(en)Z") NOVEL SULFOBETAINES, PREPARED FROM TERTIARY AMINES AND SULTONES, HAVING THE STRUCTURE R-CH(-M(+))-(CH2)N-SO3(-) IN WHICH R IS AN ALKYL GROUP HAVING FROM 6 TO 23 CARBON ATOMS, N IS THE INTEGER 2 OR 3, AND M$ IS A RADICAL HAVING THE STRUCTURE Z''-(C(-X'')(-Y''))B-N(+)(-(C(-X)(-Y))A-Z)(-(C(-X")(-Y"))C- IN WHICH M IS 0 OR AN INTEGER OF FROM 1 TO 5 AND R'' IS H- OR AN ALKYL GROUP HAVING FROM 1 TO 3 CARBON ATOMS, (V) -NR2" IN WHICH EACH R" IS, INDEPENDENTLY, HOR AN ALKYL GROUP HAVING FROM 1 TO 4 CARBON ATOMS, AND (VI) -OR"'', IN WHICH R"'' IS AN ALKYL GROUP HAVING FROM 1 TO 4 CARBON ATOMS, AT LEAST ONE OF SAID SUBSTITUENTS BEING OTHER THAN HYDROGEN ARE PROVIDED. THE FIVE OR SIX MEMBERED CHAIN INCLUDING THE -SO3(-) AND >N(+)< GROUPS PROVIDES FOR READY INNER SALT OR RING FORMATION, GIVING RESISTANCE TO DEGRADATION, SUCH AS N+(-)3-(CH2)3-SO3(-) AND N+(-)3-(CH2)4-SO3(-) NOT READILY OBTAINED WITH SIMILAR CHAINS CONTAINING OTHER NUMBERS OF ATOMS SUCH AS =N$-CH2-CH2-SO3$, WHICH WOULD REQUIRE A HIGHLY STRAINED FOUR-MEMBERED RING. A MORE EFFECTIVE DETERGENT IS PROVIDED THAN IN COMPOUNDS HAVING THE NITROGEN ATOM IN THE LONGEST CHAIN OF THE MOLECULE. THE DETERGENT COMPOUNDS ARE USEFUL, FOR EXAMPLE, IN LUBRICANTS AND COSMETICS, ALL AS IS MORE PARTICULARLY DESCRIBED IN THE SPECIFICATION WHICH FOLLOWS. WHEREIN A, B, AND C ARE, INDEPENDENTLY, INTEGERS OF FROM 1 TO 6, AND THE SUBSTITUENTS X, X'', X", Y, Y'', Y", Z, Z'', AND Z", ATTACHED TO EACH CARBON ATOM, ARE INDEPENDENTLY, SELECTED FROM THE GROUP CONSISTING OF: (I) HYDROGEN, (II) HYDROXYL, (III)HALOGEN, (IV) -(CH2)M-COO-R''

1.ApplicationNumber: US-3594411D-A
1.PublishNumber: US-3594411-A
2.Date Publish: 19710720
3.Inventor: GEORGE F. KITE
ARTHUR C. WHITAKER

4.Inventor Harmonized: KITE GEORGE F()
WHITAKER ARTHUR C()

5.Country: US
6.Claims:
(en)Z") NOVEL SULFOBETAINES, PREPARED FROM TERTIARY AMINES AND SULTONES, HAVING THE STRUCTURE R-CH(-M(+))-(CH2)N-SO3(-) IN WHICH R IS AN ALKYL GROUP HAVING FROM 6 TO 23 CARBON ATOMS, N IS THE INTEGER 2 OR 3, AND M$ IS A RADICAL HAVING THE STRUCTURE Z''-(C(-X'')(-Y''))B-N(+)(-(C(-X)(-Y))A-Z)(-(C(-X")(-Y"))C- IN WHICH M IS 0 OR AN INTEGER OF FROM 1 TO 5 AND R'' IS H- OR AN ALKYL GROUP HAVING FROM 1 TO 3 CARBON ATOMS, (V) -NR2" IN WHICH EACH R" IS, INDEPENDENTLY, HOR AN ALKYL GROUP HAVING FROM 1 TO 4 CARBON ATOMS, AND (VI) -OR"'', IN WHICH R"'' IS AN ALKYL GROUP HAVING FROM 1 TO 4 CARBON ATOMS, AT LEAST ONE OF SAID SUBSTITUENTS BEING OTHER THAN HYDROGEN ARE PROVIDED. THE FIVE OR SIX MEMBERED CHAIN INCLUDING THE -SO3(-) AND >N(+)< GROUPS PROVIDES FOR READY INNER SALT OR RING FORMATION, GIVING RESISTANCE TO DEGRADATION, SUCH AS N+(-)3-(CH2)3-SO3(-) AND N+(-)3-(CH2)4-SO3(-) NOT READILY OBTAINED WITH SIMILAR CHAINS CONTAINING OTHER NUMBERS OF ATOMS SUCH AS =N$-CH2-CH2-SO3$, WHICH WOULD REQUIRE A HIGHLY STRAINED FOUR-MEMBERED RING. A MORE EFFECTIVE DETERGENT IS PROVIDED THAN IN COMPOUNDS HAVING THE NITROGEN ATOM IN THE LONGEST CHAIN OF THE MOLECULE. THE DETERGENT COMPOUNDS ARE USEFUL, FOR EXAMPLE, IN LUBRICANTS AND COSMETICS, ALL AS IS MORE PARTICULARLY DESCRIBED IN THE SPECIFICATION WHICH FOLLOWS. WHEREIN A, B, AND C ARE, INDEPENDENTLY, INTEGERS OF FROM 1 TO 6, AND THE SUBSTITUENTS X, X'', X", Y, Y'', Y", Z, Z'', AND Z", ATTACHED TO EACH CARBON ATOM, ARE INDEPENDENTLY, SELECTED FROM THE GROUP CONSISTING OF: (I) HYDROGEN, (II) HYDROXYL, (III)HALOGEN, (IV) -(CH2)M-COO-R''

7.Description:
(en)United States Patent 01 hce 3,594,411 Patented July 20, 1971 3,594,411 SULFOBETAINE DETERGENTS, AND LUBRICANTS AND COSMETICS CONTAINING SAME George F. Kite, Springdale, and Arthur C. Whitaker,
Pittsburgh, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa. N Drawing. Filed Apr. 25, 1968, Ser. No. 724,290 Int. Cl. C07c 143/14 US. Cl. 260-50112 4 Claims ABSTRACT OF THE DISCLOSURE Novel sulfobetaines, prepared from tertiary amines and sultones, having the structure H R-( J(CH )nS0 in which R is an alkyl group having from 6 to 23 carbon atoms, 11: is the integer 2 or 3, and M is a radical having the structure wherein a, b, and c are, independently, integers of from 1 to 6, and the substituents X, X, X", Y, Y, Y, Z, Z, and Z, attached to each carbon atom, are independently, selected from the group consisting of:
(i) hydrogen, (ii) hydroxyl, (iii) halogen,
The five or six membered chain including the SO.-, and 1%I groups provides for ready inner salt or ring formation, giving resistance to degradation, such as not readily obtained with similar chains containing other numbers of atoms such as EN CH CH -SO which would require a highly strained four-membered ring. A more effective detergent is provided than in compounds having the nitrogen atom in the longest chain of the molecule. The detergent compounds are useful, for example, in lubricants and cosmetics, all as is more particularly described in the specification which follows.
This invention relates :to novel compounds in the form of particular sulfobetaines, and detergents, cosmetics, and lubricant compositions containing the same.
Known sulfobetaines such as CH CH (|3HOH S0 C2115 C2115 02115 are not effective detergents, and further, because of the four membered chain EN C--CSO;, do not readily form inner ring salt compounds. Instead, there is a tendency to form salts or complexes inter-molecularly rather than intramolecularly, as for example (IJQH5 C2115 emanation-oarso, mLoH-om so,
Other known sulfobetaines such as (|JH OH CH S0 a T 2)n a CH have detergent properties, but the inclusion of the nitrogen atom in the longest chain detracts from such properties.
