US2906753A - Acyclic hydrazinium salts - Google Patents

Description

Staes "ateit 2,906,753 ACYCLIC HYDRAZINIUM SALTS Bernard Rudner and Marguerite E. Brooks, Baltimore, Md., assignors to W. R. Grace & Co., New York, N.Y., a corporation of Connecticut No Drawing. Application February 25, 1957 Serial No. 641,810

11 Claims. (Cl. 260-2472) This invention relates to quaternary nitrogenous salts. V

In one specific aspect, it relates to quaternized derivaties of substituted hydrazines. Instill another aspect, it relates to novel acyclic hydrazinium chlorides, bromides, and iodides.

Heretofore, quaternary hydrazinium salts have been obtained on only a laboratory scale. A known preparation of these interesting compounds comprises the reaction of 1,1-disubstituted hydrazines with alkylating agents, e.g. methyl chloride. Because of the extreme difliculties involved in preparing the parent hydrazines and the limitations of their final alkylation (see 0. Westphal, Berichte de Deutsche Chemische Gesellschaft 74: 759 et. seq., 1365 et. seq. (1941), only limited types of hydrazinium chlorides have been heretofore available. Using Westphals method it is obvious that the preparation of any specific hydrazinium cation depends upon the availability of the substituted hydrazine, as well asthe ability of that substituted hydrazine to undergo al kylation with the necessary alkyl halide. Among the compounds discovered by Westphal were the triheXylhydrazinium chloride, the dodecyldimethylhydrazinium chloride, the hexadecyldimethylhydrazinium bromide and the hexadecyldimethylhydrazinium iodide. Because of the inherent limitation of his alkylation reaction, Westphal found it impossible to prepare hydrazinium chlorides of greater chain length than the dodecyldimethylhydrazinium salt. He was more successful using methyl bromide and methyl iodide as alkylating agents; however, he did not prepare hydrazinium salts having a carbon chain longer than 16 carbon atoms. Since long chain alkyl substituted hydrazines are not readily available, the only known compounds of this particular type are those prepared by Westphal. We have discovered certain distinctly different acyclic hydrazinium salts which vary both in their structure and in their utility from the compounds of Westphal. The vast utility of our novel acyclic hydrazinium salts will be discussed in detail infra. This application is a continuation-in-part of our co-pending application S.N. 546,784, filed November 14, 1955 and SN. 560,282, filed January 20, 1956 filed jointly with L. 0. Young, both now abandoned.

It is, therefore, an object of the presentinvention to provide a new generic class of acyclic hydrazinium salts which, because of their unique properties and utility, are commercially acceptable as dye, detergent and pharmaceutical intermediates as well as for a variety of other purposes.

In accordance with the present invention we have made available a new generic class of useful hydrazinium salts having the formula:

In the above formula R is an alkylaminoloweralkyl residue of 8 to 24 carbon atoms, an acyclic acylaminoloweralkyl residue of 8 to 24 carbon atoms, an acyclic acyloxyloweralkyl residue of 8 to 24 carbon atoms, and an acyclic acyloxyalkylaminoloweralkyl residue of 8 to 24 carbon atoms. R and R" are hydroxyloweralkyl, hydroxyloweralkoxyloweralkyl, hydroxypolyloweralkoxyloweralkyl, acyclic acyloxyloweralkyl, acyclic acyloxylower alkylaminoloweralkyl, and acyclic acylaminoloweralkyl radicals. R in addition may be an aliphatic hydrocarbon residue of less than 25 carbon atoms. Such a residue includes alkyl,,.alkenyl and alkadienyl radicals fitting this description. R" may also be a lower alkyl radical. Furthermore, R and R" may be carbon-containing residues which when taken collectively with each other represent the necessary atoms to complete a beterocyclic ring structure having at least five and not more than six endocyclic atoms. For example, if R is CH CH O and R" is CH CH collectively they form the morpholine structure. X is a halide having an equivalent weight of at least thirty-four. More specifically X is a chloride, bromide, or iodide anion.

It has recently been discovered that chloramine will react with tertiary amines to form trisubstituted hydrazinium chlorides. This new reaction presents practically limitless possibilities for the preparation of novel and interesting chemical compounds, which, because of their structure and inherent physical properties, have a wide range of uses. Tertiary amines are readily available bases. Chloramine is an excellent reagent since it can be economically obtained in commercial quantities by using the well known process of Harry H. Sisler et al., described in US. Patent No. 2,710,248 where chlorine and ammonia are reacted in the vapor phase to produce chloramine (monochlor amine).

By treating a particular class of tertiary amines having a structure which is embraced by the general formula supra, with chloramine, we have discovered the new generic class of hydrazinium chlorides referred to hereabove. The corresponding bromides and iodides of the present invention are preparable by metathesis.

In making the chloride compounds of the present invention it is usually suitable to contact chloramine with a solution of the selected tertiary amine, allow the reaction to proceed until the desired quantity of chloramine is consumed and then isolate and purify the resultant hydrazinium chloride by standard laboratory techniques. While chloramine is most advantageously prepared in the form of a gaseous chloramine-ammonianitrogen stream obtained from a generator constructed according to the teachings of Sisler et al., other methods are equally adaptable for the purposes of the present invention. For instance, chloramine can be made by re acting chlorine with an excess of ammonia in a halogenated hydrocarbon solvent under controlled conditions of mixing at low temperatures. Such a procedure is fully described in US. Patent No. 2,678,258 to John F. Haller. Another eifective procedure is that of Coleman et al., fully described in Inorganic Syntheses, vol. 1, 59, (1939). Alternately, the compounds of the present invention can be made directly by the procedure described in the co-pending application of Bernard Rudner, Serial No. 605,230, filed August 20, 1956, which teaches the reaction of chlorine ammonia and the tertiary amine in the presence of excess ammonia. For simplicity, when both the amine and the product are soluble in the same inert solvent, we have found the Rudner method to be apreferred technique. V

Tertiary amines suitable for the purposes of the present invention are shown hereunder in Table 1. These suggested amines are intended merely to be illustrative, since it is obvious that the homologs of these compounds embraced by the general formula set forth above would be equally applicable in the production of individual species of our new and novel class.

