United States Patent (19) (11) Patent Number: 4,883,917 Smith et al. 45) Date of Patent: Nov. 28, 1989

54 QUATERNARY AMMONIUM COMPOUNDS Primary Examiner-Paul F. Shaver 75) Inventors: Kim R. Smith; Joe D. Sauer; James E. Attorney, Agent, or Firm-Joseph D. Odenweller Borland, all of Baton Rouge, La. (57) ABSTRACT 73) Assignee: Ethyl Corporation, Richmond, Va. Disclosed herein are quaternary ammonium compounds of the formula Rl R2R3N+-(CH2)YX - wherein n 21 Appl. No.: 782,353 is 1 or 2 depending on the valence of the cation; m is an integer from 1 to 6; Y is a group selected from Z, (22 Filed: Oct. 1, 1985 -NRR2R3, -OH, -SOCl, -CH=CH2, -O-R4, 51) Int, C.'...... CO7C 91/40 -OSiR5R6R7, -OC(OR3, -CN, -SO4Q, -C=CH, 52 U.S. C...... 564/292 epoxide, -SR10, -SO2)R11, -SO)R12, 58 Field of Search ...... 564/291, 292, 281; 556/417, 413; 560/155, 171,250 56 References Cited U.S. PATENT DOCUMENTS 2,541,248 2/195i Hibbs ...... 167/22 3,054,678 9/1962 Michener et al...... 99/150 4,401,577 8/1983 Richmond ...... 564/291 X SO3Q, -Si(OR13)(OR1)-- (OR15), -OC(O)-(CH2 4,470,918 9/1984 Mosier ...... 564/29 X )-C(O)-O-(CH2)n-NRR2R3, and -NR16R17 4,480,126 10/1984 Rutzen ...... 564/291 X wherein m and p are integers, the R groups are hydro 4,675,118 6/1987 Stanley et al...... 564/291 X carbyl, Q is H or alkali metal. They are useful as fungi cides, herbicides, antiseptics and peroxygen bleach acti FOREIGN PATENT DOCUMENTS Vators. 2711577 3/1977 Fed. Rep. of Germany ...... 564/292 UX 1 Claim, No Drawings 4,883,917 1. 2 -continued QUATERNARY AMMONIUM COMPOUNDS -CH-CH BACKGROUND OF THE INVENTION N / O Quaternary ammonium compounds referred to as "quats', are nitrogen compounds having four groups -S-R10 bonded to a nitrogen atom by a covalent C-N bond. O The nitrogen atom has a positive charge which requires --Ril a counter anion or a balancing negative charge in the 10 quat compound itself. Such compounds are used as O fungicides, algicides, bactericides, bleach activators and have many other well known uses. Quats can be easily made by reacting a compound having a covalent halo gen atom with a tert-amine. 15 SUMMARY OF THE INVENTION According to the present invention a new series of quats has been discovered having at least one of a group of functional radicals bonded to a quaternary nitrogen atom through a methylene group or a series of methy OR 13 lene groups. These new compounds have all the known -Si-OR4 uses of quaternary ammonium compounds. In addition some of the new quats are useful as hair conditioning bris agents, peroxygen bleach activators. 25 DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the invention is a quater nary ammonium compound having the structure 30 R16 / and N Yr7 wherein m and pare integers from 1 to 6; n is 1 or is 2 wherein R is an alkyl group having 8-20 carbon atoms, when the cationic group has a valence of -2; X is a R is an alkyl containing 8-18 carbon atoms or is monovalent anion; R; R2 and R3 are as above; Z is a methyl, R is methyl, Y is selected from the group con halogen; R, R8, R9, R16 and R17 are alkyls containing sisting of 1-6 carbon atoms; R5, R6, R7, R10, R11, R12, R13, R14 40 and R5 are alkyl containing 1-10 carbon atoms or phenyl; and Q is an alkali metal or H. al-Z For the sake of simplifying the following disclosure R2 the chemical group:

t Rl 45 R3 aOH -O-R 50 will be represented by the letter 'A'. Thus the first R5 group of quats have the structure A-Z X wherein Z is a halogen such as chlorine, bromine, fluorine or io -O-Si-R6 dine. The more preferred halogens are chlorine and k bromine. Representative examples of these quats are: O 55 decyl dimethyl 2-bromoethyl ammonium chloride; dodecyl dimethyl 2-chloroethyl ammonium bromide; -O-C-R8 didecyl methyl 3-bromoethyl ammonium chloride; octadecyl dimethyl 4-chlorobutyl ammonium bromide; -CN hexadecyl dimethyl 2-bromoethyl ammonium bromide; O 60 dioctyl methyl 6-bromohexyl ammonium bromide; and the like. -O-S-OQ More preferably R1 is an alkyl containing 8-18 car O bon atoms, R2 is a C8-18 alkyl or methyl, Z is chlorine or bromine and m is 2. Examples of these more preferred 65 compounds are: -C-O-R9 octyl dimethyl 2-chloroethyl ammonium chloride; dioctyl methyl 2-bromoethyl ammonium bromide; CECH decyl dimethyl 2-bromoethyl ammonium bromide; 4,883,917 t 3 4. didecyl methyl 2-chloroethyl ammonium chloride; didodecyl methyl 3-hydroxypropyl ammonium iodide; dodecyl dimethyl 2-bromoethyl ammonium bromide; octadecyl dimethyl 6-hydroxyhexyl ammonium fluo didodecyl methyl 2-bromoethyl ammonium chloride; ride; tetradecyl dimethyl 2-chloroethyl ammonium chloride; and the like. ditetradecyl methyl 2-bromoethyl ammonium bromide; The more preferred compounds of this class are those octadecyl dimethyl 2-chloroethyl ammonium chloride; in which R1 is a C8-18 alkyl, R2 is a C8-18 alkyl or methyl, and the like. m is 2 and X is chlorine or bromine. Examples of these Another group of new quats of the present invention preferred compounds are: are those having the structure A-NRR2R3 2X. octyl dimethyl 2-hydroxyethyl ammonium bromide: Examples of these compounds are: 10 dioctyl methyl 2-hydroxyethyl ammonium chloride; N,N'-didodecyl-N,N,N',N'-tetramethyl ethylene diam decyl dimethyl 2-hydroxyethyl ammonium chloride; monium dibromide; didecyl methyl 2-hydroxyethyl ammonium bromide; N,N'-dioctadecyl-N,N,N',N'-tetramethyl-1,4-butane dodecyl dimethyl 2-hydroxyethyl ammonium bromide; diammonium dichloride; didodecyl methyl 2-hydroxyethyl ammonium chloride; N,N'-dioctyl-N,N,N',N'-tetramethyl-1,6-hexane diam 15 tetradecyl dimethyl 2-hydroxyethyl ammonium chlo monium dibromide; ride; and the like. ditetradecyl methyl 2-hydroxyethyl ammonium bro As with the previous group, the more preferred com mide; pounds are those in which R1 is a C8-18 alkyl, R2 is a and the like. C8-18 alkyl or is methyl, m is 2 and X is chlorine or 20 bromine. Some further examples of these are: These compounds can be readily made by reacting a N,N'-dioctyl-N,N,N',N'-tetramethyl ethylene diammo halo alcohol, X(CH2)n-OH, with a tert-amine, nium dibromide; RR2R3N. The reaction is usually conducted in an inert N,N'-didecyl-N,N,N',N'-tetramethyl ethylene diammo solvent under nitrogen at elevated temperatures for a nium dichloride; 25 period to essentially complete quaternerization of the N,N'-dioctadecyl-N,N,N',N'-tetramethyl ethylene di amine which can be followed by disappearance of the ammonium dichloride; amine group. The following example shows the prepa N,N'-ditetradecyl-N,N,N',N'-tetramethyl ethylene di ration of the hydroxy alkyl quats. ammonium dibromide; EXAMPLE 3 N,N,N',N'-tetraoctyl-N,N'-dimethyl ethylene diammo 30 nium dibromide; In a reaction vessel was placed 17.37 grams of 2 N,N',N',N'-tetradodecyl-N,N'-dimethyl ethylene diam bromo ethanol, 27.8 grams of dodecyl dimethyl amine monium dichloride; and 41.3 grams of methylethyl ketone solvent. The and the like. mixture was stirred at reflux (approx. 78° C) under The foregoing two classes of compounds can made 35 nitrogen for about 4 hours. It was then cooled and a by reacting the appropriate tert-amine having the struc precipitate formed which was identified as dodecyl ture NRR2R3 with a dihaloalkane such as ethylene dimethyl 2-hydroxyethyl ammonium bromide. This dibromide. The reaction is conducted at a temperature product was recovered by filtration. of about 20-100° C. using about 1 mole of tert-amine for It was also discovered that the above reaction is cata each equivalent of halogen atom which is desired to be 40 lyzed by the inclusion of a small amount of potassium quaternerized. In other words to replace one halogen of iodide. As little as 0.05 up to 0.5 parts by weight or the dihaloalkane 1 mole of tert-amine would be used more of potassium iodide per 100 parts of tert-amine are whereas to replace both halogens of 1 mole of dihaloal effective. The following example shows this effect. kane, 2 moles of tert-amine would be used. Typical preparations of these compounds is shown in the fol 45 EXAMPLE 4 lowing examples. In a reaction vessel was placed 32.99 grams of dode cyl dimethylamine, 0.03 grams KI, 0.3 mL water and 15 EXAMPLE 1. mL 2-chloroethanol. While stirring under nitrogen, the In a 5 liter 3-neck flask was placed 540.19 grams of mixture was heated to 100 C. After 3.5 hours, 30 mL of decyldimethyl amine, 530.6 grams of ethylene dibro 50 methylethyl ketone was added and after 5 hours 20 mide and 1600 grams of ethyl acetate solvent. The mix minutes an additional 70 mLs of methylethyl ketone ture was stirred and heated under nitrogen for 24 hours. was added to dissolve the quat that started to precipi It was then cooled and diluted with isopropanol to tate. The mixture was then cooled causing the product, cause precipitation of 0° C. of the product, N,N'-dide dodecyl dimethyl 2-hydroxyethyl ammonium chloride cyl-N,N,N',N'-tetramethyl ethylene diammonium bro 55 to precipitate. Conversion was 90% based upon amine mide. consumption. EXAMPLE 2 Another class of quats of this invention can be repre In a 500 mL 3-neck flask was placed 72.1 grams of sented by the formula decyldimethyl amine, 35.42 grams of ethylene dibro 60 A-ORX mide and 71.7 grams of ethyl acetate solvent. The mix ture was stirred and heated under nitrogen at 90 C. and wherein R is an alkyl containing about 1-6 carbon held at this temperature for 24 hours. The mixture was atoms. Some examples of these compounds are: then cooled to 5' C. to precipitate decyl dimethyl 2 octyl dimethyl 2-methoxyethyl ammonium bromide; bromoethyl ammonium bromide which was recovered 65 dioctadecyl methyl 2-butoxyethyl ammonium chloride; by filtration. didecyl methyl 2-hexoxyethyl ammonium fluoride; The next class of quats are those having the structure tetradecyl dimethyl 3-methoxypropyl ammonium io A-OH X. Some examples of these are: dide; 4,883,917 5 6 octadecyl dimethyl 4-methoxybutyl ammonium bro decyl dimethyl trimethylsilyloxyethyl ammonium bro mide; mide; and the like. dodecyl dimethyl trimethylsilyloxyethyl ammonium More preferably R1 is a C8-18 alkyl, R2 is a C8-18 alkyl chloride; or a methyl group, m is 2 and X is chlorine or bromine. 5 didodecyl methyl trimethylsilyloxyethyl ammonium Examples of these preferred compounds are: bromide; dioctyl methyl 2-methoxyethyl ammonium bromide; tetradecyl dimethyl trimethylsilyloxyethyl ammonium didecyl methyl 2-ethoxyethyl ammonium chloride; bromide; didodecyl methyl 2-propoxyethyl ammonium bromide; dioctadecyl methyl trimethylsilyloxyethyl ammonium dioctadecyl methyl 2-butoxyethyl ammonium chloride; O chloride; octyl dimethyl 2-methoxyethyl ammonium chloride; and the like. decyl dimethyl 2-ethoxyethyl ammonium bromide; These compounds can be made by reacting a trialkyl dodecyl dimethyl 2-propoxyethyl ammonium iodide; chlorosilane such as R5R6RSiCl, with a trialkyl hy tetradecyl dimethyl 2-butoxyethyl ammonium fluoride; droxyalkyl ammonium halide, A-OH X. An inert octadecyl dimethyl 2-methoxyethyl ammonium bro 15 solvent such as tetrahydrofuran, dimethoxyethane, di mide; glyme, dioxane and the like can be used but is not re and the like. quired. The reaction should be conducted under nitro These compounds can be made by reacting an appro gen at from room temperature up to reflux. The follow priate alkoxy alkyl halide (e.g. R-O-(CH2)n-X) ing examples show the preparation of a typical silyloxy with a tert-amine (e.g. RR2R3N) at an elevated temper 20 compound. ature to form the alkoxyalkyl quat. The following exam ple shows a typical synthesis. EXAMPLE 6 In a reaction vessel was placed 5.51 grams of dodecyl EXAMPLE 5 dimethyl 2-hydroxyethyl ammonium bromide. While In a 2 liter 3-neck reaction flask was placed 212.3 25 stirring under nitrogen at room temperature, 50 mLs of grams tetradecyl dimethyl amine, 86.49 grams 2 trimethylchlorosilane was added. The temperature ini methoxyethyl chloride and 425.45 grams para-dioxane tially dropped from 25 to 20 C. Heat was applied and solvent. The mixture was refluxed for 48 hours, cooled an exotherm was observed. The mixture was refluxed at to crystallize the product and the white crystalline 52 C. for 2 hours. The mixture was then cooled and a 30 precipitate formed. The precipitate was removed by product recovered by filtration and identified as tetra filtration, dried and analyzed as dodecyl dimethyl 2 decyl dimethyl 2-methoxyethyl ammonium chloride. trimethylsilyloxyethyl ammonium bromide. Another preferred class of new compounds can be Another group of compounds of the invention are represented by the structure those having the formula A-O-C(O)-R8 X 35 wherein R8 is an alkyl group containing about 1-6 car R5 bon atoms. Representative examples of this embodiment A-O-Si-R6 are: octyl dimethyl 2-acetyloxyethyl ammonium chloride; k octadecyl dimethyl 3-propionyloxypropyl ammonium iodide; wherein R5, R6 and R7 are alkyls containing about 1-10 dioctyl methyl 3-acetyloxyhexyl ammonium bromide; carbon atoms or phenyl. and the like. Representative examples of these compounds are: In a more preferred embodiment, R is a C8-8 alkyl, octyl dimethyl trimethylsilyloxyethyl ammonium bro R2 is a C8-18 alkyl or methyl group, R8 is methyl, X is mide; 45 chlorine or bromine and m is 2. Some examples of these dodecyl dimethyl triethylsilyloxypropyl ammonium compounds are: chloride; didecyl methyl 2-acetyloxyethyl ammonium bromide; octadecyl dimethyl trihexylsilyloxybutyl ammonium decyl dimethyl 2-acetyloxyethyl ammonium chloride; iodide; octyl dimethyl 2-acetyloxyethyl ammonium chloride; didecyl methyl trimethylsilyloxyhexyl ammonium fluo 50 dioctyl methyl 2-acetyloxyethyl ammonium bromide; ride; dodecyl dimethyl 2-acetyloxyethyl ammonium bro octyl dimethyl triphenylsilyloxyethyl ammonium bro mide; mide; tetradecyl dimethyl 2-acetyloxyethyl ammonium bro didodecyl methyl triphenylsilyloxyethyl ammonium mide; iodide; 55 octadecyl dimethyl 2-acetyloxyethyl ammonium chlo octadecyl dimethyl triphenylsilyloxyethyl ammonium ride. fluoride; These acyloxyalkyl quats can be made by reacting a and the like. haloalkyl alkanoate, X-(CH2)n-O-C(O)-R8, with The more preferred silyloxy quats are those in which a tert-amine, RR2R3N. Preferably an inert solvent is R is a C8-18 alkyl, R2 is a C8-18 alkyl or a methyl group, 60 used and the reaction is conducted under nitrogen at an R5, R6 and R7 are alkyl, m is 2 and X is chlorine or elevated temperature up to reflux. The following exam bromine. Still more preferred are compounds in which ples illustrate how the compounds can be made. Rs, R6 and R7 are methyl groups. Further examples of these are: EXAMPLE 7 octyl dimethyl trimethylsilyloxyethyl ammonium chlo- 65 In a glass reaction vessel under nitrogen was placed ride; 78.25 grams of ethyl acetate solvent and 32.65 grams of dioctyl methyl trimethylsilyloxyethyl ammonium bro 2-bromoethyl acetate. While stirring, 41.14 grams of mide; dodecyl dimethyl amine was added dropwise. A slight 4,883,917 7 8 exotherm was observed. Heat was applied and the tem perature raised to reflux (ca. 89 C.) which was contin O ued for 6 hours. The mixture was then cooled to -10 C. causing the product to precipitate. The product, A-O--oo X dodecyl dimethyl acetyloxyethyl ammonium bromide, O was recovered by filtration. The above compounds can also be made by reacting wherein Q is hydrogen or an alkali metal. When Q is an an appropriate acyl halide, R3C(O)Cl, with a hydroxy alkali metal, the alkali metal cation can precipitate the alkyl trialkyl quat, RR2R3N-(CH2),OH X. This X anion so that the resultant quat is internally neutral method is shown in the following example. 10 ized as follows:

EXAMPLE 8 O In a reaction vessel was placed 13.14 grams of dode cyl dimethyl 2-hydroxyethyl ammonium bromide, 21.22 is A-O-S-a-O. grams of acetone solvent and 4.72 grams of sodium O carbonate. While stirring under nitrogen, 3.27 grams of This internally neutralized sulfate quat is the equivalent acetyl chloride was added dropwise. Gas evolution of the same quat neutralized by an external anion and is occurred. The mixture was then refluxed (ca. 60 C.) for within the scope of the invention. Some examples of 6 hours. The solvent was removed under vacuum. The 20 these compounds are: residue was extracted with isopropanol to dissolve the dioctyl methyl (2-hydrosulfatoethyl) ammonium bro quat and the solution was filtered hot to remove sodium mide; chloride and sodium carbonate. The filtrate was evapo nonyl dimethyl (sodium 4-sulfatobutyl) ammonium rated under vacuum leaving as the product dodecyl chloride; dimethyl acetyloxyethyl ammonium bromide. 25 octadecyl dimethyl 2-hydrosulfatoethyl ammonium Still another embodiment of the invention are com fluoride; pounds of the formula A-CNX. These can be exem hexadecyl dimethyl 2-hydrosulfatobutyl ammonium plified by: bromide; dioctyl methyl cyanomethyl ammonium bromide; octyl dimethyl 2-sulfatoethyl ammonium bromide; didecyl methyl 2-cyanopropyl ammonium chloride; 30 dodecyl dimethyl 2-sulfatoethyl ammonium chloride; didodecyl methyl 5-cyanopentyl ammonium iodide; octadecyl dimethyl 3-sulfatopropyl ammonium bro octadecyl dimethyl 6-cyanohexyl ammonium fluoride; mide; and the like. and the like. More preferably R1 is a C8-18 alkyl, R2 is a C8-18 alkyl In a preferred embodiment, R1 is a C8-18 alkyl, R2 is a or a methyl group, m is 2 and X is chlorine or bromine. 35 C8-18 alkyl or a methyl group, m is 2 and X is chlorine These are illustrated by: or bromine. Representative examples of these com octyl dimethyl 2-cyanoethyl ammonium chloride; pounds are: decyl dimethyl 2-cyanoethyl ammonium bromide; octyl dimethyl 2hydrosulfatoethyl ammonium chloride; dodecyl dimethyl 2-cyanoethyl ammonium chloride; 40 dioctyl methyl 2-hydrosulfatoethyl ammonium bro tetradecyl dimethyl 2-cyanoethyl ammonium bromide; mide; octadecyl dimethyl 2-cyanoethyl ammonium bromide; decyl dimethyl 2-hydrosulfatoethyl ammonium bro dioctyl methyl 2-cyanoethyl ammonium chloride; mide; didecyl methyl 2-cyanoethyl ammonium bromide; decyl dimethyl 2-sulfatoethyl ammonium chloride; and the like. 45 dodecyl dimethyl 2-hydrosulfatoethyl ammonium chlo This class of quats can be made by reacting an appro ride; priate haloalkyl nitrile, X-(CH2)n-CN, with a tert didodecyl methyl 2-hydrosulfatoethyl ammonium bro amine, RR2R3N, in an inert solvent such as tetrahydro mide; furan, dioxane or diglyme and preferably under nitro tetradecyl dimethyl 2-hydrosulfatoethyl ammonium gen and under substantially anhydrous conditions. The 50 bromide; following example shows how the nitrile quats can be octadecyl dimethyl 2-sulfatoethyl ammonium chloride; made. and the like including the alkali metal salts. One method of making these sulfate-substituted quats EXAMPLE 9 is to react chlorosulfonic acid, ClSO3H, with the hy In a reaction vessel was placed 130.5 grams of diox 55 droxy quat A-OH X. This reaction is preferably ane and 40.48 grams of dodecyl dimethyl amine. While conducted in an inert solvent under nitrogen attemper stirring under nitrogen, 25.69 grams of 2-bromoethyl atures from O C. up to reflux. The following example nitrile was added dropwise. An exotherm occurred illustrates the preparation of a sulfate quat. raising the temperature to 40° C. and a white precipitate 60 EXAMPLE 10 formed. The mixture was heated to reflux and held at In a reaction vessel was placed 29.45 grams of dode reflux (ca. 95-100 C.) for 2.5 hours. The mixture was cyl dimethyl 2-hydroxyethyl ammonium bromide and then cooled and an additional 382.49 grams of para 50 mLs of methylene chloride solvent. This was cooled dioxane was added. The product, dodecyl dimethyl to 5 C. and while stirring under nitrogen, 10.21 grams 2-cyanoethyl ammonium bromide, precipitated and was 65 of chlorosulfonic acid was added dropwise over 15 recovered by filtration. minutes at 5-10 C. Then 4.75 grams of sodium carbon In another embodiment of the invention the novel ate was added to neutralize the mixture and the orange quat has the formula solution was filtered. The methylene chloride was evap 4,883,917 10 orated from the filtrate under vacuum leaving as the Temperature gradually rose to 110° C. at which time no product a light tan solid identified as dodecyl dimethyl more water came off. After 4 hours the mixture was 2-sulfatoethyl ammonium bromide. cooled and the product dodecyldimethyl (2-acetic acid The sulfato quat can also be made by the direct sulfo phenyl ester) ammonium chloride precipitated and was nation of the hydroxyalkyl quat, A-OHX, with SO3. recovered by filtration. This is shown in the following example. A still further group of compounds of the invention are the alkyne quats having the structure A-C=CH. EXAMPLE In this application the compounds will be named as In a reaction vessel was placed 8.15 grams of dode alkyne substituted quaternary ammonium compounds cyldimethyl 2-hydroxyethyl ammonium bromide and 10 such that the compound 25 mLs of methylene chloride. This solution was stirred under nitrogen and cooled to 10 C. Then, 2.62 grams of liquid SO3 was added dropwise at 10-15 C. Unreacted SO3 was then sparged from the flask with nitrogen. is named trimethyl 3-(1-propyne) ammonium chloride. Sufficient sodium carbonate was added to neutralize 15 Other examples of these acetylenic quats are: acidity and the mixture was filtered. The filtrate was octyl dimethyl 4-(1-butyne) ammonium iodide; evaporated under vacuum leaving as the product dode octadecyl dimethyl 6-(1-hexyne) ammonium fluoride; cyl dimethyl sulfatoethyl ammonium bromide. didodecyl methyl 3-(1-propyne) ammonium chloride; Another class of compounds of the invention are and the like. those having the formula A-C(O)-O-R9 X The more preferred compounds of this class are those wherein R9 is an alkyl containing from 1 to about 6 wherein R is a C8-18 alkyl, R2 is a C8-18 alkyl or a carbon atoms or a phenyl group. Representative exam methyl group, m is 1 and X is chlorine or bromine. ples of these compounds are: Examples of these more preferred acetylenic quats are: octyl dimethyl (2-acetic acid hexyl ester) ammonium octyl dimethyl 3-(1-propyne) ammonium chloride; bromide; 25 decyl dimethyl 3-(1-propyne) ammonium bromide; decyl dimethyl (3-propionic acid phenyl ester) ammo dodecyl dimethyl 3-(1-propyne) ammonium chloride; nium iodide; tetradecyl dimethyl 3-(1-propyne) ammonium bromide; octyl dimethyl (4-butyric acid hexyl ester) ammonium octadecyl dimethyl 3-(1-propyne) ammonium chloride; chloride; dioctyl methyl 3-(1-propyne) ammonium chloride; hexadecyl dimethyl (6-hexanoic acid butyl ester) ammo 30 didodecyl methyl 3-(1-propyne) ammonium bromide; nium fluoride; and the like. and the like. The acetylenic quats can be made by reacting the The more preferred compounds are those in which appropriate haloalkyne, X-(CH2)n-C=CH, with the R is a C8-18 alkyl, R2 is a C8-18 alkyl or a methyl group, appropriate tert-amine, RR2R3N. The reaction does m is 1 or 2, and X is chlorine or bromine. Some exam not require a solvent although an inert solvent can be ples of these preferred compounds are: used. The following example illustrates how the acety octyl dimethyl (2-acetic acid methyl ester) ammonium lenic quats can be made. bromide; decyl dimethyl (3-propionic acid octyl ester) ammo EXAMPLE 14 nium chloride; In a reaction flask was placed 64.28 grams of octyl dodecyl dimethyl (2-acetic acid phenyl ester) ammo dimethyl amine and 90.17 grams of methylethyl ketone. nium bromide; With stirring and under a nitrogen atmosphere, 30.76 tetradecyl dimethyl (3-propionic acid butyl ester) am grams of propargyl chloride was added dropwise over monium chloride; a 30 minute period. The mixture was then heated to and the like. 45 reflux (ca. 85° C) and held at reflux for 1 hour. It was These compounds can be made by reacting an appro then cooled and the product, octyl dimethyl 3-(1- priate haloalkanoate ester, X-(CH2)n-CO)-OR9, propyne) ammonium chloride separated as a dark gold with a trialkyl amine, RR2R3N. The reaction is con liquid. ducted in an inert solvent at an elevated temperature up Another useful quat of the invention is represented by to reflux. The following example illustrates the way 50 these compounds are made. the formula EXAMPLE 12 O M. N. In a reaction flask was placed 8.16 grams of methyl A-CH-CH2 X 3-bromopropionate and 20 mL methylethyl ketone. To 55 this was added 11.26 grams of tetradecyl dimethyl These are referred to as epoxy quats. Some representa amine and the mixture was refluxed for 6 hours. The tive examples are: reaction mixture was then cooled and the product, tet octyl dimethyl 2,3-epoxypropyl ammonium chloride; radecyl dimethyl (3-propionic acid methyl ester) ammo octadecyl dimethyl 5,6-epoxyhexyl ammonium bro nium bromide precipitated. 60 mide; The ester quat can also be made by esterification of didecyl methyl 3,4-epoxybutyl ammonium iodide; the appropriate betaine. dodecyl dimethyl 2,3-epoxypropyl ammonium fluoride; and the like. EXAMPLE 13 In a more preferred embodiment R is a C8-18 alkyl, In a reaction flask was placed 20 grams of dodecyl 65 R2 is a C8-18 alkyl or a methyl group, m is 1 and X is dimethyl betaine, 1.83 grams of phenol, 20 mLs of tolu chlorine or bromine. Some of these more preferred ene and 1 mL of conc. HCl. This was heated to reflux epoxy quats are: and water was removed using a Dean-Stark water trap. octyl dimethyl (2,3-epoxypropyl) ammonium chloride; 4,883,917 11 12 decyl dimethyl (2,3-epoxypropyl) ammonium bromide; tert-amine, RR2R3N, in an inert solvent at an elevated dodecyl dimethyl (2,3-epoxypropyl) ammonium chlo temperature of about 50° C. up to reflux. The reaction is ride; preferably maintained under nitrogen. Some of the al tetradecyl dimethyl (2,3-epoxypropyl) ammonium bro kylthio alkyl halides used in the preparation are stench mide; compounds so due caution should be maintained. The octadecyl dimethyl (2,3-epoxypropyl) ammonium chlo preparation of a typical alkylthio quat is shown in the mide; following example. dioctyl methyl (2,3-epoxypropyl) ammonium chloride; didecyl methyl (2,3-epoxypropyl) ammonium bromide; EXAMPLE 16 ditetradecyl methyl (2,3-epoxypropyl) ammonium chlo 10 ride; In a reaction vessel was placed 99.9 grams of methyl dihexadecyl methyl (2,3-epoxypropyl) ammonium bro ethyl ketone, 70.02 grams of tetradecyl dimethyl amine mide; and 30.9 grams of methylthiomethylchloride. The mix and the like. ture was stirred and heated under nitrogen to reflux (ca. 90° C.) and held at reflux for 6 hours. It was then cooled The epoxy quats can be made by reacting an epoxy 15 and the product, tetradecyl dimethyl methylthiomethyl halide, ammonium chloride precipitated as a yellow-white O solid and was recovered by filtration. / N The following example shows the preparation of an CH2-CH-(CH2)-X, 20 alkylthio quat without the use of a solvent. with a tert-amine, RR2R3N. The reaction is run in an EXAMPLE 17 inert solvent such as tetrahydrofuran, dioxane, dimeth In a glass reaction vessel was placed 86.52 grams of oxyethane and the like and under a nitrogen atmosphere didecyl methyl amine. The amine was stirred under at 20° C. up to reflux and preferably under substantially nitrogen and 29.07 grams of methylthiomethylchloride anhydrous conditions. The following example shows 25 was added dropwise over 5 minutes. The mixture was how the epoxy quats can be made. then heated to 100 C. and stirred at 100 C. for 6 hours. On cooling the product, didecyl methyl methylthi EXAMPLE 1.5 omethyl ammonium chloride solidified. In a reaction flask was placed 12.4 grams of epi A still further embodiment of the invention are the bromohydrin, 18.73 grams of dodecyldimethyl amine 30 sulfone quats having the structure and 21.34 grams of para-dioxane solvent. This was stirred and heated under nitrogen to reflux (ca. 90 C.). After 6 hours at reflux the mixture was cooled. Solvent O removed under vacuum to afford product, dodecyl A-S-R11 X dimethyl (2,3-epoxypropyl) ammonium bromide as a 35 clear gel. O Another embodiment of the invention is an alkylthio quat. These are compounds having the formula A wherein R11 is an alkyl containing 1 to about 10 carbon S-R10X wherein R10 is an alkyl containing 1 to about atoms or a phenyl group. Some examples of these com 10 carbon atoms or a phenyl group. Some examples of 40 pounds are: these compounds are: decyl dimethyl methylsulfonomethyl ammonium chlo octyl dimethyl methylthioethyl ammonium chloride; ride; octadecyl dimethylbutylthioethyl ammonium bromide; hexadecyl dimethylbutylsulfonoethyl ammonium bro octadecyl dimethylhexylthiobutyl ammonium iodide; mide; hexadecyl dimethyl decylthiohexyl ammonium fluo 45 octadecyl dimethylhexylsulfonobutyl ammonium fluo ride; ride; dodecyl dimethyl ethylthiopentyl ammonium bromide; dioctyl dimethyl decylsulfonohexyl ammonium iodide; octyl dimethyl phenylthioethyl ammonium bromide; octyl dimethyl phenylsulfonatoethyl ammonium chlo didodecyl methyl phenylthiobutyl ammonium iodide; ride; and the like. 50 dodecyl dimethyl phenylsulfonatopropyl ammonium The more preferred alkylthio quats of this embodi bromide; ment are those in which R1 is a C8-18 alkyl, R2 is a C8-18 dioctyl methyl phenylsulfonatomethyl ammonium io alkyl or a methyl group, R10 is alkyl, m is 1 and X is dide; chlorine or bromine. Some examples of these more and the like. preferred compounds are: 55 Of the above sulfone quats, the more preferred are octyl dimethyl methylthiomethyl ammonium bromide; those in which R1 is a C8-18 alkyl, R2 is a C8-18 alkyl or decyl dimethyl ethylthiomethyl ammonium chloride; a methyl group, R is alkyl, m is 1 and X is chlorine or dodecyl dimethylbutylthiomethyl ammonium bromide; bromine. Some examples of these compounds are: tetradecyl dimethyl decylthiomethyl ammonium chlo octyl dimethyl methylsulfonomethyl ammonium chlo ride; ride; dioctyl methyl methylthiomethyl ammonium chloride; decyl dimethyl ethylsulfonomethyl ammonium bro didecyl methyl ethylthiomethyl ammonium bromide; mide; didodecyl methylbutylthiomethyl ammonium chloride; dodecyl dimethylbutylsulfonomethyl ammonium chlo ditetradecyl methyl decylthiomethyl ammonium bro ride; mide; 65 tetradecyl dimethyl decylsulfonomethyl ammonium and the like. bromide; These alkylthio quats can be made by reacting an octadecyl dimethyl methylsulfonomethyl ammonium alkylthio alkyl halide, R10-S-(CH2)n-X, with a chloride; 4,883,917 13 14 dioctyl methyl methylsulfonomethyl ammonium chlo - and the like. ride; The sulfoxide quats can be made by the oxidation of didecyl methyl propylsulfonomethyl ammonium bro the alkylthio quats using the proper stoichiometry to mide; oxidize the sulfur to the tetravalent state. The prepara didodecyl methylhexylsulfonomethyl ammonium chlo tion of a sulfoxide quat is shown in the following exam ride; ple. ditetradecyl methyl octylsulfonomethyl ammonium bromide; EXAMPLE 9 and the like. In a glass reaction flask was placed 21.95 grams of the The new compounds can be made by oxidizing the O didecyl methyl methylthiomethyl ammonium chloride previous alkylthio quats using aqueous hydrogen perox from Example 17. This was warmed to 60° C. to melt ide. Care should be taken so that a large amount of the quat and 4.03 grams of 50% aqueous hydrogen unreacted hydrogen peroxide is not allowed to buildup peroxide was added dropwise over 8 minutes at 60° C. in the reaction mixture. The following example shows with vigorous stirring. The mixture was then heated to the preparation of a typical sulfone substituted quat. 15 75 C. and held at 75° C. for 2 hours. On cooling the product, didecyl methyl methylsulfoxomethyl ammo EXAMPLE 18 nium chloride was recovered as a brown liquid. In a reaction vessel was placed 20.5 grams of the A still further embodiment of the invention is an didecyl methyl methylthiomethyl ammonium chloride acyloxybenzene sulfonate (AOBS) quat of the structure made in Example 17. This was heated to 60 C. to melt 20 the quat and then 10.5 grams of 50% aqueous hydrogen peroxide was added dropwise over a 1 hour period with vigorous stirring. An exothermic reaction occurred. SO The reaction was then heated to 75 C. and held at this ACO temperature for 4 hours forming a pale yellow liquid. 25 On cooling the liquid gelled. Infrared confirmed the compound as being didecyl methyl methylsul In this embodiment X is not shown because upon fonomethyl chloride. neutralization of the sulfonic acid group the negative Another embodiment of the invention can be repre charge resides on the resulting sulfonate substituent sented by sulfoxide substituted quats which have the 30 making it unnecessary to include the Xr anion. Repre formula sentative examples of these compounds are: 3-(octyl dimethyl ammonium)propionyloxybenzene sulfonate; A-S-R12 X 35 4-(dodecyl dimethyl ammonium)butyryloxybenzene sulfonate; wherein R2 is an alkyl containing about 1 to 10 carbon 2-(octadecyl dimethyl ammonium)acetyloxybenzene atoms or a phenyl group. These compounds can be sulfonate; exemplified by the following: 6-(decyl dimethyl ammonium)hexanoyloxybenzene sul octyl dimethyl butylsulfoxomethyl ammonium chlo fonate; ride; and the like. dodecyl dimethyl decylsulfoxoethyl ammonium bro In a more preferred embodiment of the AOBS quat, mide; R is a C8-18 alkyl, R2 is a C8-18 alkyl or a methyl group, dioctyl methyl octylsulfoxomethyl ammonium fluoride; and m is 2. Examples of this preferred class are: octadecyl dimethyl phenylsulfoxomethyl ammonium 45 3-(octyl dimethyl ammonium)propionyloxybenzenesul bromide; fonate; and the like. 3-(decyl dimethyl ammonium)propionyloxybenzenesul In a more preferred embodiment of the sulfoxide fonate; quat, R is a C8-18 alkyl, R2 is a C8-18 alkyl or a methyl 3-(dodecyl dimethyl ammonium)propionyloxybenzene group, R2 is alkyl, m is 1 and X is chlorine or bromine. 50 sulfonate; Representative examples of this more preferred class of 3-(tetradecyl dimethyl ammonium)propionyloxyben compounds are: Zenesulfonate; Y octyl dimethyl methylsulfoxomethyl ammonium chlo 3-(tetradecyl dimethyl ammonium)propionyloxyben ride; Zenesulfonate; decyl dimethyl ethylsulfoxomethyl ammonium bro 55 3-(dioctyl methyl ammonium)propionyloxybenzenesul mide; fonate; dodecyl dimethylbutylsulfoxomethyl ammonium chlo 3-(didecyl methyl ammonium)propionyloxybenzenesul ride; fonate; tetradecyl dimethyl decylsulfoxomethyl ammonium 3-(didodecyl methyl ammonium)propionyloxybenzene bromide; 60 sulfonate; dioctyl methyl methylsulfoxomethyl ammonium bro 3-(ditetradecyl methyl ammonium)propionyloxyben mide; Zenesulfonate; didecyl methyl ethylsulfoxomethyl ammonium chlo and the like. ride; In addition to the usual fungicide algicide and bacteri didodecyl methyl butylsulfoxomethyl ammonium bro 65 cidal properties of the other quats of this invention, the mide; AOBS quats are also useful as bleach activators for ditetradecyl methyl decylsulfoxomethyl ammonium peroxygen bleaching compounds such as sodium perbo chloride; rate. 4,883,917 15 16 The AOBS quats can be made by reacting a haloalk The silane-substituted quats can be made by reacting onyloxybenzenesulfonate alkali metal salt, the appropriate haloalkyl trialkoxy silane,

SO3Na 5 OR 13

OR15 with a tert-amine, RR2R3N. The reaction is conducted with a tert-amine, RR2R3N. The reaction is conducted in a solvent such as methylethyl ketone, tetrahydrofu 10 at an elevated temperature of about 50-100° C. and ran, dioxane and the like at an elevated temperature up under nitrogen. The following example shows how to reflux and under a nitrogen atmosphere. The follow these compounds can be made. ing example shows how the AOBS quats can be made. EXAMPLE 21 EXAMPLE 20 15 In a reaction vessel was placed 12.82 grams of 3 Initially, 3-bromopropionyloxybenzenesulfonate so chloropropyl trimethoxysilane and 15.6 grams of tet dium salt was made by reacting 3-bromopropionylchlo radecyldimethyl amine. The mixture was stirred under ride with the sodium salt of parahydroxybenzene sul nitrogen and heated to 95 C. After 2 hours at 95°C., a fonic acid in methylethyl ketone at reflux. The solid few crystals of KI were added. After 5 hours at 95 C. intermediate precipitated on cooling. 20 the product that formed was found to be 3-(tetradecyl In a glass reaction flask was placed 20.11 grams of the dimethyl ammonium)propyl trimethoxysilane chloride. above sodium salt, 13.21 grams of dodecyl dimethyl A small amount of this product was placed on a glass amine and 100 mLs methylethyl ketone. This was re surface and rubbed to provide a water-repellant brilliant fluxed under nitrogen for 6 hours. The mixture was then 25 finish. A portion was also rubbed on a metal surface cooled and the product was recovered by removal of providing a highly polished finish. solvent under vacuum and identified as dodecyl di Another embodiment of the invention is the group of methyl propionylbenzenesulfonate. diquats which have the formula Another embodiment of the invention is a siloxane quat having the formula 30 wherein p is an integer from 0 to 6. Examples of these OR13 compounds are: di-(octyl dimethyl ammonium ethyl)ocalate dibromide; A-i-or" di-(didecyl methyl ammonium ethyl)succinate dichlo OR 15 35 ride; di-(eicosyl dimethyl ammonium ethyl)malonate diio wherein R13, R1 and R15 are alkyls containing 1-10 dide; carbon atoms or are phenyl groups. Some examples of di-(hexadecyl dimethyl ammonium propyl)glutarate these compounds are: difluoride; 3-(octyl dimethyl ammonium)propyl trimethoxysilane 40 di-(dinonyl methyl ammonium butyl)suberate dibro chloride; mide; 4-(octadecyl dimethyl ammonium)butyl triethoxysilane and the like. bromide; In a more preferred embodiment, R is an alkyl con 6-(octyl dimethyl ammonium)hexyl tridecyloxysilane taining 8-18 carbon atoms, R2 is an alkyl containing iodide; 45 8-18 carbon atoms or the methyl group, m is 2 or 3, p is 4-(eicosyl dimethyl ammonium)butyl tributoxysilane 2-4 and X is chlorine or bromine. Some examples of fluoride; these compounds are: and the like. di-(octyl dimethyl ammonium ethyl)succinate dichlo In a more preferred embodiment R is an alkyl group ride; containing 8-18 carbon atoms, R2 is an alkyl containing 50 di-(decyl dimethyl ammonium propyl)glutarate dibro 8-18 carbon atoms or a methyl group, R3, R3, R1 and mide; Rare methyl, m is 2 or 3 and X is chlorine or bromine. di-(dodecyl dimethyl ammonium ethyl)adipate dichlo Some examples of these more preferred compounds are: ride; 2-(octyl dimethyl ammonium)ethyl trimethoxysilane di-(tetradecyl dimethyl ammonium propyl)succinate chloride; 55 dibromide; 3-(decyl dimethyl ammonium)propyl trimethoxysilane di-(octadecyl dimethyl ammonium ethyl)succinate di bromide; chloride; 2-(dodecyl dimethyl ammonium)ethyl trimethoxysilane di-(dioctyl methyl ammonium ethyl)succinate dichlo chloride; ride; 3-(tetradecyloxy dimethyl ammonium)propyl trimeth 60 di-(didecyl methyl ammonium propyl)glutarate dibro oxysilane bromide; mide; 2-(dioctyl methyl ammonium)ethyl trimethoxysilane di-(didodecyl methyl ammonium ethyl)adipate dichlo chloride; ride; 3-(didecyl methyl ammonium)propyl trimethoxysilane di-(ditetradecyl methyl ammonium propyl)succinate bromide; 65 dibromide. 2-(ditetradecyl methyl ammonium)ethyl trimethoxysil These compounds can be made by reacting the appro ane chloride; priate hydroxy alkyl quat, A-(CH2)n-OH, with a and the like. diacyl halide, XCO)-(CH2)-C(O)x in an inert sol 4,883,917 17 18 vent at 30' up to reflux, preferably under nitrogen. The grams of glutaryl dichloride over a 1 hour period while following example shows a typical preparation. sparging the mixture with nitrogen. This was held at reflux (90° C) for 30 minutes to give a brown solution EXAMPLE 22 of di(dioctyl methyl ammonium ethyl)glutarate dichlo Initially a hydroxyethyl quat was made by reacting 5 ride which could be recovered by evaporation of the 100 grams of dioctyl methyl amine with 42 mLs of methylethyl ketone under vacuum. 2-chloroethanol in 200 grams of methylethyl ketone We claim: - solvent at reflux for 5 hours to obtain a methylethyl 1. Tetradecyl dimethyl 2-methoxyethyl ammonium ketone solution of dioctyl methyl hydroxyethyl ammo chloride. nium chloride. To this was added dropwise, 59.04 10 ck : sk k

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