US2299782A - Surface active materials - Google Patents

Description

Patented Oct. 27, 1942 UNITED STATES 2,299,782 SURFACE ACTIVE MATERIALS Charles F. H. Rochester, N.

Allen and Charles V. Wilson, Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February 29, 1940, Se-

i'galgNo. 321,599. In Great Britain March 30,

2 Qiaims. (Cl. 260290) This invention relates to surface activeimaterials and more particularly to cationic surfa-ce active materials and particularly to surface active materials of the cationic ammonium salt type.

During the past several years, a number of Surface active materials have been found. These materials may be classified as anionic, cationic, or non-ionic, depending upon whether or not they are ionizable substances, and if so, whether the anion or the cation is surface active. A number of these surface active materials have dispersing or wetting properties and have come to be known as dispersing and wetting agents.

Some of these known surface active materials (also known as capillary active materials, lipophyle materials or materials which possess interface modifying properties) which are cationic and of the ammonium salttype are quite soluble in water, and while possessing high surface activity in most cases, they are frequently difiicult to obtain in a pure condition which is desirable for certain purposes, such as incorporation of the surface active materials in photographic emulsions (as described in the copending application of Burt H. Carroll, Serial No. 321,595, filed of even date herewith), now U. S. Patent 2,271,623, dated February 3, 1942.

We have now found that the known cationic surface active ammonium salts can be converted into perchlorates. In this form the materials are readily isolated from reaction mixture and are frequently obtained in the crystalline state. In the crystalline state, the agents are generally white in appearance and have sharply defined melting points. Conversion to the perchlorates is accompanied by a diminution of surface active characteristics.

For the most part, the anions occurring in the known cationic surface active ammonium salts are halides, sulfate, alkylsulfate, toluenesulfonate, nitrate and carboxylic acid anions, e. g. formate and acetate. We have found it advantageous to convert these known salts to the perchlorates by treating an alcoholic or aqueous solution of the known salt with a water-soluble perchlorate, e. g. sodium or potassium perchlorate or perchloric acid. Alcohols which are completely miscible with water are advantageously employed, e. g. methyl. or ethyl alcohol.

The following examples will serve to illustrate the preparation of our new cationic surface active ammonium salts. These examples ar not intended to limit our invention. The parts given in the following examples are parts by weight.

EXAMPLE 1.N- (n-nonyl) -pyrz'dz'nium perchlorate the air.

647 parts of n-nonyl-p-toluenesulfonate and 175 parts of pyridine were mixed together and heated at to C. for three hours, under reflux. Upon cooling the reaction product, it solidified. 413 parts of this crude N-(n-nonyD- pyridinium p-toluenesulfonate were dissolved in 750 parts of warm methyl alcohol. To the resulting dark solution was added a warm aqueous solution of sodium perchlorate (270 parts in 200 partsof water). Upon chilling the resulting mixture for a short time, the pyridinium perchlorate separated out. It was filtered off and dried in 312 parts (91% yield) of the pyridinium perchlorate as white crystals melting at 79 C. were obtained.

The n -nonyl-p-toleunesulfonate employed in the aboveeggample can be prepared according to the method for preparing lauryl-p-toluenesulfonate described in the Jour. Am. Chem. .Soc. 55, 347 (1933).

EXAMPLE 2.-N-(n-heptylthiomethyl) perchlorate 6 parts n-heptylthiomethyl chloride (prepared -pyridinium by treating an equimolecular mixture of n-heptyl mercaptan and formaldehyde with a molecular equivalent of hydrogen chloride, at 0 to 10 C.) and 2.7 parts of pyridine were mixed together and warmed for 15 minutes on the steam bath. The development of a slight color and an increase in viscosity of the reaction mixture indicated the formation of N-(n-heptylthiomethyl) -pyridinium chloride.

v The viscous syrup, thus prepared, was dissolved in 25 parts of methyl alcohol at 40 to 50 C. To the warm methyl alcoholic solution were added 5 parts of sodium perchlorate, dissolved in 10 parts of water. On chilling the resulting mixture, 9 parts of N -(n-heptylthiamethyl) -pyridinium perchlorate separated out in the form of fine, white, silky needles, melting at 89 C.

