US2569326A - Unsymmetrical quaternary ammonium alkyl sulfates - Google Patents

Description

Fatenteci fsegai. 2&1, E g? UNSYMMETRICAL QUATERNARY AMltIO- NIUM ALKYL SULFATES Joseph B. Niederl, Brooklyn, N. Y., William F. Hart, Easton, Pa., and Martin E. McGreal, Sommersworth, N. IL, assignors to J. B. Niederl & Associates, Inc., New York, N. Y., a corporation of New York No Drawing. Application July 30, 1948, Serial No. 41,728

13 Claims. (Cl. 260-2471) This invention relates to unsymmetrical quaternary ester-salts of morpholine and thiamorpholine and to the process by which they are produced.

This application carries forward work done in connection with certain of the compounds described in our Patent No. 2,380,325 relating to Asymmetric Quaternary Ester-Salts of Morpholine, issued July 10, 1945. The present invention differs, however, in both the process as well as the types of compounds produced.

As to the process, in the present invention a more direct method is used. Instead of first preparing a reactive quaternary ammonium halide and reacting this halide with appropriate metal salts of a mono-alkyl sulfate, in the present invention a tertiary amine is reacted directly with an unsymmetrical dialkyl sulfate as follows:

Although in the present invention the alkyl radical in the anionic part of the molecule is different from any radicals in the cationic part of the molecule, all the radicals in linked to the quaternary nitrogen atom need not to be different, which is another distinguishing mark between the present invention and the patent cited above.

In addition to the improvement in process, the present invention offers two more distinct features. One of these features is the production of quaternary ammonium alkyl sulfates in which the carbon content of the anion is exactly the same as the total carbon content in the cation Y==R4. Thus through the presentinvention the production of perfectly balanced ionics (Equionics") has become possible. In these balanced ionics a still more perfect intramolecular synchronization of groups, possessing a priori desirable physical, chemical and physiological properties, has been realized.

The other new feature given in the present invention is the production of quarternary ammonium alkyl sulfates in which the alkyl radical in the sulfate group has a higher carbon content, than the total of carbon atoms present in the cationic part of the molecule (Y R4).

While some of the symmetrical quarternary ammonium alkyl sulfate described in our patent application Serial No. 787,468, filed November 21, 1947 (Y R4) but where the difference in carbon content between Y and R4 is very small, approximate the behavior of the products claimed in the present invention, nevertheless these latter products differ radically from the quaternary ammonium compounds of comparable carbon content known heretofore. Usually in these latter compounds the anion is very small in comparison to the cationic portion of the molecule. The anion in such products is usually presented by ionizable chlorine while the cationic part of the molecule, in case of capillary active substances, contains at least 15 or more carbon atoms linked to the quaternary ammonium nitrogen atom.

Utilizing the reaction scheme presented in this invention, chemical compositions can be created with predetermined properties. Thus, it is possible to produce substances in which detergency is conferred upon the anion alone or upon both, the cation and the anion. The hydrophilic action of these types of compounds is then quite different from the cationic quaternary ammonium types of compounds possessing a dwarf sized anionic grouping. Thus a gradual and staggered solubility behavior can be induced in these new types of compounds claimed in the present invention. It is possible to produce substances ranging from complete water solubility to complete insolubility and from completely all soluble substances to complete insolubility in non-polar solvents. These characteristics allow a wider range in practical and industrial applications, than with detergents which incorporate surface-activity either in the anionic part of the molecule alone (sulfonated oils, mono-alkyl sulfate salts) or only in the cationic portion of the molecule (invert soaps). Thus these new compounds are valuable as wetting, emulsifying and dispersing agents particularly in cases, where both the anionic as well as the cationic types, as well as the non-ionic detergents fail. Many of thecompounds are potent germicides and fungicides.

The tertiary amines utilizable in this invention, can be of the aliphatic, aromatic, alicyclic or simple or mixed heterocyclic types. They may be plain or further substituted by hydroxyl, alkoxyl and acyl groupings. The following tertiary mines have been found perfectly suitable for use in the present invention: tri-methyl amine; tri-ethyl amine; tri-ethylol amine; the tri-propyl-, the tri-butyland tri-amyl amines; N,N dimethyl amino ethanol; N,N diethylamino-ethanol; dimethyl-aniline; diethyl-, dipropyl, di-butyl, di-amyl-anilines; N,N-dimethyland N,N di ethyl benzyl amines; tri-benzylamine; N,N-dimethyland N,N-diethylalpha as well as beta naphthyl amines; N,N-dimethylcyclo-hexyl amine; N-methyl and N-ethyl-piperidine, pyridine, quinoline. iso-quinoline; nicotine and a whole series of N-alkyl morpholines, thiamorpholines. thiamorpholine-oxides and thiamorpholine-dioxides.

