TRIESTERS

ABSTRACT OF THE DISCLOSURE
Novel cationic triesters of phosphoric acid and processes for their preparation are described. These compounds are useful in hair care formulations and also possess bacteriostatic and bacteriocidal properties.

Description

PHOSPHORIC ACID TRIESTERS

Background of the Invention The present invention relates to novel phosphorus derivatives.
More particularly, the present invention relates to novel cationic triesters of phosphoric acid having the general formula:
R~ - +++

(I) R~ - O - P = O 3X

_ R2 wherein Rl, R2 and R3 are the same or different and can be represented by the following formula:

~R4 - ~ - R7 ~

wherein R4, R5 and R6 are the same or different and are alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ether, containing from 1 to about 22 carbon atoms with the proviso that at least one of R4, R5 and R6 contains at least 8 carbon atoms: R7 is hydroxyalkylene of from 2-12 carbon atoms, and X is an anion such as Cl , Br or the like.
The novel compounds of the present invention may be prepared by several processes including the following:

Process A: REACTION OF A HYDROXYL GROUP CONTAINING QUATER-NARY AMMONIUM COMPOUND WITH PHOSPHOROUS OXYCHL.ORIDE

A suitable tertiary amine having the general structure (III) lR6R4 - N

(wherein R4, R5 and R6 are as hereinbefore defined) is ,: :- - , , -,-: :; :, ;-, :, . ` ::: : :, :, quaternized with a compound having the structure (wherein R7 is as hereinbefore defined and X is halogen such as Cl, Br or I), employing an appropriate solvent, reaction apparatus and reaction conditions. More specifically, the quaternization reaction is carried out in a glass or glass-lined reactor equipped with a heater, overhead strirrer, thermometer and reflux condenser utilizing a solvent such as the lower alkanols, water or mixtures thereof to insure good mixing and temperature control. Reaction temperatures may range from about 70C to 120C but are generally governed by the reflux temperature of the reaction mixture. The progress of the reaction is monitored by argentometric deter-mination of halide ion formed during quaternization. Schema-tically, this reaction can be shown as follows:
~R6 -- R6 --0 R4 - ~ (III) + X - R7 - OH R - N~ - R - OH X~
~ 4 1 7 _ R5 _ To isolate the quaternary ammonium compound, a portion of the solvent is distilled off and acetone is added while the reaction mixture is kept between 40-50C. Upon cooling, a crystalline precipitate forms which is isolated via suction filtration and vacuum drying.
The second step of this reaction can be shown schematically as follows:

l~ 3 ' ~

.. . . .

., .
-~ ` .

LR4 ~-R7-OH~ X + POC13 ~ LR4 1~ 7~O I O ~7 ~ R4~

16 ~ N ~ R4l ~ +3HC1 The reaction of the hydroxyl group containing quaternary ammo-nium compound with phosphorus oxychloride is generally carried out by dispersing the quaternary ammonium compound in a low boiling, low polarity solvent such as methylene chloride and adding the required phosphorous oxychloride gradually at room temperature. Once all of the phosphorous oxychloride has been added, the temperature is raised to the boiling point of the reaction mixture and the mixture refluxed for up to 18 hours.
The solvent is recovered via distillation and the phosphoric acid triester purified by recrystallization from hot acetone.
Another process which has been found effective is as follows:
Process B: REACTION OF A TERTIARY AMINE WITH A PHOSPHATE
ESTER HALIDE

The initial step, the preparation of the phosphate ester in-termediate, can be shown schematically as follows:
HO ~ OH + 3 CH2 CH Y X
OH
o X Y CHCH20 P OCH2 CH Y X ( IV) CH~ -CH Y X
OH

i ' J ., ~ ~

;

wherein X is a halogen function, and Y is alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms which alkylene chain may optionally be substituted with lower alkyl, alkoxy, hydroxy or hydroxyalkyl, of not more than 10 carbon atoms each.
The subsequent step, the reaction of the phosphate ester with the tertiary amine, may be shown schematically as follows:

X--Y--CH-CH2----~--O--CH2-CH--Y-X
OH O bH

OH

+3 R4 ~ / R5 Xe, R4- ~ -y-cH-cH2-o-p-o-cH2-lcH-y- ~ -R4, X
R6 OH ¦ OH R5 o R6 CH2-CH-Y- ~ -R4, Xe In general, the reaction is carried out in a glass reactor equipped with an overhead stirrer, addition funnel, reflux condenser and an external heating and cooling unit.

~ 0~
Three parts of the substituted oxirane, CH2-CH-Y-X, are placed in the reactor and one part concentrated phosphoric acid added dropwise while stirring vigorously. The rate of phosphoric acid addition is adjusted to keep the reaction temperature between 65-95C, preferably 85-90C. A halogen .

': ' , ~' ' ' ~ :

; ~

containing epibiphosphate intermediate is formed. Three parts of a suitable tertiary amine are added in small in-crements while keeping the reaction temperature between `-1 ..... ..... ... . . .

:~ : : . ,, . , . .:

~1~7~ J~P 134 90-100C. After com~letion of the amine addition, the reaction mixture is heated at 100-120C until an argento-metric titration of an aliquot portion indicates completion of the reaction.

After cooling, the reaction mixture is dissolved in hot methanol/acetone. The desired product i5 obtained by isolating and drying the precipTt:ate which is formed upon cooling of the methanol/acetone solution.
The novel phosPhoric acid triester compounds of the present invention are cationic surfactants which are capable of so~bing readily onto hair fibers or other negativel~
charged surfaces to reduce static interactions. If R4, R5 15 or R6 have carbon skeletons in excess of 16 carbon atoms, the application of such compounds to hair eliminates "fly-away'l and provides excellent wet and dry combing.

Normally, cationic quaternary ammonium salts are not readily 20 compatible with a broad range of other surfactants.
Surprisingly, the novel compounds of the present invention are readily compatible with a wide range of surfactants such as anionic surfactants of the sodium lauryl sulfate or sodium laurylether sulfate types; amphoteric sur-25 factants such as betaines, sultaines and phosphobetaines;and nonionic surfactants such as ethoxylated sorbitan esters.
This unexpected compatibility permits the compounds of the present invention to be easily included in conventional shampoo and creme rinse formulations. The compounds of 30 the present invention can he utilized from about 0.1% to about 20~ by weight depending on the composition in which it is utilized. If amoun~s greater than 20% by weight are utilized, the resulting compositions may be harsh and irritating when used as shampoos or creme rinses.

.

Still further, it has been found that if R4, R5 or R6 in formula (II) of the novel phosphoric acid triester compounds of the present invention are of a carbon chain length of from 8 to 14 carbon atoms, then these compounds exhibit outstanding bacteriostatic and bacteriocidal properties. Compounds with these properties may be utilized at from about 0.1% to about 5.0% by weight of the total composition. If less than about 0.1% is utilized, the desired properties will not be achieved and if greater than about 5.0% is utilized, the resulting com-position may be harsh and irritating.
The following examples illustrate the invention and are notto be construed as imposing any limitations thereon.

46.53 G. of epicholorohydrin are placed in a 500 ml. glass reactor equipped with an overhead stirrer, water cooled con-denser, addition funnel, thermometer and heating mantle.
19.0 g. of 85.5% phosphoric acid are then added via a dropping funnel while stirring vigorously with the rate of addition being adjusted to maintain a temperature of 80-85C. As the exothermic reaction subsides, the reactor is heated to keep the reaction mixture at 80C for a period of 1 hour. 148 g. of octadecyldimethylamine are then added to the reactor and the mixture is stirred for 20 hours at 102C. Completion of the - reaction is ascertained by argentometric titration of the generated chloride ion.
After cooling to approximately 40C, the reaction mixture is diluted with 200 ml. ethanol, transferred into a 2 1. beaker and 1000 ml. acetone are added. A tan precipitate is formed which is isolated by suction filtration and recrystallization from an ethanol/acetone mixture results ~1~
. . ~

- :: . , ~ ,;, ,: , . . .

- : . - '.: : ~ : ::: ... . :-.
- , : . -,; .: . : .

in a tan powder. Argentometric titration of chloride ion and saponification assays show this material to have a pu-ity of 98.6%. ~he product contains a novel triester of phosphoric a~id of .he following structure:
+++

CH2~CH-CH2-~ C18H37 ¦ CH3 o=P-o-c~2-cp-cH2 ~ C18~ 7 3Cl~

CH2-CH-cH2-~-c 8H3 O~ C~3 EXAMPLE II
Using the glass reactor described in EX~PLE I, 93.52 g.
of epichlorohydrin are reacted with 38 g. 85.5% phosphoric acid at 8~-90C for a period o~ 2 hours. 213.2 g. of dodecyldimethylamine are then added over a period of 3 10 hours while the temperature is kept at 85-90C. Additional heating at 100+5C for 72 hours produces argentometric titration values for chloride ion which are indicative of better than 90% completion. The reaction product is isolated in accordance with the procedure in EXA~LE 1 15 yieldins a light tan free-flowing powder and assays show the purity to be 99.0%. The product contains a novel triester of phosphoric acid of the following structure:

C}~2-CP-CH2- ~ ~C12H25 1 O OH CH
o=p-o-c~2-cH-cH2-l~ Cl2H2' 3Cl~
l CH3 CH2-CH-cH2-lN C12 2~ .

. , -~ ~

~ 67~ J3P 134 g EX~MPLE III
Employing the apparatus described in E~MPLE 1, 19.0 g. of concentrated phosphoric acid are added dropwise to 4~.53 g.
of epicholorhydrin while keeping the reaction temperature between 85-90C.

176.5 g. of a molten ~0/50 mixture of eicosyldimethyl amine and docosyldi~ethylamine are added over a period of 2 hours keeping the temperatu-e at 100C. Following an additional 12 hours at 100C, the temperature of the reaction mixture is raised to 140C for 90 minutes. - -After cooling the desired product is isolated by crystalli-zation from hot ethanol, suction filtration and drying.
15 Argentometric titration indicates an activity of 94.6~.

The structure is determined to be the same as the structure of EXAMPLE II except that the C12H25 substituent is replaced by a mixture of C20H41 and C22H45 in a 1:1 ratio.
E ~PLE rv - EmDloying a 2 1. glass reactor equipped with an overhead stirrer and a reflux condenser 140.28 g. of epicholorohydrin are reaeted with 57 g. of 85.5~ phosphoric acid and the reaction is conducted at 85-90C over a period of 2 hours.
To this reaction product 548.6 g. of 3-oleoamidopropyl dimethylamine are added and the temperature raised to 95-100C. After 22 hours an argentometric titration ~hows the reaction to be approaching completion and the reaction is allowed to cool. Following crystallization from ethanol/acetone, suction filtration and vacuum drying an-off-white powder is obtained. The product contains a nov^el triester ~f ~hosphoric acid of the following structure:

:: .. . :

:

~BP 134 OH C,H3 H O ~++

2 CH CH2 N~ -CH2-CH2-CH2-N-C-C17H35 lCH3 H2 CH CH2--N--CH2-CH2--CH2--N--C--C17H3; 3C1~3 IO~H3 H jO
CH2 CI H CEI2 ~ -CH2-CH2 -CH2-N-C C17H35 E _ Using the reaction vessel and conditions des~ribed in EXAMPLE III, 112.2 g. o epicholorohydrin are reacted with 45.6 g. of 85.5% phosphoric acid. 458.4 g. of stearamido-5 ethyldiethyla~lne are then added to the reaction mixture which is maintained at 95C for 20 hours. Completion of reaction is estimated by argentometric titration and the product contains a novel triester of phosphoric acid of the follow: Lnq structure: _ ~++
OH C~2H5 ~ ,~
CH2-CH-CH~-~N -CH2-C~2-N-C-C17H35 ~ C2H5 O OH C2~5 H O
O=P-OCH2-~H-CH2-~--C~2C~2-N-C-C17H35 3Cl~
I C2H5 .
O C ~ ~ O
~ ~,2 5 , ll CH2 ,C~ CH2 ~ -CH2-CH2-N-C-Cl~H35 OH C2~5 , EXAMPLE V~
.
297 g. of octadecyldimethylamine and 80 g. of ethylene chlorohydrin are dissolved in absolute ethanol to a total ~ . .
- , ~ . . , , ~ .

volume of 1500 ml. This mixture is then heated in a 2 1.
round bottom flask equipped with a reflux condenser. After 6 days, titration for chloride ion indicates the reaction to be 91~ complete and the reaction is terminated. The desired stearyldimethyl~2-hydroxyethylammonium chloride is isolated by precipitatio~ with acetone. After recrystall-i-zation from an ethanol/acetone mixture, filtration and vacuum drying, a white powder is obtained which, by chloride titration, is assayed to be 98.9% pure.
228.7 g. of this stearyldimethyl-2-hydroxyethylammonium chloride is then placed in a 2 1. 3-neck round bottom flask equipped with an overhead stirrer, addition funnel and reflux condenser. 1200 ml. of methylene chloride are 15 added and the quaternary ammonium compound is dispersed by vigorous agitation. 30.70 g. of phosphorous oxychloride, POC13, is added dropwise over a period of 1 hour. ~he reaction mixture is then refluxed for 18 hours, methylene chloride is removed via distillation and the triester 2C purified by recrystallization fFom hot acetone.

The product contains a novel triester of phosphoric acid of the following structure:
CH3 +~1 CH2-CX2-0N -Cl8H37 o=p-O-CH2C ~ N C18H37 3Cl~3 CH2 CH2 -~-Cl 8H17 CH

EXA~PLE VII
213.14 g. o~ dodecyldimethylamine are dissolved in 1200 ml.
25 absolute ethanol, and B0 y. of ethylene chlorohyd-in are added and the resulting reaction mixture is refluxed 'or L2~

72 hours. Dodecyldimethyl-2-hydroxyethylammonium chloride is obtained in 84% yield via precipitation with acetone, recrystallization with ethanol/acetone, filtration and vacuum drying. 175.9 g. of the above dodecyldimethyl-2-S hydroxyethylammonium chloride is reacted with 30.70 g. ofphosphorous oxychloride using the equipment and reaction conditions described in EXAMPLE ~.

The product contains a novel triester of phosphoric acid of the following structure:
1 2CH2 N C12~25 l++

o=P-ocH2c~2~N-cl2~25 3C19 gH2CH2~-C12H25 305.6 g. of stearamidoethyldiethylamine are dissolved in 2000 ml. absolute ethanol. 64 g. o~ ethylene chlorohydrin are then added and the reaction mixture refluxed for 120 hours. Approximately 3/4 of the ethanol is then removed 15 by flash e~aporation and acetone is added to saturation at the boiling point and the reaction mixture is allowed to cool to room temperature. The white precipitate formed is isolated, ~acuum dried and identified as stearamido-ethyldiethyl-2-hydroxyethylammonium chloride.
277.2 g. of this stearamidoethyldiethyl 2-hydroxyethyl-ammonium chloride are reacted with 30.7 g. of phosphorous oxychloride using the equipment and reaction conditions described in E'XAMPLE U The product contains a no~el triester 25 of phosphoric acid of the following structure:

., .
.
:, . ~

C2H5 7 _ ~+ I

l C2H5 o=p-OCH2CH2~ -C~2CF~2N C C17 35 3Cl~

O C2H5 E[ O
CH2CH2~ -CH2CH2 ~ C C17 35 EX~MP~E IX
A hair care product is prepared as follows:

One hundred fifty parts by weight of a 30% active solution 5 of a phosphobetaine of the following structure:

R - C - N ~ (CH2)2-~ ~ CH2 - CHOH - CH2 - O - P - OO

CH2COONa ONa wherein R is a CIl-C13 mixture in a 1:1 ratio is mixed with 200 parts of distilled water at ambient room tem-perature followed by the addition of 77 parts by weight of a 26% active solution of cationic triphosphate ester of 10 EXAMæLE I and the resulting solution is mixed until clear and homogeneous. This was followed by the addition of 150 DartS by weight of a 30~ active solution of an ampholyte - made by the process as described in-U.S. Patent No.
2,970,160 and represented as follows:

R - C - N - (CH2)2 ~ N ~
CH2COONa wherein R is a Cll-C13 mixtur in a 1:1 ratio.
200 parts of 72% polyoxyethylene (80) sorbitan monococoate are then added followed by 12 g. of polyethylene glycol 6000`distearate and the resultinq mixture is heated to 70C for 20 millutes. The solution is cooled to 35C and 20 the pH ad,usted to 7.0 - 1 with 15% HC1 solution.
Preservative and fragrance are added and sufficient deionized water to bring the total mass to 1000 grams.
:

- .

The inished product is clear with a viscosity of 1225 cps at 25CC as measured using a Brookfield viscometer with #2 spindle at 12 RPM. The product produces excellent foaming and cleaning properties and exhibits conditioning effects 5 on hair as ascertained via beauty salon half head studies.
These studies involve separating each subject's hair into two parts and placing a shampoo composition with the novel compounds of the present invention on one part and the same composition without ~he novel compounds on the 10 o,her part and subjectively rating the results according io the same guidelines.

EXAMPLE X
The following detergent hair or skin cleanser is prepared 15 according to the procedure outlined in EXAMPLE IX:
Ingredient wt/wt ~
cocoamidopropylsultaine 5.00 tridecyl ether ~4) sulfate 5.00 tris-stearylamino phosphate ester 0.30 propylene glycol 1.00 thickener 2.00 preservative 0.10 dye 0.02 fragrance 0.20 2~ deionized waterq.s. to 100%

The p,~ of the above was adjusted to 5.5 with dilute HCl.

EXAMPLE XI
30 A cleaner, softener and sanitizing composition was prepared according to the following formula:

JB~ 134 Ingredient wt/wt %
cocoamidophosphobetaine10.0 tris-stearylamido phosphate ester 1.0 soaium citrate 10.0 glycerine 1.0 optical brightener 0-5 fragrance 0.3 deionized waterq.s. to 100%

10 The pH of the abo~e was adjusted to 7.0 + 1 with 15% HC1.

The composition of EXAM2LE XI is tested for detergency with two comm~rcially available compositions utilizing the following procedure:
Standard soiled wool fabric, from Test Fabrics, Inc., is used to evaluate the relative cleansing ability o a given composition. A Terg-O-Tometer, Model 7243, is used to simulate the cleansing action. The conditions controlled 20 are as follows:
1. washing time (5 minutes) 2. washing speed (100 rpm.)

3. rinsing time (5 minutes)

4. rinsing speed (100 rpm)

5. wash and rinse tempera~ure (105F) The test cloth is made from wool challis and comes in ten-yard rolls. A soil mixture, consisting mainly of lamp black, oils and commercial solvents, is applied to the cloth with a printing roll so that only half of the 8-inch wide 30 cloth becomes soiled.

This-test cloth-is cut into 4 x 8 inch strips so that half o each strip is soiled and half unsoiled. A Gardner Color Difference Meter is used to obtain the initial color 35 ~alue (degree o whiteness) for both the soiled and unsoiled portion of each strip. Three of these strips along with tr.ree 4 x 8 inch cotton filler strips are placed in the .

. . , ~ . ,.

. . ~ , Terg-O-Tometer beaker containing 1000 ml. of a 10~ aqueous solution of the test composition. Prior to this, the solution is agitated for two minutes and allowed to equilibrate at 105F. The samples are agitated for five 5 minutes, removed, squeezed out, and returned to the agitating beaker containing 1000 ml. of clean 105F tap water. After five minutes of agitating, the strips are removed, sque~zed out and laid flat to dry. When dry, they are again evaluated using the Color Difference Mater to 10 determine how much soil has been removed as well as how much soil has been deposited on the unsoiled portion of the cloth. The relative cleansing effectiveness is indicated by the spread between the initial and final whiteness measurements which is characterized as ~R.
15 A /\R of two units is considered significant. When the commercial compositions were compared to the oomposition of EXAMPLE XI, the following results were obtained:
~R
Commercial Composition I 5.7 Commercial Composition II 8.0 Composition of EXA~LE XI 8.4 EXAMPLE XII
A pour-on creme rinse is prepared having the following 25 composition:
90 Wt~Wt phosphoric triester of E~MPLE I 1.10 ethyldihydroxypropyl para-amino benzoic acid 0.55 benzyl alcohol 0.55 stearyl alcohol 0.88 isostearyl alcohol 0.33 fragranc:e 0.11 hydroxyethyl cellulose 0.83 3~ sodium hydroxide 0.21 deionized water q.s. to 100~

: .

This composition exhibits excellent wet combing and con-ditioning properties.

EXAM~LE XII.[
5 In order to demonstrate the antimicrobial properties of the novel compounds of the present invention, the following standard Minimum Inhib:Lting Concentration test was performed to determine the lowest effective concentra-tion of the novel compounds that will inhibi. the growth 10 of various test organisms. First, 200 mg. each of the compounds of EXAM2LES II and VII are placed in 100 ml. of distilled water resulting in a concentration of 2.00 mg/ml.
and then 10 serial two fold dilutions are made to a final concentration of ~.0038 mg/ml. Thus, a range of concentra-15 tions of from 0.0038 mg/ml. to 2.00 mg/ml. are prepared.Separately, 1000 ml. of a standard Antibiotic Medium #3 is innoculated with 1 ml. of a 24 hour broth culture of each of the test organisms and the resulting solutions are dispersed in 2 ml. portions into 13mm x lOOmm test tubes 20 at 4C. Two test tubes for each of the test organisms are prepared.

Then, 0.4 ml. of each concentration of the compound to be tested is placed in each of the ~est tubes, which are then ~5 shaken and placed at a temperature of 35C for a period of 18 hours. The end point of the activity is determined by streaking utilizing a calibrated loop to Trypticase Soy Agar to determine the last tube (concentration) with growth and the next greatest concentration is deemed the 30 minimum inhibiting concentration. The results are shown below in Table I:

- . , : ~ :: : , . :

5(~

Table I
Test Minimum ~biting Concentration Organism _ _ m~/ml Compound of Compound of l~:X~PLE I EXAMPLE VI I
Staphylococcus aureus 0.063 0.029 Staphylococcus epidermis 0.016 0.024 Pseudomonas aeruginosa0.433 0.367 Aspergillus niger 0.096 0.125 Trichophyton mentagrophytes 0.010 0.006 Candida albicans 0.071 0.188 These results, when compared to a control bacteriostatic and/or bacteriocidal agent such as cetyl pyridinium 15 chloride, showed that the novel compounds of the present invention exhibit bacteriostatic and oacteriocidal properties at relatively low concentrations and would be good antimicrobial agents.

- 20 While the present invention has been described and illus-trated with reference to certain preferred embodiments thereof, those skilled in the art will appreciate that various modifications, changes, omissions and substitu-tions can be made without departing from the spirit of the 25 invention. It is intended, therefore, that the invention be limited only by the scope of the appended claims.
-::

: - . : . : . : .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-1. A compound of the formula:

wherein R1, R2 and R3 are the same or different and can be represented by the following formula:
wherein R4, R5 and R6 are the same or different and are alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ether, containing from about 1 to 22 carbon atoms with the proviso that at least one of R4, R5 and R6 contains at least 8 carbon atoms; R7 is hydroxylakylene of from about 2 to 12 carbon atoms; and X- is an anion.
2. A compound in accordance with claim 1 of the formula:

.

3. A compound in accordance with claim 1 of the formula:

4. A compound in accordance with claim 1 of the formula:

wherein Ra is a mixture of C20H41 and C22H45 in a 1:1 ratio.

5. A process for the preparation of a compound of the formula:

wherein R1, R2, R3 and X- have the same meanings as in

claim 1, which comprises the steps of:
a) quaternizing a tertiary amine with a compound of the formula:

wherein R7 has the same meaning as in claim 1 and X is halogen, to form a hydroxyl group containing quaternary ammonium compound and reacting the hydroxyl group containing quaternary ammonium compound with a phosphorus oxyhalide; or b) reacting epichlorohydrin with phosphoric acid to form a halogen-containing epibiphosphate and reacting the epibiphosphate intermediate with a tertiary amine.
6. A process for the preparation of a compound of the formula:

wherein R1, R2, R3 and X- have the same meanings as in claim 1, which comprises the steps of:
a) quaternizing a tertiary amine with a compound of the formula: X - R7 - OH
wherein R7 has the same meaning as in claim 1 and X is halogen, to form a hydroxyl group containing quaternary ammonium compound; and b) reacting the hydroxyl group containing quaternary ammonium compound with a phosphorus oxyhalide.

7. A process for the preparation of a compound of the formula:

wherein R1, R2, R3 and X? have the same meanings as in claim 1. which comprises the steps of:
a) reacting epichlorohydrin with phosphoric acid to form a halogen-containing epibiphosphate; and b) reacting the epibiphosphate intermediate with a tertiary amine.