1 2 3 g d cenyldiethanolamine a Palmitoylaminoethylimmobis(ikpalmitoyloxyethane).

TABLE I Parent amine Product hydrazinium salt etyldiethanolamine eli ylhexyl)ethanolamine D n nylaminopro aml Decyhmmobis-(4-butano1 6, 6 pentamethylheptyl-Z) methylhydroxyethylamine " Dodecyliminobis(2- to 2.1101) Didodecylethanolan iing 9; Dllaurylethanolamine '10. D1tetradecylaminopropanol- 11- Pentadecenyliminobisethanol 12. Oetylmethylhydroxybutylamine 13. 0ctadecenyldiisopropanolamine. 14, Oetadecenyldi-isopropanolamine .15. Dloctadecylaminoethanol 16. Dodecyl m nobis(fl-hydroxyethoxyethane) ,17. Dodecylnnmobis(fl-hydroxyethoxyethane) 18. Dihexadecyl (hydroxytetraethoxyethyl) ami11e -19. 0ctadecad1enylbis(hydroxytetracosanethoxyethybamine. V t 20. Methyltetracosanyl(hydroxytetradecaethoxyethyD- amme.

.21. Dodecenylaminoethyldimethylamine 22. N-hexadeicgl-N,N,N- is-(hydroxyethybpropylened .'am1ne-,. I g Y 23. N, N-di0ctadecyl-N,N-bis- (hydroxytetraethoxyethyl) propylenediamine-1,2. j g 24., (Z-ethylhexanoylaminopropyl)diethylamine 25. Lauroylaminoethyldiethanolamine 26. N-lmoleoyl-N-(fi-hydroxyethyl)aminopropyldifllydrox ypolyethoxyethynamine- 27. N (behenoy l aminometh y1)m0rpholine 28. Tris-(2-pelargonoyloxyethyl)amine 29. 2- (palmltoyloxypropyhiminobis (2-propanol) N, N -bis (stearoyloxyethyl) aminoethyliminobis- (hy droxydiethoxyethane). I

1 The amines set forth in Table 1, supra, may bedivided into three general types; viz: 1) those synthetically derived from'fats, (2) those synthetically derived from lower olefins, and (3) those synthetically derived from petrochemical amines. V. a I

Typel amines are prepared as follows: naturallyoccurring fatty glycerides are hydrolyzed to acyclic acids 'RCOOH, where R is a parafiinic or olefinic residue, having from 7 to'21 carbon atoms. These acids are, treated with ammonia intthe presence of a catalyst to give a cyanide RCN, often by way of amide formation.- Thisproduct his hydrogenated catalytically to convert the cyanide to a "mixture containing primary and/or secondary plus vtertiary amines. The primary and secondary amines thus formed can be alkylated with e.g. methyl chloride, ethl ylene oxide, acrylonitrile, or formaldehyde and sodium 'cyanide. The nitriles formed by the last named reagent combination can then be reduced to .amines and the amine can be 'acylated or alkylated, etc.

It is noteworthy that the fatty amines are often obftainedas'mixtures. The coconut oil fatty acyclic residue is 8% 'octyl, 9% decyl, 47% dodecyl, 18% tetradecyl, 8% hexadecyl, octadecyl, 5% octadecenyl; the soy residue is hexadecyl, 10% octadecyl, octadecenyl, octadecadienyl; tallow is 30% hexadecyl, 25% octadecyl, 45% octadecenyl. It is, of course, possible 'by fractional distillation or other procedures ,to .get nearly pure homologues from these'fatty amine mixtures. The fatty amines may also be hydrogenated to,conv ert them to mixed lalkyl residues substantially free of unsaturated compounds. I v V 1 The second general type of amine is prepared as follows':' propylene, butylene, isobutylene, 'can be dime'rized, trimelized, etc., and the resulting olefinic mixture maybe condensed with elgf urea, ammonia or amines to vgive eventually primary or secondary amines. These compounds may be further treated to give the tertiary amine. liquation 1 is exemplary of this processz v tomnmcma-nmoorrm as s'ulphate. Such commercial products as the Primeens 1,1-bis-(2-hydroxyethyl)-l-n-octylhydrazinium qhloride l,l-bis-(2-ethylhexyl)-1-(2-hydroxyethyDhydrazimum ehlorrde.

yl-l-(3-hydroxypropyl)hydrazm1um chloride. droxybutyD-l-decylh d'razinium bromide. 1,1-bis-(2-hydroxyethyD-1-(10-un ecenybhydrazmmm chloride. V 1-(2AA,6,6-pentamethylheptyl-2)-1-(2 hydroxyethyl)-1-met;hylhyd.raz1mum lodlde l-dodecyl-l ,l-bis- (2-hydroxypropyl)hyd ra zinium chloride. l,1dic1odecyl-1-(Z-hydroxyethyl)hydraz n um ehlorlde. 1,l-didodecyl-l-(Z-hydroxyethyl)hydrazimumiodrde. 1-(B-hydroxypropyD-I,l-ditetradecylhydrazlmum chloride. 1,1'-bis-(Z-hydroxyethyl)-1-(G-pentadecenybhydrammum chlorlde. 1-cety1-l-(hydroxybutyl-ll)-1-n1ethylhydraz1n1um bromide. v 1,1-bis-(Z-hydroxypropyD-l- (ii-octadecehyllhydrazrnrum chloride. 1,l-bisf(Z-hydroxypropyD-I-(9-0ctadecenyphydrazmmm lodlde. 1,l-dioctadecyl-l-(2-hydr0xyethyl)hydrazimum chlor de. 1, l-bis- (fl-hydroxyethoxyethyl)-1-do decylhydraz n um chlonde. 1,l-bis-QQ-hydroxyethoxyethyl)-1-d0decy1hydra21n1um odide. V

1,l-dihexadecyl-l-(hydroxytetraethoxyethyl)hydrazmium ehloride. 1,l-bis-(11ydroxytetracosanethoxyethyl)-1-(10,13-oetadecad1enyl) hydrazlruum chloride.

l methyl-1-(hydroxytetradecaethogryethyl)-1-tetrac0sanylhydrazinium chloride.

1,1-dimetl1yl-1-[2-(5,5,7,7-tetrametl1yl-2octenyl-1)aminoethyllhydraziniumchloride.

1,1-b1is- (g-hydroxyethyD-l-B- (N-hydroxyethyl-N-hexadeeyl) ammopropyl] ch ori e. v V 1,1-bis- [B- ydroxytetraethoxy) ethyl]-1- [2- (die ctadeeylammo) -propyl1hydrazmmm chlohydrazinium and Amine'ODT are obtained by the process described hereabo've. I

Acylation with acids of compounds such as dimethyl- 'aminoethylaminc, triethanolamine, and tetra(2-hydroxypropyl)ethylenediamine gives amines of the third general type, viz: fatty esters and amides containing a tertiary amino group. For example, propylene oxide is reacted with ethylene'diamine and then with stearic acid to give the commercial products known as Quadrol Monoand Distearates. See Equation 2 below:

1 V H2NozmNm+ 40113611011,

a V I V v v. O V I CH3 7 V ([311 (HOCHCHzhNOHzGH2N(CHzCH-OH):

. $HI3 o H 0 on H on 011011 a 11 as Oz- C a V 2 J CHEM: 02H CH3 NCHiCHzN I fHooHo omenon I H3 7 fCHa V Qiladrol Monostearate In discussing the several methods by which chloramine may be made available for reaction with the tertiary amine, we indicate choice of-the reaction medium could be varied extensively. We have successfully obtained our novel compounds by conducting the reaction of chloramine and theappropriate tertiary amine in anhydroussolution usingas a solvent either 'an excess of the reactant amine or an unrea ctiv e organicliquid. Thereaction may also be carried out" in aqueous solution if such conditions appear to be preferable. The term unreactive as applied to the organic liquid solvent is intnd'edto embrace those solvents that do not react preferentially with chloramine, ammonia or the reactant amine under the conditions employed. It is obvious, therefore, that the choice of solvent is one of-economy and simplicity. For good absorption (and, therefore reaction) it may be desirable iojbubble chloramine through a long column of solution comprising a tertiary amine dissolved in a relatively T pi jelventg s iv e a g which's'efl e this purpose include hydrocarbons, e. g. heptane, cyclohexane, benzene, xylene. and the like; ethers, e.g. diethyl ether, diamyl ether, dioxane and anisole; amides, e.g. dimethylformamide and dimethylacetamide; halohydrocarbons, e.g. chloroform, carbon tetrachloride, trichloroethylene, trichlorobenzene; and nitroaromatics, 'e.g. nitrobenzene. For special purposes water and other hydroxylic solvents such as ethanol and Z-ethoxyethanol may be used.

The novel bromides and iodides of the instant invention are preferably prepared by the metathetical reaction between the hydrazinium chloride and e.g. an alkali salt of the desired anion. In short, the method comprises mixing e.g. aqueous solutions of the reactant salts with heat if necessary, or mixing organic solutions of the two components. As an alternative procedure two dry components can be melted together to form our novel compounds. 'The desired hydrazinium salt is then isolated and purified using standard techniques more fully described in the specific examples that follow. It is often unnecessary, in specific instances, and therefore undesirable in those instances, to isolate the hydrazinium chloride before conversion to the bromide or iodide.

Our novel compounds have good detergent properties which make them effective for general use in the textile industry. Not all surfactants are good detergents. In order for a surfactant to be an excellent detergent it must have (1) ability to Wet and spread on liquid and solid surfaces, (2) ability to form a low and stable foam, (3) ability to emulsify oily materials, (4) ability to peptize aggregates of solid particles, (5) ability to deflocculate or stabilize dispersed systems of solid particles. This latter property is necessary to prevent soil redeposition on a surface of a clean fabric. Our novel compounds possess to a measurable extent these desirable properties. Furthermore, they may be converted to synergistically effective detergents by methods described in the co-pending application of Bernard Rudner S.N. 619,- 691, filed November 1, 1956.

In addition to the primary \utility in the textile field, our novel compounds have other diverse applications. For instance, they .produce brightly colored dyestufis when treated with aqueous solutions of acid dyes (ie those substances containing sulfonic, carboxylic, or other acid groups). The resulting products, the hydrazinimum salts of the acid dyes, vary in physical properties with the chain length of R group and the particular dye used. Products ranging from solvent soluble dyes to insoluble pigments have been prepared in this manner. The addition of carbon tetrachloride to aqueous solutions of our novel compounds results in stable oil and water emulsions. Since our novel hydrazinium salts possess considerable anti-oxident power, such emulsions are particularly useful as cutting oil additives for machine shop work.

Our products also exhibit utilities as added to electroplating processes. For instance, the addition of a small amount of any of our hydrazinium salts to an electroplating solution results in the deposition of a clearer, brighter, more coherent covering film on the electroplated object. Moreover, our compounds are excellent dispersing agents for water insoluble components in electro-plating.

Our compounds are good additives for froth flotation agents. In general froth flotation agents do not possess good Wetting out (viz: surfactant) characteristics. The addition of any one of our'novel compounds to such an agent greatly enhances its ability to wet'the surface of the air bubbles formed during a froth flotation. The hydroxyalkyl, hydroxyalkoxyalkyl and hydroxyalkylaminoalkyl members of our generic group were especially useful for this latter purpose.

Our novel hydrazinium cations may also be combined, by metathetical reaction, with a sulfonamide anion. The metathesis is readily accomplished in anhydrous or aqueous solution or by the fusion of two salts at relatively low temperatures. The new salts produced by this method comprise a hydrazinium cation of the surface active type and an anionic portion consisting of a chemotherapeutically active sulfonamide derivative. Such products are exceedingly valuable in the formation of self-sterilizing, Water or solvent soluble or dispersible medications. Their advantageous properties include wetting power, antioxidant action, dispersibility, self-sterilization, diminished alkalinity and enhanced stability.

The scope and utility of our invention is further illustrated by the following examples:

Example I A chloramine generator was constructed according to the teachings of Sisler et al., supra. The generator consists of a horizontal Erlenmeyer flask, the bottom of which contains an outlet tube which is directed into the reactor containing liquid tertiary amine. 'Ammonia and chlorine (which may be diluted with nitrogen) are introduced separately into the top of the flask through concentric conduits. Chloramine and ammonium chloride are formed in the flask at the point where the chlorine and ammonia vapors come into contact. A rod is provided in the chlorine inlet stream to prevent any plugging of that stream with ammonium chloride. The outlet end of the flask is masked with glass wool to collect any ammonium chloride particles which otherwise would be directed into the bath of the amine. The chloramine yield for any one set of gas flow meter readings is determined by removing the reactor and generating the chloramine directly into a series of three chilled traps. Under the conditions of chloramine generation, only ammonia, chloramine, and nitrogen can pass through the glass wool into the traps. Since the traps are maintained at at least 70 C., the ammonia and chloramine condense therein and react relatively slowly (compared to the chlorine-ammonia reaction velocity) to form nitrogen and ammonium chloride. By allowing the low temperature condensate to come to room temperature slowly, the chloramine is converted quantitatively to non-volatile (at 2030 C.) ammonium chloride, while the ammonia and nitrogen escape by volatilization. Therefore titration of the white residue (obtained on evaporation of the condensate) for chloride gives a direct measure of the chloramine generated. This can be related back to a measure of the chlorine used to obtain the chloramine yield. There is an alternate procedure which is suitable for use when chloramine is actually being consumed by reaction with a tertiary amine. The amount of chlorine used in a run, which is the limiting reagent quantity for yield calculation, can be measured directly, e.g., by Weight of the chlorine cylinder before and after use, or by use of flow meters. The amount of ammonium chloride retained within the generator is determinable by titrating an aliquot of the aqueous solution of all of the solid remaining within the chloramine generator after the reaction has been completed. The chloramine yield, expressed as percent of the theoretical yield, can then be calculated from the formula i where A is the total number of moles of chlorine passed into the generator and B is the'number of equivalents of chloride retained within the generator. The chloride content of the generator thus serves as an indicator of chloramine efiiciency.

Percent Example II '7 mal HCl showed that it contained about lower fatty acid amides. It was, however, at least 85% 4-(oleoyl- The product of Example '11 was treated in chloroform solution with a chloramine-ammonia gas stream by a method similar to that described in Example I. The resulting product was 40 g. of a whitish wax, 4-amino-4- [3(oleoylamino)propyl]morpholinium chloride, somewhat less resistant to oxidation than the products of Examples VII and X. It was recrystallizable from water as flat plates which slowly yellowed. On the melting point block the novel product went soft and transparent at about 50 C. and melted with gasevolution at about 135 C. It forms characteristic salts with penicillin and the sulfa drugs which vary from water soluble to water dispersible. Its salts with detergent sulfates are water soluble, but with the surfactant naphthalenesulfonates the products are waterinsoluble. The preparative reaction is shown below in Equation 4.

K4) 0 I ornom 7 fl uO a a 0+ own,

CHQOHZ V /CH2CE:1 u ss ca aN 0 01-3 HZN oHioH: Example IV A 2 g. portion of the product of Example HI dissolved 6 in 100 ml. of water was slurried for 2 hours at room temperature with the wet, freshly precipitated and wellwashed Ag O from 6 g. of AgNO The mixture was decanted and' the residue, containing silver chloride and 7 silver oxide, was washed with two ml. portions of water and then washed with two 50 ml. of isopropyl alcohol. The combined wash and decantate was split into two parts. To one of these portions, ml. of a 10% HBr solution was added. The strongly acid solution was evaporated dry in a nitrogen stream at room. temperature. The residue was recrystallized from ethyl acetate to give a 50 'water-insoluble tan wax. On the melting block this wax V decomposed at about 142? C. It was soluble in chloroform. The preparative reactions yielding 4-arnino-4- [3-(oleoylamino)propylJmorpholinium bromide are shown below in Equations 5 and 6.

. Hz Example V I i The second portion of the split solutionof Example IV '7 stirring at 165-180 for four hours.

was treatedwith ml. of 'HI'as a 10% solution. The procedure of Example IV was then substantially repeated. The hydraziniurn iodide also appeared as a tan wax slightly less stablethan the bromide. On the .melting block it decomposed at about 138--C.. This new product Was insoluble in water butsoluble in chloroform. It is 4-amino-4-[3-(oleoylamino)propyl]morpholinium iodide.

' Example VI 7 A chloramine-ammonia gas mixture was passed into 20 ml. of 8-hydroxyethylmorpholine and 50 ml. of xylene for 47 minutes. Because this reaction was exothermic, use of a cold water bath was required to maintain the temperature at approximately 30 C. The copiouswhite precipitate that formed during gasificationblocked the inlet tubes and necessitated cutting the reaction period short. Use of an agitator and increased amounts of solvent eliminated this 'difliculty in subsequent runs. The filtered, washed and dried solid, weighing 14.6 g., con sisted of glistening oil-white plates, melting at'l49152" C. By chloride titration, it represented 96% pure 4-amino-4- (Z-hydroxyethyl)morpholinium chloride. The amount of product obtained represented approximately 60% of the theoretical yield. Tworecrystallizations from absolute alcohol gave transparent, gleaming plates melting at 154155 C. The pure product was very water-soluble, recrystallizable from absolute alcohol, and decreasingly soluble in less polar solvents. The preparative reaction is shown hereunder in Equation 7. I

Example VII product ran clear at about 61 C. with gas eyolution and darkening. The novel compound is about as soluble in water as the product of Example III; however, it is more soluble inldiethyl ether and acetone. The preparative reaction is shown below in Equation 8.; l

Example VIll I thoroughly mixed molten brown mass of the salt, annnoethylpiperazine distearate was held with occasional After. cooling,'the

"product was taken up in three times its volume of chloroform, dried over anhydrous magnesiumsulfate,decanted free of salts, saturated'with chlorarnine and then filtered. Evaporation to dryness and recrystallization from ethyl acetate gave about92% pure "4-stearoyl l-arnino l-l2- (stearoylamino)ethyl]piperazinium chloride. The novel product appeared as a tan wax melting at about 168: C.

, with a preliminary phase change at about 110 C. Its preparative reactions are shown below in Equations 9 and 10.

A tared open flask containing 0.5 mole (142.2 g.) stearic acid was heated to 70 C. until the acid became almost completely molten. To this mixture was cautiously added 0.52 mole (52 g.) dimethylaminopropylamine to form, with evolution of heat, aminopropyldi- 'methylaminium stearate.

The temperature of the reaction mixture was raised to 150 C. over a period of 3% hours, by which time the flask had lost 8.5 g. of weight. After an additional three hours at 150 C. the flask had lost 12 g. in weight, slightly more than the theoretical amount, according to Equation 11:

-r'nal HCl in isopropyl alcohol, gave a satisfactory equivalent weight. Calculated: 368, obtained: 370.

ExampleX 50 g. of the product of Example IX were treated in 1000 ml. of chloroform with 2.5 equivalents of chloramine from the generator. From this reaction mixture was obtained 42.9 g. of product, appearing as a tough yellow wax, softening at 45 C. and decomposing at about 130 C. The product, 1,l-dimethyl-l-[3-(stearoylamino)propyl]hydrazinium chloride has the structural formula it r nHnoNno mNcm 01' .It was recrystallizable from water as nacreous plates.

Example X] A 1 g. portion of the product of Example X and 25 ml. of hot water was treated with one g. potassium iodide in of hot water. An immediate precipitate resulted. The reaction mixture was cooled, filtered, and slum'ed in 20 ml. of boiling water. The slurry was allowed'to cool and about 97% pure 1,1-dimethyl-1-[3- (stearoylamino)propyl1hydrazinium iodide was obtained therefrom. This new product appeared as a yellowish granular material melting at about 136 C. Its preparative reaction is shown below in Equation 12.

Example XII g. of lauric acid were heated for three hours and 50 minutes at 147-153 C. with 51 g. of dimethy1aminopropylamine. The resulting product was vacuum distilled to give 110.5 g. of distillate between 17l19 4 C. at 2 mm., mostly inthe range of -194 C. The lauroylaminopropyldimethylamine thus obtained was similar in its properties to the product of Example IX. Titration to a Brom Phenol Blue end point with 0.2071 normal HCl in isopropyl alcohol indicated that the product amine had a molecular weight of 287. The calculated value for this amine is 284.

Example XIII 50 g. of the distilled aminoamide of Example XII were dissolved in 1000 ml. of chloroform. This solution was treated with 2.5 equivalents of chloramine from the generator, yielding only ammonium chloride as the precipitate. Evaporation of the solvent and trituration of the residue with diethyl ether gave 48 g. of a partially crystalline cohesive white wax, becoming soft and transparent at 53 C. but not decomposing at 210 C. Trituration with acetone gave a cleaner looking product which, on being vacuum dried, was found by analysis to be 98% pure 1,1-c1imethyl-1-[3-(lauroylamino)propyl] hydrazinium chloride. Recrystallization from water gave pearly plates softening and going transparent under pres sure at about 72 C.

Example XIV To 30 ml. of xylene solution, containing -0.5 g. of chloramine, was added 1.5g. N-(3-aminopropyl)morpho' line at room temperature. The clear mixture was allowed to stand overnight, during which time a thick red oil, containing some solid, formed. The oil, crude 4- amino-4-(3-aminopropyl)morpholinium chloride which was isolated by decantation, weighed slightly more than 1 g. This novel product was purified by dissolving it in a limited quantity of Z-propanol (which freed it from ammonium chloride) and pouring it into 3 volumes of ether. The thick brown oil thus obtained as precipitate could not be transformed into a solid by chilling, vacuum drying,- or trituration. The purified product was readily soluble in water, and markedly soluble in 2-propanol, but decreasingly soluble in acetone and ether. It forms a diliturate melting at 300 C., and atannate that evolved gas at 205 C.

mNomomNoo ClNH:

[ILN C b 1- NH: Example XV -am ino )ethyl]hydrazinium chloride. appeared as a brown somewhat hygroscopic solid melting with decomposition at approximately 75 C; It was 4) i C mar n-N :contains approximately 85% propylenediamine, having an average molecular weight of 0.00607 mole per minute. pleted, the product was separated from the above mixture by filtration. A wet filter cake weighing 230 g. was

stripped off and the cake was taken up in 1 liter of benv zene. The chloramination was repeated, the solvent was againstripped OE and the cake was partitioned between an aqueous mixture containing ethanol and diethyl ether. By this procedure Was obtained 231.4 g. of almost pure 1 ethyl l (2 hydroxyethyl) 1 [2 (p stearoyl- The novel product Example XVII A mixture of hydroxyethylated diamines of the general-formula V canton onion nNomomomnozmon is available commercially'as Ethoduomeen T-l3. This -mixture is prepared by reacting tallowamine with acrylonitrile, reducing the'nitrile to CH NH and reacting with approximately 3 moles of ethylene oxide according to Equation 14.

R in the above equation is derived from tallow fatty acids and is hydrogenated during the reduction vof the nitrile. It is largely a mixture of hexadecyl and octadecyl in a ratio of approximately 1:3. Thermanufacturer ofEthoduorneen T-l3 states that his product, assold, of the tetrasubstituted 558 (by neutralization).

Ethoduomeen T-13, 100 g. in 1000 ml. n-heptane was treated for 45 minutes with a chloramine-ammonia gas stream from the generator at an average flow rate' of After the reaction was comthereby obtained. .The wet mass was purified by dissolving in butanol, filtering and salting out with 8 times its volume of acetone, filtering and repeating twice more with decreasing acetone-butanol ratios. The final product, obtained after being vacuum dried'at 104 F., was

a firm cohesive amber gel,- 95% pure 1,1-bis,(2 -hydroxyethyl) 1 [3 (N tallow N B hydroxyethyl)aminopropyl-l-lhydrazinium chloride. The preparative reaction is shown below in Equation 15.

(15) I canon n mou l [CJO-IBHSPMNCIZHOIII (Ca 4 32 It is entirely possible'that the novel product has the obvi ous alternate structure:

I Example XVIII A diamine base similar to that of Example XVII was prepared in a like manner using only 2 moles of ethylene oxide. This product, available commercially as Ethoduomeen T-12, is presumably a mixture of amines having the possible alternate structures shown below as-110mm C1H4OH cmomomw HOH4C: H

A 100 g. portion of this amine base was dissolved in 1 liter of an aromatic solvent commercially available as Solv D (largely C H C -H' The resulting solution was subjected to a chloramine stream from the generator for a period of90 minutes. When the reaction was completed, the mixture was allowed to settle and then-decanted. The decantation residuewas' treated-with twice its volume of dry acetone to coagulate the slimy precipitate. It was then filtered, washed well with acetone and vacuum dried to give a very tacky hygroscopic brown solid. This solid was taken up in chloroforrn, filtered free of ammonium chloride, and evaporated to one-tenth its volume without the formation of a precipitat e. The resulting solution was treated with 4 volumes of acetone, decanted, and vacuum dried to yield a thick brown glue. This product was about 92% pure hydrazinium chloride mixture presumable largely, l,1-bis(2- hydroxyethyl) 1- [l3 -ootadecylamino) propyl] hydrazinium .chloride. It was soluble in water, chloroform and ethanol. Its aqueous solutions had a soapy feel and foamed appreciably. The original solvent D filtrate was evap- .orated dry to give a very dark; oil containing additional quantities of product. The total yield of the product was about 65 Aqueous solutions of this novel compound treated with an aqueous solution of'sodium dirnethyldithiocarbamate gave glistening prisms of the hydraiinium N,N-dimethyldiethiocarbamate melting at about 68-695 Physically it appears as a thick brown paste readily miscible with water. a 1

A 100 g. portion of Ethoduomeen T-40 was dissolved in 1 liter of Solv D and reacted according to the procedure described in Example XVIH. The reaction mixture was decanted free of solvent for. evaporation and added to an equal volume of acetonen'(about 200 ml). This mixture was stirred, filtered free of ammonium chloride containing a small quantity of product, and the filtrate was combined with the Solv D decantate and evaporated to dryness to give crude hydrazinium chloride, which appeared as. a viscous brown oil. Fractional precipitation from dioxane, acetone, and ethoxye thanol successively by diethyl ether gave on vacuum drying a pale brown oil pure (calculated as a mixture with 30% hexadecyl, 70% octadecyl with 30 C HQO groups). When treated with. the appropriatefreagents, it, formed a'soft .waxy.hexafluorophosphate, and iodide, a 1 liquid 'watersoluble bromide, and a picrate; Eachof these salts were prepared from mixing aqueous solutions of the novel hydrazinium chloride in the appropriate reagent. The picrate appeared as rosettes of fine golden needles meltmg about 250 C. The major component of the hydrazim'um chloride mixture obtained as a product was 1,1- bis-(hydroxynonaethoxyethyl) -1-[3-(N-octadecyl-N-(hydrgxynonaethoxyethyl) amino propyl] hydrazinium chlo- I'l e.

Example XX A chlorarnine-ammonia gaseous mixture was bubbled into a trichloroethylene solution of tallow-bis-hydroxypolyethoxyethylamine, a product known commercially as Ethomeen T-25. The parent amine is represented by its manufacturer as having a structure:

wherein x+y=15. The compound has an average molecular weight of 937. R represents tallow, a mixture of fatty moieties thoroughly described earlier. A white precipitate formed in the reaction mixture as the reaction progressed. Extraction of this precipitate with ethanol, gave fine, transparent, off-white prisms of tallow-bis-hydroxypolethoxyethylhydrazinium chloride, which melted at 198-201 C. and decomposed at 218-233 C.

Example XXI A commercial mixture similar to that of Example XX known as Ethomeen 8-25 is a mixture of homologs of the general formula:

In the formula, R is a fatty hydrocarbon residue derived from soybean oil containing a mixture of hexadecyl, octadecyl, octadecenyl, and octadecadienyl chains as previously described in the specification. In this product x+y can vary from 2 to at least 25 and has an average of 15. Ethomeen S-25 has an experimentally determined neutralization of the equivalent of 939. Four batches of 200 g. of this amine mixture were each dissolved in 1000 m1. of xylene. The resulting solutions were subjected to a chloramine stream of 0.004 mole per minute from the generator for a period of 60 minutes. They were filtered and the filtrates were combined and resplit into three portions. Each of these solutions were again subjected to chloramination. They were refiltered and rechloraminated, refiltered and the filtrates were evaporated to dryness in a vacuum to give 875 g. of a wet paste. This material was vacuum dried at about 47 C. for 24 hours to give 765.9 g. of about 97% pure 1,1-bis-[B-(hydroxysesquixethoxy)ethyl]-l-soyhydrazinium chloride as a viscous white amber oil. This oil was very soluble in water and also soluble in xylene.

Example XXII A commercial product similar to that described in Example XXI marketed as Ethomeen l8+60 is described by its manufacturer as having the structural formula:

' wherein x+y=50, and R is derived from commercial stearic acid, largely C I-I with about 6% C I-I and about 1% C H The average molecular weight of this compound is given as 2484. The chlorarnine-ammonia gas mixture was bubbled into a trichloroethylene solution of this base. The reaction resulted in the immediate formation of a precipitate which was primarily ammonium chloride. The solid was extracted with isopropyl alcohol, and this extract was combined with the reaction filtrate. Evaporation of this solution gave as a tan, waxy product, a hydrazinium chloride of the probable struc- Example XXIII Since the Ethomeens are readily water soluble, they can be advantageously converted into hydraziniurn chlorides in aqueous solution. While this procedure appears to ofier no particular advantage, per se, it is demonstrative of the flexibility of the chloramine tertiary amine reaction. Aqueous chloramine, prepared according to the procedure of R. A. Coleman (US. Patent No. 2,404,695) was added to 0.5 g. of Ethomeen 18/60 in 10 ml. of ice water using three equivalents of titrable chloramine to one of the amine. The reaction mixture was allowed to stand overnight at 5 C. The resultant clear solution was treated with a small quantity of sodium bisulphite, cautiously neutralized with acetic acid, and evaporated to dryness. Extraction of the residue with isopropyl alcohol yielded, after evaporation, a 0.1 g. of the waxy product of Example XXII, soluble in water and benzene, but insoluble in hexane.

Example XXIV An amine available commercially is Ethomeen 8-60, structurally the same as the amine of Example XXII, but where R: the soy mixture detailed in the specification, was added in a 100 g. portion to a mixture of 800 ml. of Solv D and 200 ml. of chloroform. It was treated with chloramine, according to the procedures described in the previous examples. Using a work-up procedure similar to that of Example XIX an acetone-insoluble solid, very largely ammonium chloride, was obtained. The actone soluble portion of the precipitate and residue obtained on evaporation of the filtrate appeared as an ivory paste. This paste was purified by washing with isopropyl alcohol. The washing procedure fractioned the product to some extent into more saturated and less saturated portions. The pasty unfractionated material 1-soy-1, l-bis- (polyethoxyethyl hydrazinium chloride runs clear at about C. and it is very soluble with water. An aqueous solution of this material when treated with aqueous sodium sulfathiazole gives a precipitate, which when separated, appears as mats of fine lustrous plates melting at about 171-172" C. They are poorly soluble in cold Water and dispersible hot.

Example XXV A commercial product available as Ethomeen 18/20 averaging was added in a 100 g. portion to one liter of Solv D.

This solution was treated for 1 hour with 0.00656 mole -1,l-bis(hydroxytetraethoxy)ethyl l-octadecylhydrazinium chloride. The product was slightly thicker and darker than that of Example XXII. Itforms yellow gums when treated with potassium hexafluorophosphate and potassium mercuriiodide.

100 ml. was treated with 4 molar equivalents of chlor-- amine. After all the chloramine had reacted, the material was filtered. The filtrate contained chloride, indicating the formation of solvent soluble hydrazinium chloride. It was then taken up in xylene and exhaustively chloraminated with intermittent filtrations. The filtrate was finally stripped of solvent, washed well with hexane and a minimum quantity of water. The residue thus ob- .tained appeared as a yellow oil about 88% pure 1,1-bis- (2-ethylhexyl)-l-(Z-hydroXyethyDhydraZinium chloride, containing some unreacted amine. The product was not completely miscible with water. It was soluble in chloroform and xylene. It formed no hexafluorophosphate salt. However, it did form a gummy picrate.

Exam le XXVII An amine mixture available commercially as Ethomeen 2C-1l, C denoting coco, in the specification supra; '11 denoting an average of 1 C H O (per molecule) was added in a 50 g. portion to 950 ml. of Solv D. This solution was subjected to the chloramine stream from the generator at a rate of 0.0045 mole of chloramine per minute over a period of ninety minutes. It was allowed to stand overnight. On standing a relatively small quantity of ammonium chloride precipitate formed. The yellow filtrate evacuated in vacuo and washed well with hexane was vacuum dried to give a very thick yellow brown oil. This novel oil was dispersible in water and soluble in chloroform. It was purified to a thick clear yellowish paste of 1,l-di-coco-l-(2-hydroxyethyl)hydrazinium chloride which ran clear at about 69 C.

Example XXVIII A commercially available product known as Quadrol Monooleate is made by esterifying ethylenediaminetetra-isopropanol (Quadrol) with 1 equivalent of oleic acid. The thick brown oil, 47.6 g. in 1000 ml. of Solv D,

(aindriecl) soft tan solid. This was by analysis. a 65% oleoyloxypropyl 2 hydroxypropyl)aminoethyllhydrazinium chloride. The reaction filtrate was evaporated dry" giving 48 g. of a dark viscous oil, chiefly base and product in 70:30 ratiomThis was treated with the acetone wash of the filtration residue, stirred, and decantedz'i It was washed by decantation with three additional 100 ml.

16 portions of acetone. The air-dried brown residue thereby obtained was mixed with the extract of the filtration residue to'give 22- g. of chloroform-soluble, light brown hydrazinium chloride. It was washed free of ammonium .chloride by use of aqueous potassium carbonate, leaving a brown semi-solid product 86% pure by analysis.

' Example XXIX V A product similar to the starting amine of Example XXVIII available industrially ,as Quadrol Dioleate, is presumably 'a mixture containing the di'es'ters:

The commercial mixture, '50 g. in 1000 ml. of chloroform, was reacted with chloramine and worked up essentially as described in the preceding example. Approximately 90% of the crude hydrazinium chloride was found to be in the filtrate. Once stripped of solvent, this product was dark brown, viscous oil, weighing 51.7 g. and analyzing as about a 58:42 mixture of unreacted base and hydrazinium chloride. Free base was removed by repeated trituration with ether, leaving the desired product as a dark brown semi-solid mixture, one of the chief components of which was probably 1- (2-oleoyloxypropyl) 1 (2 oxypropyl) 1 [2 (N 2 oleoyloxypropyl-N 2 oxypropyl)aminoethyllhydrazinium chloride.

Example XXX The commercially available salt tn'ethanolamine oleate C17H33CO2H.N(C2H4OH)3 was heated at 135 C. in a N atmosphere at about mm. (water aspirator) vacuum until the theoretical amount of water was lost according to Equation 16 below. The product thus obtained was reacted and worked up by the procedure of Example XXVIII to give a thick oil, dark brown 1,1- bis (2 -hy droxyethyl) 1 [oleoyloxyethyHhydrazinium chloride. The novel product was 87% pure and obtained in about an 80% yield based on the starting 7 amine. It'did not form a hexafluorophosphate. It was clearly water dispersible and showed good emulsifying properties. It was soluble in chloroform. The preparative reactions are shown below in Equations 16 and 17.

- In addition to the above examples, wehave prepared 17 many other novel representatives of this type. Among these are: 1

, 18 compounds rat repellency tests were conducted. These testscomprise'isolating a specimen rat for a period of 96 TABLE II Reactant amine Name of product Structure Physical properties of product;

i or derivative Tallow-bis-(hydrox- Tallow-bis-(hydroxyethoxy- M.P. 222 0.; no PF; comyethoxy-ethoxyetho xyethyl) hy drazinium C g- H 3- N[(C3H O) H]z 01 pound. ethyD-amine. chloride. I

Stearamido-methyl- Dimethylstear-amidomethyl- 0. CH; Baste; no PF hydrolyzable.

dimethylamine. hydrazinium chloride. IT I a CnHggCNHCHgIII-CH; C1

Oleylamidopropyl Dimethyloleoyl-amidopropyl- O H OH; Not obtained pure; wax.

dimethylamine. hydrazinium chloride. H

CnHnCNCgHglTT- C Hg 01 Quadrol monostea- Chloramine adduct of ethylene- Impure, thick dark oil.

rate. diamine tetra-i-propauol ll monostearate. C H C 0 CH;

or H NC1H NCHgl'I3OH HOCHC H 2 QuadwI distearate Chloramine adduct of ethylene- Mixture of isomers Similar to monoester.

diamine tetra-i-propanol di- Eth 18/12 ii fi l ii a th n1 1: Not obtained pure used as in omeen isy roxye y -oc ade'cyl-hydrazinium chloride. [CNHI'IIIHCQHAOED 21 1 Example XXXI.

Example XXXI 50 g. Ethoduomeen T-13 (see Example XVII) in approximately one liter of xylene was submitted to chloramination for two hours, then allowed to stand. Since the clear supernatant liquid contained negligible quantities of ionic chloride, it was decanted off and discarded. The semi-solid residue was treated with 750 ml. of 2- propanol, filtered free of ammonium chloride, and evaporated to dryness to yield 59 g. of orange-yellow, thixotropic 1,1 bis-(2-hydroxyethyl)-1-EZ-(N-hydrotallow-N- 2-hydroxyethyl) aminop-ropyllhydrazinium c h 1 o r i d e. This, dissolved in 200 ml. anhydrous chloroform, was treated with a solution of grams mixed tolylene diisocyanate isomers (commercially available as Nacconate 80) dissolved in 100 ml. of chloroform. The mixture was refluxed for two hours, then evaporated dry. Evaporation left 73 g. of a granular polymer, light amber in color as formed but buflf once crushed. This polymer, formed as shown in Equation 18, is soluble in common organic solvents and self-dispersible hot in water. Application to textiles gives a relatively permanent antistatic power while increasing the hand or softness of the fabric.

Example XXXII To further demonstrate the utility of some of our novel hours with two food containers, one of which contains twenty g. of untreated food and the other 20 g. of food treated with 2% by weight of a material to be tested as a rat repellent. Repellency is measured by means of a Repellency Index, K, obtained by using the formula shown below:

In the above formula T is equal to the daily consumption of treated food, U is equal to the daily consumption of untreated food, the subscripts of 1, 2, 3 and 4 refer to the four days during the testing period, X is the weight of untreated food remaining after the fourth day and W is the body weight of the animal in kilograms. A value of represents complete repellency. Samples of our novel soy-bis-(hydroxypolyethoxyethyl)hy drazinium chloride and tallowbis (hydroxysesquiethoxyethyl)hydrazinium chloride were used as the treating material in the tests described hereabove. The first of these compounds gave a repellency index of 93 and the second a repellency index of 92. These results clearly show our novel compounds to be effective as rat repellents.

Our novel compounds show useful antiseptic powers. This is not due to the presence of the hydrazinium moiety alone, but rather is produced by the combination of hydrophobic and hydrophillic groups possessed by some of our compounds. Thus products obtained from the Ethomeens have only weak bacteriostatic activity, which grows still weaker as the degree of ethoxylation increases. However, our novel acylaminoloweralkylhydrazinium salts are markedly anti-microbial. Thus, when tested by the standard Oxford cup technique, 1,1- dimethyl l[3-(lauroylamino)propyl]hydrazinium chloride, is more effective than phenol as a bacteriocide.

In addition, it is possible, by extension of Example XXXI, to prepare polymeric esters, ketals, etc. as well as polymeric mixed amide-esters and urea-urethanes 1. As a new chemical compound 1,1-dimethyl-1-(ste ar- 6. New chemical compounds having the general for mula wherein R is an acyclic radical containing 8 to 24 carbon atoms selected from the group consisting of alkylaminoloweralkyl, alkylcarbonylaminoloweralkyl, alkylcarbonyloxyloweralkyl and alkylcarbonyloxyloweralkylaminoloweralkyl; R is an acyclic radical containing 1 to 25 carbon atoms selected from the group consisting of unsubstituted aliphatic hydrocarbon, hydroxyloweralkyl, hydroxyloweralkoxyloweralkyl, hydroxypolyloweralkoxyloweralkyl, al-

20 kylcarbonyloxyloweralkyl, alkylcarbonylaminoloweralkyl and alkylcarbonyloxyloweralkylaminoloweralkyl; R is an acyclic radical selected from the group consisting of lower alkyl, hydroxyloweralkyl, hydroxyloweralkoxyloweralkyl,

f hydroxypolyloweralkoxyloweralkyl, alkylcarbonyloxyloweralkyl and alkylcarbonyloxyloweralkyl aminoloweralkyl;

' R and R, taken together with the N on which they are both substituents form a non-aromatic ring selected from the group consisting of morpholine and piperazine; and X is a halide anion having an equivalent weight of at least 34.

7. Compounds according to claim 6 wherein R is alkylcarbonylaminoloweralkyl, R is unsubstituted aliphatic hydrocarbon, R" is lower alkyl and X is chloride.

8. Compounds according to claim 6 wherein R is alkylaminoloweralkyl, R and R" are hydroxyloweralkyl and X is chloride.

9. Compounds according to claim 6 wherein R is alkylcarbonylaminoloweralkyl, R and R" are taken together with the N on which they are both substituents to form a morpholine ring and X is chloride.

10. Compounds according to claim 6 wherein R is alkylcarbonyloxyloweralkylaminoloweralkyl, R and R are hydroxyloweralkyl and X is chloride.

11. Compounds according to claim 6 wherein R is al- I .kylcarbonyloxyloweralkyl, R and R are hydroxylower- .alkyl and X is chloride.

References Cited in the file of this patent Wohlz Berichte, vol. 64 (1931), pp. 1381-1389. Westphal: Berichte, 74-759 et seq.; 1365 et. seq. (1941).

Claims (2)

1. AS A NEW CHEMICAL COMPOUND 4-AMINO-4-(3(OLEOYLAMINO) PROPYL-MORPHOLINIUM CHLORIDE.

6. NEW CHEMICAL COMPOUND HAVING THE GENERAL FORMULA