It has now been found that superior detergent and surface active compositions are the sulfobetaines of the empirical formula t Rt 3- oH, ,-so,
in which R is an alkyl group having from 6 to 23 carbon atoms, n is the integer 2 or 3, and M is a radical having the structure 2!! wherein a, b, and c are, independently, integers of from 1 to 6, and the substituents X, X, X", Y, Y, Y", Z, Z, and Z, attached to each carbon atom, are, independently, selected from the group consisting of:
(i) hydrogen, (ii) hydroxyl, (iii) halogen,
in which m is 0 or an integer of from 1 to 5 and R is H or an alkyl group having from 1 to 3 carbon atoms, (v) NR in which each R is, independently, H
or an alkyl group having from 1 to 4 carbon atoms, and (vi) -O-R", in which R' is an alkyl group having from 1 to 4 carbon atoms, at least one of said substituen-ts being other than hydrogen. Examples of the radical R are hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and tetracosyl. Branched chain hydrocarbon radicals, as the radical R are also useful. These include: 2-ethylhexyl, 3-methylhexyl; S-ethyl nonyl; 2,5-dimethyl decyl, 2-methyl-10-propyl dodecyl, 6,10-dimethyl-Z-tetradecyl, 6-isopropylhexadecyl, 4,8,12,16-tetramethyl-Z-octadecyl, S-methyl docosyl and propylene dimer, trimer and tetramer. As examples of the substituents X, X, X", Y, Y, Y", Z, Z, and Z, the following are representative: hydrogen, hydroxyl, chlorine, bromine,
These substituents may be the same or different, i.e., they are independently, any of the described radicals, as long as at least one of them is other than hydrogen. For many purposes, it is preferred that at least one of these substituents is hydroxyl.
In addition to the advantages hereinafter enumerated, the subject sulfobetaines exhibit some properties of each of the nonionic, cationic, and anionic detergents. They are effective in hard water, and are resistant to degradation by chemicals. One reason stable compounds are believed to exist is the stability of the inner salt or ring compounds wherein the ring contains five or six atoms. Rings with this number of atoms are much more stable than rings having a larger or smaller number of atoms. The following represent rings which may be obtained with the compounds of the invention:
C e so; 9
In the products having hydroxyl groups, enhanced physiological properties such as skin afterfeel are obtained. Similarly, such products have improved solubility in bydroxylic solvents and improved compatibility with cosmetic bases. Accordingly, they are useful in such solutions as electroplating baths, metal cleaning solutions, and the like. Other uses of particular importance are as ashless detergents in lubricants such as hydrocarbon motor oils, and in cosmetics or salves such as skin creams, as emulsifiers and dispersants. In the latter utility they provide a pleasant, smooth afterfeel on the skin.
Although any known method is useful for preparing the sulfobetaines of the invention, a particularly useful method is by the reaction of a 1,3- or 1,4-alkanesultone with a tri(substituted alkyl)amine. Suitable sultones have the empirical formula in which R and n have the meaning given above.
Useful 1,3- and 1,4-n-alkanesultones are as follows: 1,3-nonanesultone; 1,4-nonanesnltone; 1,3-decanesultone; 1,4-decanesultone; 1,3-undecanesultone; 1,4-undecanesultone; 1,3-d0decanesultone; 1,4-dodecanesultone; 1,3-tridecanesultone; 1,4-tridecanesultone; 1,3-tetradecanesultone; 1,4-tetradecanesultone; 1,3-pentadecanesultone; 1,4- pentadecanesultone; 1,3-hexadecanesultone; 1,4-hexadecanesultone; 1,3-heptadecanesultone; 1,4-heptadecanesultone; and the 1,3- and 1,4-alkane sultones of octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, and pentacosane. Examples of useful branched chain compounds are S-mcthyl-1,3-nonanesultone, 7- methyl-1,3-dodecanesultone, 8,12-diethylhexanedecanesultone, 5,8,12-trimethyl-1,4-oetadecanesultone; 4-methyl, 9- isopropyl 1,3 cosanesultone; and 6,12,16,20-tetramcthyl-1,4-tetracosanesultone.
The sultones employed can be obtained in any suitable manner. One method involves bringing together an alpha olefin with S0 in gaseous form in an inert medium, such as nitrogen, at a temperature of about 10 to about 25 C. at about atmospheric pressure, for about 0.1 to 0.5 second.
4 The useful tertiary amines have the formula V X X Z N 6- Z 3 I I? b (XCY").
in which X, X, X", Y, Y, Y", Z, Z, and Z" and a, b and e have the meaning given above. Among the tri(substituted alkyl)-amines, the following are given as examples: trimethanol amine; triethanol amine; tripropan-3-ol amine; trihexan-6-olamine; N,N-dimethanol alanine; methyl ester of N,N-dimethanol-[i-alanine; N,N-diethanol 3 aminopropionic acid; 2-chloro-N,N-diethylethyl amine; 2-chlor0- N,N-dimethylethyl amine; N,N-dimethyl-2-amino-l-butan01; methyldiethanolamine; dimethylethanolamine, triisopropanolamine; dimethylaminomethyl-amine; N,N dimethyl (N,N'-diethyl)aminomethylamine; methyldiisopropanolamine; dimethylaminomethylamine; N, N dinolamine.
Examples of sulfobetaines falling within the invention are:
The reaction ofa sultone with a (substituted trialkyl) amine, taking trimethanol amine as an example, may be represented by the following equation:
No by-products are formed in this reaction.
The process can be carried out by bringing the reactants together at a temperature of from about 100 to about 200 0., preferably about 125 to about 175 C., at autogenous pressure of about atmospheric pressure to about 500 pounds per square inch gauge, or even higher, for about two to about twenty hours, preferably for about six to about ten hours. Solvents are not necessary, but any inert solvent, particularly polar solvents, for example, lower alcohols, such as methanol, cyclic ethers, such as dioxane, ketones, such as acetone, amides, such as dimethylformamide, etc. can be employed. The sulfobetaine can be recovered from the reaction product in any convenie'nt manner. For example, one method involves decolorization of an isopropanol solution of the reaction product with activated carbon, extraction with hexane, evaporation to dryness, and recrystallization from methanol or isopropanol.
The following examples illustrate the invention.
EXAMPLE 1 Six and one-half grams of a mixture of sultones, 75%
by Weight of which was the sultone and 25% by weight of which was the sultone a( 2)1z 2)2SO2 was refluxed with slightly less than one equivalent (on sultone )of triethanol amine in fifty milliliters of dodecane at atmospheric pressure and a temperature of 215 to 220 C. over a period of five to six hours. The reaction mixture was cooled to room temperature, hexane added and extracted with water. The aqueous solution was evaporated to dryness to give 8.5 grams of a mixture containing the following compounds:
and
9 CH3 (CH2)12--CH-( CH2) r30 N -CH CH2O HOCHz CH CHzCHzOH EXAMPLE 2 The detergent properties of the mixture obtained above, and of a standard detergent, tridecylbenzenesulfonate (TDBS), were compared with each other. The data are presented below in Table l.
EMMPLE 3 The sulfobetaine of Example 1 makes an excellent detergent, in the following formulation:
Ingredient: Parts by weight Sodium tripolyphosphate 20-50 Sulfobetaine of Example 2 5-20 Sodium silicate 5-15 Sodium sulphate 10-20 Carboxylmethyl cellulose, i.e. sodium salt thereof 0.1-1
Tarnish inhibitors and other conventional additives are of 'benefit. When dissolved in water, a liquid detergent is obtained.
EXAMPLE 4 Ingredient:
Refined mineral oil, API gravity 249 and viscosity SUS 210 F. of 76 Sulfobetaine of Example 1 1 Antioxidants such as trialkyl phenols or naphthylamine, anti-Wear agent such as P S -terpene reaction product, pour point depressors, and the like Usual amounts EXAMPLE 5 A sun screening lotion is provided by emulsifying the following materials:
Parts by weight Ingredient: Parts by weight P-aminobenzoate 2 Polyethylene glycol 20 Menthol 0.1 Ethanol or isopropanol 35 Perfume 0.2 Sulfobetaine of Example 1 0.5 Water 45 We claim:
1. Sulfobetaines of the empirical formula RO-(OH;).,--S 03 the in which R is an alkyl group having from 6 to 23 carbon atoms, 11 is the integer 2 or 3, and M is a radical having the structure wherein a, b and c are, independently, integers of from 1 to 6, Z is hydroxyl and Z and Z" are, independently, hydrogen or hydroxyl.
7 8 2. The composition of claim 1 in which M is 4. The composition of claim 1 in which R is a branched chain alkyl radical. 0H (5H2)q References Cited Jfiwnnron 5 UNITED STATES PATENTS JHQ)o 3,346,628 10/1967 -Riezebos et al 260501.12
0H JOHN D. RANDOLPH, Primary Examiner in which 0, p and q are, independently, integers of from 10 W, GLYNN, Assistant Examiner 1 to 6, and R contains from 8 to 17 carbon atoms. U S Cl X R 3. The composition of claim 2 in which 0, p and q are, independently, integers of from 1 to 3. 25233.4, 152; 260327, 481; 42460