Of the unsymmetrical di-alkyl sulfates the following methyl sulfates have been used in the masses 3 chemical transformation described in the presen invention:

Also the following methyl-cyclo-alkyl sulfates have been found useful:

Methyl-cyclohexyl- Methyl- (a-methyl) cyclohexyl- Methyl- (4t-butyl) cyclohexylflask. After thoroughly mixing the contents, the flask is tightly stopper-ed and the reaction mixture heated on a steam bath at a temperature of 90 C. for a period of six hours. At the end of this time the reaction mixture is allowed to cool and then permittedto stand at room temperature for additional 24 hours. After this time the reaction product is washed with 50 cc. of ether at room temperature. The ether layer containing any nonreacted starting materials is allowed to separate and is then decanted off. This washing operation is once more repeated. The etherwashed reaction product, is then recrystallized from hot ethyl acetate. The product, N-ethyl- N,N,N-tri-n-amy1 ammonium hexadecyl sulfate melts at 82-85 C. (uncorn).

Using the above procedure or the method given in the succeeding example, the following additional equionics were produced:

Reactants Compounds: sulfates Amine Methyl-Sulfate N,N,N-'Irimethyl-N-ethyl Amman. n-amyl n-amyl N ,N,N-Trimethyl-N-ethylol Ammon. n-amyl D N ,N-Dimethyi-N,N-diethyl Ammon. n-hexyL. -n-hexy] N,N-Dimethy1-N,N-dlethyl Ammon. cyclohexyl -cyclohexyl:, N,N-Dimethyl-N,N-di-ethylol Ammon. n-hexyl Di-ethylol-methyl -n-hexyl. N,N-Dimethyl-N,N-diethyl0l Ammon. cyclohexyl .do -cyclohexy1 N,N-Dimethyl-Morpho1inium n-hexyl N-Niethyi Morpholine. -n-hexyl. N-Methyl-Pyridinium n-hexyl Pyridine Do. N-Methyl-Pyridinium cyclohexyl ..do -cyclohexyl. N,N-Dimethyl-Piperidinium n-heptyl N-Methyl-mpcndme. -n-hepty1. N,N,N-Tri-ethyl-N-methyl-Ammon. n-heptyl. Tn-ethyl amine Do. N,N,N-Tri-ethylol-N-methyl-Ammon. n-heptyl ri-ethyloL. Do. N- ethyl-N-ethyl-Piperidinium n-octyl N Ethy1-p1per1d -n-octyl N,N,N-Trimethyl-N- henyl-Ammon. n-nonyl Dimethylanihne n-nonyl N,N,N-Trimethy1-N- enzyl-Ammon. n-decyl. Benzyl -d1mcthyl. -n-decyl N-Methyl-Quinolium n-decyl Qumolme Do. N,N-Diethyl-N-methyl-N-phenyl-Ammon. lauryl Diethylanilin -laury1. N,N,N-Tri-iso-amyl-N-methyl Ammon.cetyl.. Tn-iso-amyL. -oetyl. N- ethyl-N-lauryl-Piperidinium octadecyl N-Lauryl-piperidine. -octadecy1 N-Methyl-N-ethyl Morpholiniu n-heptyi N-Ethyl morpholine. -n hept Methyl-(-t-amyl) cyclohexy1-; Methyl-( i-tt-octyl) cyclohexyl-sulfates.

Replacement of the methyl group in all the above cited methyl-alkyl sulfates by an ethyl radical, slows down the reaction, but does not preclude also the utilization of these types of mixed alkyl sulfates for the preparation of types of unsymmetrical quaternary ammonium alkyl sulfates claimed in this invention.

The process utilized has as its outstanding feature the choice of the reactants, i. e. a tertiary amine and a methyl-alkyl sulfate, which are heated together, in equimolar quantities, either in the presence or absence of a suitable solvent. The procedure involved is very much the same as described in the concomitant patent application Serial No. 787,468 and in the Journal of the American Chemical Society, vol.- 70, page 618 (1948). The present invention itself as well as the pertinent reaction mechanism involved were presented before the Organic Chemistry Division at the Chicago meeting of the American Chemical Society, in April 1948. It was established, by independent syntheses that the short chain alkyl radical, in the present case, the methyl group, migrates to the nitrogen atom leaving the larger alkyl radical or cycloalkyl radical with the sulfate group, as illustrated above, and as is necessary for the production of the types of compounds claimed in this invention.