In a similar manner, n-heptylthiomethyldimethylbenzylammonium perchlorate, melting at 167 C. and n-dodecylthiomethyl-pyridinium perchlorate, melting at 114 to 115 C. were prepared.

EXAMPLE 3.-N -(n heptorymethyl) pyridiniumperchlorate 176 parts of n-heptoxymethyl chloride (prepared by treating an equimolecular mixture of n-heptyl alcohol and formaldehyde with a molecular equivalent of hydrogen chloride at 0 to 10' C.) and 90 parts of pyridine were mixed together. A reaction took place immediately, considerable heat being evolved. The crude N-(n-heptoxymethyD-pyridiniurn chloride thus formed was cooled and dissolved in 400 parts of warm methyl alcohol. To the warm methyl alcoholic solution was added a warm aqueous solution of sodium perchlorate parts dissolved in parts of water). On chilling the resulting mixture, 253 parts of the N-(n-heptoxymethyl) -pyridinium perchlorate separated out as white crystals, melting at 71 to 73 C.

In a similar manner, the following pyridinium erchlorates were prepared from pyridinium hlorides:

M.P., C. T-(n-hexoxymethyll-pyridinium perchlorate 66 r-(n-octoxymethyD-pyridinium perchloheated in an open dish on the steam bath for about 2 hours to remove ether and methyl alco-' hol. 200 parts of an oil which is essentially n-heptoxymethyldimethylbenzyl ammonium perchlorate were thus obtained. Upon chilling to C., the oil set to a viscous mass.

In a similar manner, the following ammonium perchlorates were obtained:

'M. P. C.

n-Nony1dimethylbenzylammonium perchlorate 65 n Heptoxymethyldiethylbenzylammonium perchlora e oil n-Nonyldiethylbenzylammonium perchlorate oil p ter -Butylphenoxyethoxyethyldiethylbenzylammonium perchlorate oil EXAMPLE 5.-N-carbo-n-nonomymethylpyridinium rate 82 (n-nonoxymethyl) -pyridinium perchlorate l- (n-decoxymethyl) -pyridinium perchlorate 102 l- (n-undecoxymethyl) -pyridinium p e rchlorate '70 1 B-cyclohexylethoxymethyl) -pyridinium perchlorate 68- -'70 1 (B phenylethoxymethyl) pyridinium perchlorate oil T-citronelloxymethylpyridinium perchlorate oil sT-geranioxymethylpyridinium perchlorate N-cinnamyloxymethylpyridinium perchlorate N-rhodinoxymethylpyridinium p e r c h l 0- rate oil N-(3,7-dimethyloctanoxymethyl) -pyridinium perchlorate 25 N-abietyloxymethylpyridinium p e r c h lo.-

rate 011 N ('y-phenyl-n-propoxymethyl) pyridin ium perchlorate oil N-(fl-n-amyloxyethoxymethyl) -pyridinium perchlorate 8586 N-sandaloxymethylpyridinium p e r c h l o-' rate 31-34 The pyridinium chlorides employed to-prepare the foregoing perchlorates were prepared as illustrated in Example 3 by mixing pyridine with the appropriate oxymethyl chloride. The oxy-. methyl chlorides were always prepared by treating an equimolecular mixture of the appropriate alcohol (e. g. n-hexylalcohol, fi-cyclohexylethyb alcohol, citronellol, rhodinol, abietyl alcohol -or fi-n-amyloxyethyl with a molecular equivalent of hydrogen chloride, at 0 to 10 C. In the case of Sandaloxymethyl chloride, the alcohol involved is actually a mixture of alcohols, viz. those occurring in Sandalwood oil. Where the perchlorate obtained is an oil at ordinary temperatures, it was purified by extracting impurities therefrom with diethyl ether and driving off residual ether by warming theoil.

EXAMPLE 4.-n-Heptoxymethyldimethylbenzylammonium perchlorate To 85 parts of dimethylbenzylamine were added 100 parts of n-heptoxymethyl chloride. The mixture became quite hot. It was stirred and allowed to cool to room temperature. The thick viscous syrup thus obtained was essentially n-heptoxymethyldimethylbenzylammonium chloride.

This viscous syrup was dissolved in 125 parts of warm methyl alcohol and to the warm alcoholic solution was added a warm aqueous solution of sodium perchlorate (150 parts dissolved in 100 parts of water). An oil separated at once and some sodium chloride precipitated. Suflicient water was added to redissolve the sodium chloride. The oily layer was separated from the aqueous layer. The oily layer was shaken with diethyl ether to remove unchanged amine and unchanged n-heptoxymethyl chloride. The oily product was separated from the ether and then alcohol) and. formaldehydeperchlorate 5 parts of n-nonylchloracetate (prepared by treating chloracetic acid with n-nonyl alcohol) and 2 parts of pyridine were placed in 25 parts of dry benzene and the solution was heated on a steam bath,.-under reflux, for 18 hours. The solution became very dark and the N-carbo-nnonoxymethylpyridinium chloride failed to crystallize out upon cooling the solution. Thesolventbenzene was removed by distillation on the steam bath.

The residue from the aforesaid steam distillation, consisting essentially of crude N-carbo-nnonoxymethylpyridinium chloride, we dissolved in 20 parts of methyl alcohol. To the methyl alcoholic solution was added 4 parts of sodium perchlorate dissolved in 10 parts of water. Upon chilling the resulting mixture, 2.3 parts of the pyridinium perchlorate, as a yellow flaky salt, separated out. It melted at 92 C.

In a similar manner, 'y-( -phenylbutyroxwpropylpyridinium perchlorate, melting above 200 C was prepared. The 'y-(v-phenylbutyroxm- 'propylpyridinium chloride employed to prepare EXAMPLE 6.-N-(p-capro:ruethyl) -pyridini1um perchlorate 1.5 parts of p-chloroethyl caproate (prepared by the interaction of ca'proyl chloride and ethylene chlorohydrin) were mixed with 2 parts of pyridine and the mixture was heated for 2 hours at to C., under reflux. On cooling the reaction mixture, a viscous mass of crude N-(B- caproxyethyl) -pyridinium chloride was obtained.

This crude pyridinium chloride was dissolved in 15 parts of methyl alcohol and to the methyl alcoholic solution were added 5 parts of sodium perchlorate dissolved in 10 parts of warm water. Upon chilling the resulting solution, an oil separated. The oily layer was removed and washed with diethyl ether to remove unchanged reactants. The oil was then heated on the steam bath to remove residual ether. The resulting oil was essentially N-(p-caproxyethyl)-pyridinium perchlorate.

EXAMPLE 7.--N- (n-butoxyethoxyethyl) -pyridinium perchlorate 3.1 parts of n-butoxyethoxyethyl chloride (prepared from Butyl Carbitol and phosphorous pentachloride according to'the method of Palomaa and Kenetti, Ber. 64, 798, (1931)) and 1.5

parts of pyridine were mixed together and heated, under reflux, for 3 hours at 125 to 135 C. Upon cooling, a viscous mass resulted which was essentially N- (n-butoxyethoxyethyl) -pyridinium chloride.

The aforesaid pyridinium chloride was dissolved in 15 parts of warm methyl alcohol and to the warm alcoholic solution, 2.5 parts of sodium perchlorate, dissolved in 10 parts of warm water, were added. After chilling to C. for several hours, an oily layer separated. The oily layer was removed from the aqueous layer and washed with diethyl ether to remove unchanged reactants. The oil was then heated on a steam bath to remove residual ether. The 011 thus obtained was essentially N-(n-butoxyethoxyethyhpyridinium perchlorate.

EXAMPLE 8.-N

ethyl) p ter butylphenomyethoxy -p 1 rz'clinium perchlorate parts of methyl alcohol and to the alcoholic solu tion were added 17 parts of sodium perchlorate dissolved in 20 parts of warm water. Upon cooling the resulting mixture, 23 parts of the pyridinium perchlorate separated out as a white flaky crystalline material, melting at 64 to 69 C.

In a similar manner, the following related perchlorates were obtained:

3 2 4 -oo11icHiocHzoH, N c1o.

M. P. C. 4-methyl 63-64 4-ethyl oil 4-isopropyl 133 4-ter-amyl oil 4-cyclohexyl 105 2,4-dimethyl oil 3-methyl-6-isopropyl 78-80 2-methyl-5-lsopropyl 87-89 2-phenyl oil 4-phenyl 134 2-benzyl 135 4 -benzyl 67 2-hydroxymethyl 146-147 4-chloro 79 2,4-dichloro 88-90 4-bromo 61-63 2-iodo 75 4,4-chlorophenyl 79-81 2-isopropyl-5-methyl-4chloro 88 4-methoxy 62-64 4 -aceto 98 4-propio 69 4-n-butyro 61-63 4-a1lyl-2-methoxy oil Z-carboxy 124-126 4-phenylazo 105-107 perchlorate dissolved EXAMPLE 9.N (pJorrhylphenoxyethoryethyl) pyridinium perchlorate 2.5 parts of p-formalphenoxyethoxyethyl chloride (prepared by reacting'one molecular proportion of p-hydroxybenzaidehyde with four molecular proportions of p,fi-dichlordiethyl ether at 160 to 180 C. for 10w 15 hours, in the presence of solid sodium hydroxide) and 1 part of pyridine were mixed together and heated, under reflux. on an oil bath for 3 hours at to C. Upon cooling, the reaction mixture set to a viscous gum.

This gummy product was dissolved in 10 parts of warm methyl alcohol and to the methyl alcoholic solution were added 2 parts of sodium in 6 parts of water. Upon chilling the resulting mixture to 0 C. for several hours, 2.3 parts of the pyridinium perchlorate separated out melting at 105 C.

In a similar manner, the following perchlorates were obtained:

a 2 4 -ocmcmocmcm NZc1o.

M. P. C. 3-formyl 104-106 2-methyl-4-formyl-5-isopropyl 106 2-isopropyl-4-formyl-5-methyl 97 2-methoxy-4-formyl 153 2-ter-amyl-4-formyl oil 2-formyl-4-chloro 88-90 2-formyl-4-bromo 56 EXAMPLE 10.N p naphthoxyethoxyethyl pyridinium perchlorate -ing mixture was allowed to stand in an ice chest for 5 hours, when an oil separated which quickly soldified upon stirring. The solid pyridinium perchlorate was filtered off and washed with diethyl ether. It melted at 78 to 81 C.

In a similar manner, N-(a-naphthoxyethoxyethyl)-pyridinium perchlorate and 2(3) -phenanthroxyethoxyethyl pyridinium perchlorate were obtained. Each was obtained as an oil.

EXAMPLE 11.N-(p-methylphenozypropowypropyl) -pyrz'dinium perchlorate 6.5 parts of p-methylphenoxypropoxypropyl chloride (prepared by reacting one molecular proportion of p-cresol with four molecular proportions of 'm"-dichloro-di-n-propyl ether at to 180 C. for 10 to 15 hours, in the presence of solid sodium hydroxide) and 2.5 parts of pyridine were mixed and heated, under reflux, at 125 to 135 C. for 3 hours. Upon cooling, the reaction product was taken up in 15 to 20 parts of methyl alcohol. To this solution, were added 6 parts of sodium perchlorate dissolved in 12 parts of water. The pyridinium perchlorate separated as an oil ich solidified after chilling at C. for several The oily product was washed with diethyl ether us. The pyridinium perchlorate was recrystaland dissolved in 30 parts of hot methyl alcohol. ad from ethyl alcohol and '7 parts of a white To this hot methyl alcoholic solution, 15 parts of 'stalline salt, melting at 64 to 65 C., were sodium perchlorate in 15 parts of warm water was tained. added. On cooling the resulting solution, 13.5 [n a similar manner, N-(p-phenylphenoxyproparts of the crude perchlorate melting at 8286 xypropyl) -pyridinium perchlorate, melting at separated. When the salt was recrystallized from J C., and N.-(ter-butylphenoxypropoxypropyl)- methyl alcohol, the purified perchlorate melted ridinium perchlorate,a.n oil, were obtained. at 98-100 C. The salt has the following for- :AMPLE l2.-N-(p-cresylthioethoxycthyl)-pyridinium perchlorate 6.3 parts of p-cresylthioethoxyethyl chloride 1 repared by reacting one molecule proportion of thiocresol with four molecular proportions of 3'-dichl0rodiethyl ether at 160 to 180 C. for

I to 15 hours, in the presence of solid sodium EXAMPLE 16.-N -(w hydroxydecyD- pyridinium zdroxide) and 3 parts of pyridine were mixed perchlorate gether and heated at 125 to 135 C. for 3 )lllS, under reflux. The reaction product was 5 g i of decamethylene chlomhydrm and 20 s of pyridine were mixed together and fggg g g gi 1 g l fl ggi g; ag: the mixture was heated, under reflux, in an oil lded 6 parts of sodium perchlorate, dissolved in bath 3 at a temperature Upon cooling the mixture it set to a white 3 parts of water. The pyrldlnlum perchlorate eparated as an oil which solidified upon chilling cake was 1155mm )r several days at 0 C. The crude material was f fnethyl alcOhOl- 0 the resulting soluacrystamzed from methyl alcohol and 5 of a tlon, dlethyl ether was added until aploudmess ,hite crystalline Salt melting at to 460 developed. Upon chllllng the resulting cloudy we obtained solution to 0 C. for 2 hours, 10 parts of the pyridinium chloride separated out.

lXAMPI-E ll ll -Py 2 parts of the pyridinium chloride we e disdinium perchlorate solved in 10 parts of methyl alcohol and to the resulting solution were added 2 parts of sodium perchlorate dissolvedin 8 parts of warm water. Upon chilling the resulting solution to 0 C., 1.5

4.5 parts of w-phenyltetraoxyethyl chloride prepared by reacting one molecular proportion 35 finfiiffifilenlliyid etfifffi it it tt it 2. Paris of W i Perchlorate Separated or 10 to 15 hours, in the presence of solid sodium out as wmte nd It melted at 51 to 52 lydroxide) and 1.8 parts of pyridine were mixed EXAMPLE 17.-N-methyl-n-(n-nonyl) -pyridinium logether and heated, under reflux, at 125 to 135 perchlorate 3. for three hours. The reaction mixture was :ooled and taken up in 20 parts of methyl alcohol. To the resulting methyl alcoholic solution, 5 parts of sodium perchlorate, dissolved in 10 parts of water, were added. The pyridinium perchlorate separated as an oil whichdid not solidify even upon several weeks chilling at 0 C. The oil was washed several times with diethyl ether and then heated on a steam bath to remove traces of ether.

The oil still failed to solidify upon prolonged chilling at 50 (n nonyl) pyridlmum-p-toluenesulfonate separated out. It was collected on a filter and Exmm: 14-N. '-deca y e y washed with cold acetone and dried in the air. pip d n um p r h ra 220 parts of faintly yellow crystals, melting at 134 C. were obtained. 5 parts of decamethylene bromide and 3.5 parts of N-methylpiperidine were mixed together and 55 parts of 'pyndlmum' heated for a few minutes in an on bath at p-toluenesulfonate were dissolved in 32 parts of A vigorous reaction ensued and the mixture bewarm methyl alcohol and to the'resultmg Solucames1id tion were added 32 parts of sodium perchlorate, The solid product was dissolved in 20 parts of dissolved in 32 parts of water Upon chilling the warm methyl alcohol and to the warm alcoholic resulting mixture to 23 Parts the solution were added 5 parts of sodium perchlorate methyl'a'mmmyl)Pyridmium Perchlorate dissolved in 10 parts of warm water. Upon chillmated It was filtered \15ing 9- chilled ing the resulting mixture at 0 C. for several tunnel because of its low meltmg Pomthours, 3 parts of the piperidinium perchlorate In a Similar manner, r' separated out as white crystals. The crystals pyridinium-P-t0111ene5111f011ate, melting at 88 melted at 186 to 190 C. C., N-methyl-a(n-octyl) -pyridinium-p-toluenesulfonate, melting at 116 to 118 C., N-methylm 15' M'n'nonyl'z'phenylpynmldazolmm a. (n decyl) pyridinium p-toluenesulfonate,

perchlorate melting at 99 C., N-methyl-d-(n-undecyh- Five and seven-tenths parts of Z-phenylpyrimipyr nium-p-t0luenesulfonate, m ing at to dazole and 9 parts of n-nonyl p-toluenesulfonate and N- thyl-v-n0nylpyridinium-p-to1- were heated for 3 hours at Mil- C. and cooled. u ate. melting at to 162 C. can be h N-n-nonyI-Z-phenylpyrimidazolium 4 1 prepared and converted to the corresponding enesultonte separated as an oil. 75 p rates.

142 parts of d-(n-nonyl) -pyridine and 142 parts (10% excess of methyl-p-toluenesulfonate were mixed well and allowed to stand at room temperature. An exothermic reaction took place,

45 the temperature rose to 125 C, and the reaction mass finally solidified. The solidified mass was dissolved 700 parts of a warm mixture of 6 parts of acetone to 1 part of methyl alcohol. Upon cooling the resulting solution, N-methyl-a- EXAMPLE 18.-N heptcrymethyl a- (n-nonyl) pyridinium perchlorate 2.2 parts of (n-nonyl) -pyridine and 1.7 parts of n-heptoxymethyl chloride were mixed togeth'er. Heat was evolved and a gummy product resulted. The gummy product was dissolved in 10 parts of warm methyl alcohol and to the resulting solution were added 3 parts of sodium perchlorate dissolved in 10 parts of warm water. An oil separates out immediately. The oil was separated from the aqueous alcoholic layer and then dissolved in methyl alcohol. The methyl alcohol solution was treated with water until a faint cloudiness developed. The solution was then chilled to C. N-heptoxymethyl-a-(nnonylJ-pyridinium perchlorate separated out as white crystals, melting at 61 C.

EXAMPLE pyridinium perchlorate 6.7 parts of n-heptyl picolinate and 5.6 parts of methyl-p-toiuenesulfonate were mixed together and heated for 3 hours at 125 to 135 0., under reflux. The reaction mixture solidified upon cooling and was recrystallized from a small volume of acetone. The recrystallized product was washed with diethyl ether and allowed to dry. In this manner, 6.5 parts of the pyridiniump-toluenesulfonate were obtained as bufl crystals, melting at 108 C. A portion was converted to the perchlorate in the manner illustrated in the above example.

Similarly, the following pyridinium p-toluenesulfonates were prepared and converted to the corresponding pyridinium perchlorates.

M. P. C. N methyl a- (carbo-n-octoxy) pyridinium-p-toluenesulfonate 110 N methyl -p-carbo-n-heptoxy) -pyridinium-p-toluenesulfonate 85 N methyl -p-(carbo-n-o'ctoxy) -pyridinium-p-toluenesulfonate 88-89 N nonyl p-(carbo-n-octoxy) -pyridinium-p-toluenesulfonate 100 EXAMPLE 20.--N-methyl-a-tridecylpyridinium perchlorate 2.6 parts of a-(n-tridecyl) -pyridine and 1.4 parth of methyl iodide were mixed together and allowed to stand overnight at room'temperature. The resulting solid reaction product was dissolved in 10 parts of warm methyl alcohol. To this solution were added 3 parts of sodium perchlorate dissolved in parts of warm water. The resulting mixture was allowed to stand in an icebox for several hours when white crystalsof the pyridinium perchlorate separated out. These crystals (2.1 parts) melted at 20 C. and are advantageously filtered off using a chilled funnel.

N (n -heptoxymethyl)--trideeyl-pyridinium perchlorate, melting at 23 C. was similarly prepared from N-(n-heptoxymethyl)-a-tridecylpyridinium p-toluenesulfonate which was obtained as a gum by the interaction of -(n-tridecyD-pyridine with methyl-p-toluenesulfonate.

EXAMPLE 21.0ctyl dimethyl sulfonz'um perchlorate arate. This oil was thrown out by the addition 19.-N-methyl-a- (carbo-n-heptomy) EXAMPLE 22.n-Decyl-1-phenyZ-3,5-dimethylpyrazolium perchlorate A mixture of 2.7 parts of n-decyl iodide and 1.7 parts of 1-phenyl-3,5-dimethylpyrazole was heated for 3 hours at 120-150 C. The reaction product was dissolved in 15 parts of methyl a1- cohol and treated with 3 parts of sodium perchlorate in 10 parts of water. On chilling for several hours an oil separated. It was removed from the aqueous alcoholic layer and washed with ether to remove any unchanged n-decyl iodide or pyrazole, and then warmed on the steam bath for a few minutes to remove volatile solvents. There was thus obtained 4 parts of a crude oily product which is essentially n-decyl- 1-phenyl-3,5-dimethylpyrazolium perchlorate.

EXAMPLE 23.Tetramethylene-bis-1-phenyl 3,5 dz'methylpyrazolium perchlorate A mixture of 2.2 parts of tetramethylene bromide and 3.4 parts of 1-phenyl-3,5-dimethylpyrazole was heated for 3 hours at-120-150 C. The product, which was essentially tetramethylene-bis-l-phenyl 3, 5 dimethylpyrazolium bromide, fails to solidify on cooling. It was dissolved in 15 parts of methyl alcohol and treated with a warm solution of 3 parts of sodium perchlorate in 10 parts of water. On chilling for several hours, the tetramethylene-bis-1-phenyl-3,5-dimethylpyrazolium perchlorate separated as an oil. It was removed from the alcoholic-aqueous layer and dissolved in 15 parts of warm acetone. On chilling this solution, 1.5 parts of tetramethylene-bis-1-phenyl-3,5-dimethylpyrazolium perchlorate separated as a white salt melting at 216-218 C.

The cationic surface active quaternary ammonium perchlorates having a cation which contains a chain of at least eight members are especially useful substances for incorporation in photographic emulsions. Advantageously, such members are from the group consisting of carbon, oxygen and sulfur atoms. One or more aromatic rings, such as a benzene ring for example, can take the place of one or more of the eight or more atoms. Thus, a benzene ring can take the place of one atom, while a naphthalene ring (two benzene rings fused together) can take the place of two atoms. The atoms attached to the.eight or more atoms in the chain (where valence permits) can be hydrogen, oxygen, sulfur, carbon or halogen for example. Any aromatic ring system in the chain can carry simple substituents. The organic group containing a chain of eight or more atoms can be directly attached to the quaternary ammonium nitrogen atom or indirectly thereto by means of a group of atoms. Cationic surface active quaternary ammonium perchlorates having an ammonium cation containing a lipophylic organic group which contains a chain of from nine to twelve members selected from the group consisting of carbon atoms, oxygen atoms, sulfur atoms and aromatic ring systems are especially useful. More specifically, the N-alkoxymethylpyridinium perchlorates, the alkoxymethyldimethylbenzylammonium perchlorates and alkoxymethyldiethylbenzylammonium perchlorates, in which the alkoxy group is one of the formula CnH2n+1O wherein n represents a positive integer of from 6 to 10 i that we have provided are especially useful, as are the quaternary pyridinium salts characterized by having attached to one of the carbon atoms of the pyridine nucleus an organic group containing a chain of at least eight atoms.

It is, therefore, apparent from the foregoing perchlorate derivatives of a variety of surface active materials, of which the ammonium type are prepared. Hence, we do not wish to be restricted in our invention, excepting insofar as is necessitated by the prior art and the spirit of the appended claims.

What we claim as our invention and desire to be secured by Letters Patent of the United States is:

. CERTIFICATE OF CORRECTION;

Patent 2,299,782.

CHARLES F. H. ALLEN, ET AL.

1. A cationic surface active quaternary ammonium perchlorate of the foiiowing general formula:

wherein n represents a positive integer of at least 8.

CHARLES F. H. ALLEN. CHARLES V. WILSON.

October 27, ,19lr2.

It is hereby certified that error appears in the printed" specification of the above numberedpatent requiring correction as'follows': Page 1;, first column, line 114., for "molecule" nonyl" read -N-n-nony1--; with this correction therein the case in the Patent 0ffice.

(Seal) read --mo1ecu1ar--;

line 68-, for "ll-nand that the said Letters Patent should be read that the samemay conform to the record of fdanuary, A. D. 1911.5.

Henry Van- Arsdale I CERTiFICATE OF coRREcrmm; Patent 2,299,782. October 2'], ,19u2.

-' CHARLES F. H. ALLEN, ET AL.

printed specification It is hereby certified that error appears in the 'follows': Pagehi, firet of the above numberedpatent requiring correction a; column, line 111., for "molecule" nonyl' read --N-n-nonyl--; and that the said Letters Patent should be read with this correction therei the case in the Patent 0ffice.

Signed and sealed this 5th day of January, A. D. 1911.5.

Henry Van Araqele (Seal) Acting Commhissioner of Peten'ta read --mo1ecular-; line 68', f r 'H-nn that the Same may conform to the record of