Example 1.Equionics One tenth mol portion of tri-n-amyl amine (B. P. 125128/l2 mm.) is mixed under warming with one tenth mol of methyl-n-hexadecyl sulfate (M. P. 73 C.) in a round bottomed Pyrex Example 2.Carbon content of anion larger than cation One tenth mol of N-methyl morpholine and one tenth mol of methyl-lauryl sulfate (M. P. 47-48 C.) is placed into a round bottomed Pyrex flask. A water reflux condenser is then attached to the flask and, 200 cc. of toluene added to the reaction mixture. The mixture is then refluxed for six hours. After this time, the reaction mixture is allowed to cool and is then filtered or centrifuged. The residue is then washed with 30 cc. of di-ethyl ether to remove any unreacted starting materials. After decantation of the ether layer the residue is crystallized from hot ethyl acetate. The final product, the N,N-dimethyl-morpholinium lauryl sulfate melts at Gil-62 C. (uncorn).

Using the above procedure or the method given in the preceding example, the following N,N- dialkyl-morpholinium alkyl sulfates were prepared:

aaeasae Reacting N-alkyl-thiamorpholines, N-alkylthiamo'rpholine oxides and N alkyl thiamorpholine-dioxides with methyl-cetyl sulfate and using the procedures as given in Example 1 or 3. Morphoiinium alkyl sulfates of the following formula Clix-CH2 RI as described in Example 2 the following com- N pounds were produced: cm-cfiih Compounds: Cetyl Sulfates Amine N,N-Dimethyl-thiamorpholinium N-Methyl-thiamorpholine. N-Methyl-N-lauryl-thiamorpholinium N-Lauryl-thiamorpholine. N-Methyl-N-myristyl-thiamorpholinium. N-Myristyl-thiamorpholine. N,N,-Dimethy-thiamorpholinium oxide N-Methyl-thiamorpholine-oidde. N -Methyl-N-lauryl-thiamorpholinium oxide N -Lauryl-thiamorpholine-oxido.

N -Methy]-N-myristyl-thiamorpholinium oxide N,N-Dimethyi-thiamorpholinium-dioxide N-Methyl-N-lauryl-thiamorpholiniumdioxide.-

N-livliethyl-N-myristyl-thiamorpholinium-diox-.

N-Myristyl-thiamor holine-oxide N-Methyl-thiamorp oliue-dioxide.

N-Inuryl-thiamorpholine-dioxide.

Niglyristyl-thiamorpholine-diox- Reacting various types of tertiary amines with methyl-lauryl sulfate under conditions as given in Examples 1 and 2 the following quaternary ammonium lauryl sulfates were prepared:

Compounds: Lauryl sulphates Tert. Amine N,N,N,N,-Tetra-methyl-ammonium 'Iri-methyl-amine. N,N ,N-Tri-ethyl-N nethyl-ammonmm. Tri-ethyl-amine. N ,N,N-lri-ethylol-N-methyl-ammonium Tri-ethylol-emine. N-Methyl-pyridinium Pyridine. N-Methyl-piperidiniurn-. Piperidine. N-Methyl-quinolium Quinoline. N,N ,N -Irimethy1-N-phenyl-ammonium Dimethyl-anilme. N,N-Di-ethyl-N-methyl-N-phenyl-ammonium Diethyl-amline. N,N,N-Trimethyl-a-naphthyl-ammonium. Dimethyl-a-naphthyl amine. N,N,N-Trimethyl-fl-naphthyl-ammonium Dimethyl-fl-naphthyl amine.

What we claim is: 1. Quarternary ammonium alkyl sulfates of the following formula:

wherein, R1, R2 and R: represent organic residues of which at least two may form together with the nitrogen atom a heterocyclic nucleus, R4 and Y represent alkyl groups, the number of carbon atoms present in the alkyl group Y being at least equal to the sum of the number of carbon atoms present in the cation.

2. Quaternary ammonium alkyl sulfates of the following formula CHz-CH: R;

wherein R1 and R2 represent alkyl groups and Z a member of the group consisting of O-, -S-, SO, and SO2-, while Y is an alkyl group different from the alkyl groups R1 and R2 as well as from the group CH CH and wherein the number of carbon atoms present in the alkyl group Y is at least equal to the sum of the number of carbon atoms present in the alkyl groups R1 and R2 and the group CHr-CHrwherein R1 and R: represent alkyl groups while Y is an alkyl group different from thegroups R1 and R2 and the group 4. N,N-dimethyl morpholinium cetyl sulfate of the following formula 5. N,N-dimethyl morpholinium n-hexyl sulfate of the following formula 6. N-methyl-N-lauryl morpholinium octadecyl sulfate of the following formula CHQCH! CH3 7. Thiamorpholinium alkyl sulfates of the following formula:

CHzCH! cinch, Ra

wherein R1 and R2 represent aliryl groups, while Y is an alkyl group having a number of carbon atoms at least equal to the sum of the number of carbon atoms in the alkyl groups R1 and R2 and the group CHaCHr- 8. Pyridinium allryl sulfates of the following formula:

comprising reacting at elevated temperature a tertiary amine of the formula with an unsymmetrical dialkyl sulfate of the formula R4O.SOz.OY, wherein R1, Ra, Ra, represent organic residues of which at least two may form together with the nitrogen atom a heterocyclic nucleus. while R4, and Y are alkyl groups, the number of carbon atoms present in the alkyl group Y being at least equal to the sum of the number of carbon atoms present in the tertiary amine and in the alkyl group R4, and Y being different from the alkyl group R4 and from any alkyl group present in said tertiary amine.

10. A process of producing quaternary ammonium alkyl sulfates of the following formula a iz.

comprising reacting at elevated temperature a tertiary amine of the formula with an unsymmetrical dialkyl sulfate of the formula R4O.SO2.OY, wherein R1, R2, and R3 represent alkyl groups of which at least two may form together with the nitrogen atom a heterocyclic nucleus, while R4 and Y are alkyl groups, the number of carbon atoms present in the alkyl group Y-being at least equal to the sum of the number of carbon atoms present in the alkyl groups R1, R2, R3, and R4, and Y being different from any of the alkyl groups R1, R2, R3, and R4.

11. A process of producing quaternary ammonium sulfates of the following formula cllrglka comprising reacting at elevated temperature a tertiary amine of the following formula CHz-CH: R1

, wherein R1 represents an alkyl group and Z is a member of the group consisting of O--, S--, 40-, and SO2, with an unsymmetric dialkyl sulfate of the formula 12.20.802.01 wherein R2 and Y are alkyl groups, the number of carbon atoms present in the alkyl group Y being at least equal to the sum of the number of carbon atoms present in the alkyl groups R1 and R2 and the group CHz-CHQ- and Y being different from any of the groups R1 and R2 and the group 12. A process of producing morpholinlum alkyl sulfates of the following formula CHr-CH: R1 0 lll o.so,.oY1-

CH( zI i1 comprising reacting at elevated temperature a morpholine compound of the formula wherein R1 is an alkyl group, with an unsymmetrical dialkyl sulfate of the formula wherein R2 and Y are alkyl groups, the number of carbon atoms present in the alkyl group Y being at least equal to the sum of the number of carbon atoms present in the alkyl groups R1 and R2 and the group 13. A process of producing thiamorpholinium alkyi sulfates of the following formula comprising reacting at elevated temperature a thiamorpholine compound of the formula CHzCH: R1 S CH:CH|

wherein R1 is an alkyl group, with an unsymmetrical dialkyl sulfateof the formula R2O.SO:.OY

wherein R2 and Y are alkyl groups. the number of carbon atoms present in' the alkyl group Y being at least equal to the sum of the number of carbon atoms present in the alkyl groups R1 and R2 and the group CHICHr- S\' CHaCHz- JOSEPH B. NIE'DERL. WILLIAM F. HART. MARTIN E. MCGREAL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Schonhofer et a1. May 26, 1936 Bertsch et a1 Jan. 11, 1938 Number Number 10 Name Date Bruson Apr. 26, 1938 Gunther Sept. 20, 1938 Hahl et a1 Mar. 28, 1939 Epstein Oct. 24, 1939 Harris May 21, 1940 Wibaut et a] June 24, 1941 Bertsch Sept. 23, 1941 Munz et a1. Feb. 3, 1942 Niederl et al. July 10, 1945 MacMullen et a1. Feb. 19, 1946 FOREIGN PATENTS Country Date France Apr. 10, 1933 OTHER REFERENCES Shelton, Jour. Am. Chem. Soc., vol.'68 (1946)

Claims (1)

1. QUATERNARY AMMONIUM ALKYL SULFATES OF THE FOLLOWING FORMULA: