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US3444200A - Aryl-alkyl quaternary ammonium compounds - Google Patents

Aryl-alkyl quaternary ammonium compounds Download PDF

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US3444200A
US3444200A US500203A US3444200DA US3444200A US 3444200 A US3444200 A US 3444200A US 500203 A US500203 A US 500203A US 3444200D A US3444200D A US 3444200DA US 3444200 A US3444200 A US 3444200A
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chloride
amine
methyl
quaternary
mole
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Eugene J Miller Jr
Harlan E Tiefenthal
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Armour Industrial Chemical Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines

Definitions

  • This invention relates to a novel class of aryl-substituted 1 alipha ic quaternary compounds, and more particularly,
  • the quaternary compounds of the present invention can be represented by the following structural formula wherein R is selected from alkyls of l to 3 carbons and R, and R, are both selected from (t) alkyls of l to 3 carbons, and (2) --(CH,CH,O),,H for R: and
  • R with p and w being integers from 1 to with the total of p and w not exceeding 60
  • A is anion having a valence of l to 2
  • n is an integer from 1 to 2
  • x and y are integers from 0 to 19 and the total of x and y is an integer from 8 to 19
  • R is selected from phenyl, naphthyl, and phenyl substituted with from 1 to 2 groups selected from methyl. hydroxy, and methoxy.
  • R R and R are methyl. in another subclass.
  • R is methyl
  • R is -(CH,CH;O),,l-l, and R; is (CH,CH O),,H with p and w being integers from I to 20 and with the total of p and w not exceeding 30.
  • the other variables have the meanings previously defined.
  • R, and R are methyl and R is Cll
  • t is methyl.
  • R is phenyl
  • R is methyl
  • n is l
  • A is chloride
  • the quaternary compounds contain at least one long chain aryl-substituted aliphatic group, or, more specifically, an aralkyl group.
  • the alkyl portion of the aralkyl group conta ns a total of 18 carbons.
  • the alkyl portion of the aralkyl groups contain ll, l6 or 22 carbons. More generally, the total of .r and y. which is three less than the total of carbons in the alkyl portion of the aralkyl, may range from 8 to 19.
  • the compounds also contain at least one, or up to three, short chain alkyl groups which are bonded to the nitrogen atom. Whil methyl groups are preferred, the alkyl groups may also comprise ethyl, propyl, etho-, or propo-, or mixtures thereof.
  • R represents the aryl substituent.
  • the carbon to which the aryl group is attached varies with the respective values of x and 3'.
  • unsaturated alkylene chains such as oleyl
  • the double bond migrates up and down the chain (isomerization by hydrogen ion transfer) resulting in a mixture of isomeric products.
  • arylating oleyl there is a tendency for the C -C and the C aryl isomers to predominate, but smaller mole percentages of other isomers, such as the C C C1 and C isomers are also produced.
  • the mole percent of the C C isomers is usually quite small or even negligible.
  • the relative proportions of the various isomers may vary depending on the arylation p.ocess. See J. Org. Chem. 30, 885-888 (1965). However, the total of x and y will remain constant for the particular unsaturated chain, viz. 15 for oleyl, B for t.nd.cyl, 19 for behenyl, etc.
  • arylation oleic acid is converted to arylsubstituted stearic acid.
  • palmitoleic, erucic, and IO-undecenoic acids can be converted to the c ..responding aryl-substituted carboxylic actds. Ordinary commercial grade oleic acid contains several percent of palmitoleic acid, and therefore a mixture of aryl-substituted stearic and palmitic acids is obtained by arylation.
  • aryl substitucnts are phenyl, hydoxphenyl, tolyl, anisyl, and naphthyl. More generally. the phenyl nucleus may be substituted with l or groups such as methyl, hydroxy, and mcthoxy. Other groups coming within this subclass are cresyl, resorcyl, xylyl. etc.
  • the cationic portion of the molecule will be associa ed with an anionic portion.
  • the particular anion is not cmical, and generally the anion may be any of those whicl are commonly pres eat in quaternazy compounds, such as monovalent or divalent anions.
  • n will be t for monot'tlent anions and 2 for divalent anions.
  • Chloride salts of the quaternary are particularly desirable where the compounds are to be employed as cationic emulsifiers, but other salts can be used such as hydroxides, sulfates, nitrates, hydrochlorates, perchlorat s. hypochlorates, l'ormates, acetates, etc. Eor certain purposes the anion shouldbe seletted to provide water solubility or water dispersibtlrty.
  • the aryl fatty acids such as arylstearic acid or arylp lmitic acid, may be prepared by the arylation of oluic acid or palmitolerc ac d.
  • a catalyst is ordinarily required for such arylation, :5 rs well known in the art.
  • aluminum chloride may he employed as the catalyst.
  • the fatty acid is preferably first converted to the cyano derivative, which is reacted with the arylating agent in the presence of aluminum chloride.
  • the aryl cyanoaliphatic compound by procedures well known in the art, can then be convened to the corresponding primary amine (by hydrogenatron). then to the tertiary amine (by alkylation with short chain alkyl groups or alkoxy groups), and finally quatemrz ed by a suitable quaternizing agent such as methyl chloride or dimethyl sulfate.
  • phenylstearic acid (or other aryl-substituted long chain fatty acid) can be converted to the wrresponciiug rritriie, the nitriie converted to the primary amine, the primary lmln; convened to the tertiary amine, and the tertiary amine quatemize l.
  • the prima y amine such as phenyl tearyl amine, can be convened to the quaternary by reaction with methyl chloride.
  • the primary amine can also be ethoxylated o propexylatcd by reaction with ethylene oxide or propylene oxide before being quaternized. It will be understood that suchproceduresarewellknownintheart.
  • Phenylstearic acid, hydroxyphenylstearic acid, and tolylstearic acid were prepared from commercial grade olcic acid which contained a few percent of palrnitoleic acid by a Fricdel-Cratts reaction using aluminum chloride as the catalyst and benzene. phenol. and toluene, respectively, as the arylating agents. Thereafter, phenylstearonitrile was preplred on a continuous nitrile unit over bauxite catalyst at 280-300 C. from I127 g. phenylstearic acid. A crude yield of 833.5 g. of phenylstearonitrile was obtained comprising a mixture of isomers. predominantly, the C. to C and the C isomers with lesser proportions of other isomers.
  • hydroxyphenyloctadecylamine was preplr d in 91.5% crude yield and 8l% distilled yield from distilled hydroxypherrylstearonitrile prepared as described in Example I. Tolyloctadecylamine was prepared in 97% crude yield from the distilled nitrile.
  • Example lll Phenyloctadecylaminc (50 3.. 0.l mole) prepared as described in Example ll and NaHCO, (25 g., 0.31 mole) in ml. isopropanol were treated with methyl chloride at -80/70 p.s.i. in a 300 cc. stirred autoclave for 3.5-4 hours. Carbon dioxide was removed by periodic venting of the reaction vessel. The reaction mixture was then diluted to an approximately 50% solution of quaternary in isopropanol.
  • the product was a mixture of isomers of N,N,N-trimethyl-N-phenyloctadecylammonium chloride.
  • nil free amine, 0.9%.
  • Example [V Tolylstearonitrile (806.8 g., 2.27 moles) was reduced in a two-liter Parr autoclave over 2% (by wt.) alcohol Raney nickel cataly t in he presence of ammonia (360 psi/' C.) and hydrogen (800 p.s.i. total pressure/ 135-135 C.) in five hours.
  • the crude amine was obtained as an amber oil, 800 g. (98% crude yield).
  • Analyris.-Neut. equivalent 362 (Calcd. 359.6); Primary amine, 881%; Secondary amine, 0.31 meg./g.
  • Amlysi.r.Neut. equivalent 362 (Cllcd. 359.6); Primary amine, 98.8 k.
  • Example V Xylylstearonitrile (579.! g., 1.56 moles) was reduced in a one-liter Magnedash autoclave over 2% (by wt.) alcohol washed Raney nickel catalyst in the presence of ammonia (480 psi/I35 C.) and hydrogen (800 p.s.i. total pressure/B5440 C.) in eight hours.
  • the crude was obtained as an amber oil, 576.4 g. (99% crude yre Ana1 r.ri.r.-l ⁇ 'eut. equiialent. 366.0 Calcd. 375.7); Primary amine, 100.5%; Secondary amine, 3.l4%.
  • Example VII stirred, was chargedwith 25.0 (0.052 mole) NJ- A 500 ml. alas motor was elnr etl with 4: tr. (0.116 M W mole) of anisyloctadocylsmine, 19: 9232 mole) or 3 5?. u l 9 M M aodillm bicarbonate and 200 ml. or isopropanol. 'nie re- ""E C actor wit sealed and the reaction mixture heated to s 9 i .”E" 60-70 C. Gaseous methyl chloride was introduced at hour at 70785 50% 60-70 p.s.i.g.
  • a 500 ml. glass reactor was charged with is g. (0.032 I Bump xm 1 m f naphmylocmecylamim. 10.1 2 mole) f
  • a 500 ml. glass reactor was charged with 12.7 g. (0.027 sodium bicarbonate and 50 1 of isopropanoL h moie) of N,N-d l-(Beta-hydroxyethyl)tolyloctadecylatmne actor was sealed and the reaction mixture hand to 0 and 41.6 g. f lsopropanol.
  • the reactor was sealed and 70 C methyl chloride was immduccd at 040 heated to 80 C.
  • the o- Example x1 actor was sealed and the temperature raised to 70' C.
  • a 500 ml. glass reactor was charged with 50.0 g. (0.203 Gaseous methyl chloride was introduced at 70 p.s.i.g. and mole) of phenylundecylamine, 37.9 g. (0.45 mole) of the reaction mixture maintained at 60-7 C./60-70 sodium bicarbonate and 50 g. oi isopropanol.
  • the reactor p.s.i.g. for four hours with periodic venting.
  • the reactor was scaled and thc tennt-rature raised to A 200 ml. 3-neck round bottom flask, equlpped with an C.
  • Gaseous methyl chloride was i' troduccJ at 75 p.s.i.g. addition funnel, thermometer, reflux condenser and msg- 75 and the reaction mixture maintained at 70-80 C./ 70-80 7 p.s.i.g. for six hours with periodic venting.
  • Sodium chlw ride and excess sodium bicarbonate were removed by &1- tration and the iaopropanol solutionot quaternary was concentrated under reduced pressure.
  • the resultant prodquaternary 88.9;
  • Example XX A 500 ml, glass reactor was charged with 40.8 g. (0.119 mole) of N,N di(Beta hydroxyethyl)phenylundecylamine, 2.5 g. (5% by wt.) of sodium bicarbonate and about 100 ml. of isopropanol. The reactor was sealed and the mixture heated to 70' C. Gaseous methyl chloride was introduced to 75 p.s.i.g. and the reaction mixture maintaineo at 75-80' C./70-75 p.s.i.g. for five hours with periodic venting. The sodium chloride and excess sodium bicarbonate was removed by filtration yielding an isopropanol solution of the quaternary ammonium salt.
  • Example XXI A 500 ml. glass reactor was charged with 37.1 g. (0.072 mole) of N.N-di(Bcta-hydroxyethyl)phcnvldocosylamine, 5.0 g. (0.059 mole) of sodium bicarbonate and about 100 ml. of isopropanol. The reactor was scaled and the mixture heated to 75' C. Gaseous methyl chloride was introduced at 0 p.s.i.g. and the reaction mixture maintained at 75-80' C./70-75 p.s.i.g. for five hours with periodic venting. The sodium chloride and excess sodium bicarbonate were removed by filtration, yielding an isopropaaol solution of the quaternary ammonium salt.
  • Example XXII A twotrter Parr autoclave was charged with 761.0 g. (2 6 moles) of toty1tallowamine," 512.9 g. (5.7 moles) and 150 ml. of isopropanol. The reactor was sealed and the mixture heated to 65-75 C. Gaseous methyl chloride I introduced at 70-75 p.s.i.g. and the reaction mixture maintained at 65-75 C./ 70-75 p.s.i.g. for about eleven hours. Socium chloride and excess sodium bicarbonate were removed by filtration with the aid of additional isopropanol.
  • the isopropanol solution containing the N,N.N- trimethyl-N-tolyltallow" ammonium chloride was then concentrated to the maximum concentration at which it still remained AnalysiL-Petoent quaternary, 73.8; Free amine, 0.25%;Amioe-HC1, nil.
  • Example XXlll A 500 ml. glass reactor was charged with 69.2 g. (0.1 mole) of di-(xylyloctadecyl)amine, 10.9 g. (0.13 mole) of sodium bicarbonate and 95 ml. of isopropanol. The reactor was sealed and the temperature raised to 80' C. Gaseous methyl chloride was introduced at 85 p.s.l.g. and the reaction mixture maintained at 80-85 C./85-90 p.s.i.g. for three hours with periodic venting.
  • Example XXIV A 500 ml. glass reactor was charged with 34.9 g. (0.063 mole) of N,N-di.- (alpha-methyl Beta hydroxyethyl)- phenylbehenylamine, 2.0 g. of sodium bicarbonate and 35 g. of iaopropnnol. The reactor was sealed and the mixture heated to 75" C. Gaseous methyl chloride was introduced to 75 p.s.i.g. and the reaction mixture maintained at .5-80' C./701-75 p.s.i.g. for ten hours with periodic venting. Sodium chloride and excess sodium bicarbonate was removed byfiltration, yielding an isopropanol solution of the quaternary ammonium salt.
  • Quaternary ammonium compounds represented by the formula whe'ein R is selected from the group consisting of alkyl radicals having from 1 to 3 carbon atoms, and
  • R is selected from the group consisting of alkyl radicals having from 1 to 3 carbon atoms, (CH,CH,0),H, and
  • CIIa cmnomr and R is selected from the group consisting of alkyl radicals having from I to carbon atoms, and
  • p and w are integers from 1 to 40 and the sum of p and w is less than R. is selected from phenyl, naphthyl, and phenyl substituted with from 1 to 2 groups selected from methyl. hydrosy, and methoxy; r and y areintegersfromotr l9andthesumotxandyisan integertromS to I9;Aisananion;andnisaninteger from 1 to2,saidcompoundscomprisingisomericmixtures with respect to the position of R to the alkyl chain.
  • R is methyl.
  • R. is -(CH;CH,O),H, and R, is -(CH;CH.O).H wherein pandwareintegersfrom 1 toZOandthesumofpand w is less than 30.
  • R is methyl
  • R3 is wherein p and w are integers from I to 20 and the sum of p and w is less than 30.
  • A is selected 9 from the group consisting of Cl--, 50.”, OH, NO; and Br.
  • A is selected from the group consisting of Cl, S0,, OH-, NO; and Br.
  • R is hydroxyphenyl
  • A is selected from the group consisting of C1, 50,-, OH", NO; and Br'.
  • R R3 and R are each methyl, and R is hydxoxyphenyl.

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Description

. 3,444.20. ARYLALKYL %I(J)ATERNARY AMMONIUM t MPOUNDS g ICIILMIBGIQMMMIIIWLMQIM den m mbrane-ligaments, toArnoorlndumlalCbenlealCompan aeorpontlol of Delaware No Drawing. Filed Oct. 21, 1965, Ser. No. 500,203
Int. Cl. C070: 87/30 US. CL 260-7. Claims ABSTRACT OF THE DISCLOSURE United States Patent: i
This invention relates to a novel class of aryl-substituted 1 alipha ic quaternary compounds, and more particularly,
used for other purposes, such as for fabric treatm nt and in textile processing.
The quaternary compounds of the present invention can be represented by the following structural formula wherein R is selected from alkyls of l to 3 carbons and R, and R, are both selected from (t) alkyls of l to 3 carbons, and (2) --(CH,CH,O),,H for R: and
or R, with p and w being integers from 1 to with the total of p and w not exceeding 60, A is anion having a valence of l to 2, n is an integer from 1 to 2, x and y are integers from 0 to 19 and the total of x and y is an integer from 8 to 19, and R is selected from phenyl, naphthyl, and phenyl substituted with from 1 to 2 groups selected from methyl. hydroxy, and methoxy.
lrt one subclass, R R and R are methyl. in another subclass. R, is methyl, R, is -(CH,CH;O),,l-l, and R; is (CH,CH O),,H with p and w being integers from I to 20 and with the total of p and w not exceeding 30. In these subclasses, the other variables have the meanings previously defined.
in still another subclass, R, and R; are methyl and R is Cll|((ll:).C'll(Clh),CIh-
l where x, y, and K, have the meanings previously defined.
Y 4. PM .7 I1, I-
In a further subclass, t, is methyl. rt, a (cu,cn,o),,u
where x. y and R have the meanings previously defined.
In another relatedembodiment, R, is
-(JIHCH|O) U R is i CH1 cacmo).a
with p and w being integers from I to 20 and with the total of p and w not exceeding 30. The other variables have he meetings previously defined, or R, is phenyl, R is methyl, n is l, and A is chloride.
It will he noted from the toregoing formula that the quaternary compounds contain at least one long chain aryl-substituted aliphatic group, or, more specifically, an aralkyl group. In one specific embodiment the alkyl portion of the aralkyl group conta ns a total of 18 carbons. In other specific embodiments, the alkyl portion of the aralkyl groups contain ll, l6 or 22 carbons. More generally, the total of .r and y. which is three less than the total of carbons in the alkyl portion of the aralkyl, may range from 8 to 19. The compounds also contain at least one, or up to three, short chain alkyl groups which are bonded to the nitrogen atom. Whil methyl groups are preferred, the alkyl groups may also comprise ethyl, propyl, etho-, or propo-, or mixtures thereof.
In the formula, R, represents the aryl substituent. The carbon to which the aryl group is attached varies with the respective values of x and 3'. With unsaturated alkylene chains, such as oleyl, under most reaction conditions the double bond migrates up and down the chain (isomerization by hydrogen ion transfer) resulting in a mixture of isomeric products. In arylating oleyl, there is a tendency for the C -C and the C aryl isomers to predominate, but smaller mole percentages of other isomers, such as the C C C1 and C isomers are also produced. The mole percent of the C C isomers is usually quite small or even negligible. The relative proportions of the various isomers may vary depending on the arylation p.ocess. See J. Org. Chem. 30, 885-888 (1965). However, the total of x and y will remain constant for the particular unsaturated chain, viz. 15 for oleyl, B for t.nd.cyl, 19 for behenyl, etc. By arylation, oleic acid is converted to arylsubstituted stearic acid. Similarly palmitoleic, erucic, and IO-undecenoic acids can be converted to the c ..responding aryl-substituted carboxylic actds. Ordinary commercial grade oleic acid contains several percent of palmitoleic acid, and therefore a mixture of aryl-substituted stearic and palmitic acids is obtained by arylation.
Among the preferred aryl substitucnts are phenyl, hydoxphenyl, tolyl, anisyl, and naphthyl. More generally. the phenyl nucleus may be substituted with l or groups such as methyl, hydroxy, and mcthoxy. Other groups coming within this subclass are cresyl, resorcyl, xylyl. etc.
Since quaternaries are in the form of salts, the cationic portion of the molecule will be associa ed with an anionic portion. The particular anion is not cmical, and generally the anion may be any of those whicl are commonly pres eat in quaternazy compounds, such as monovalent or divalent anions. To provide for complete neutralrzattorg the formula indicated that n will be t for monot'tlent anions and 2 for divalent anions. Chloride salts of the quaternary are particularly desirable where the compounds are to be employed as cationic emulsifiers, but other salts can be used such as hydroxides, sulfates, nitrates, hydrochlorates, perchlorat s. hypochlorates, l'ormates, acetates, etc. Eor certain purposes the anion shouldbe seletted to provide water solubility or water dispersibtlrty.
As previously indicated, the aryl fatty acids such as arylstearic acid or arylp lmitic acid, may be prepared by the arylation of oluic acid or palmitolerc ac d. A catalyst is ordinarily required for such arylation, :5 rs well known in the art. For example, aluminum chloride may he employed as the catalyst. With this process, the fatty acid is preferably first converted to the cyano derivative, which is reacted with the arylating agent in the presence of aluminum chloride. The aryl cyanoaliphatic compound, by procedures well known in the art, can then be convened to the corresponding primary amine (by hydrogenatron). then to the tertiary amine (by alkylation with short chain alkyl groups or alkoxy groups), and finally quatemrz ed by a suitable quaternizing agent such as methyl chloride or dimethyl sulfate.
For direct arylation of fatty acids other catalysts are prefened, such as activated clays. or hydrofluoric actd. A process employing HF as the catalyst is described in Patent 2,275,3l2, while the use of an activated clay is dCSCl'lbui in Patent 3,074,983. An improved HF process is described and claimed in copending application, Scr. No. {51,02l, filed Apr. 26, 1965, entitled Process for Arylatrng Unsaturated Fatty Compounds." The ar'ylated fatty acid can then kt. used to prepare the quaternary compounds of the present invention. For example, phenylstearic acid (or other aryl-substituted long chain fatty acid) can be converted to the wrresponciiug rritriie, the nitriie converted to the primary amine, the primary lmln; convened to the tertiary amine, and the tertiary amine quatemize l. Alternatively, the prima y amine, such as phenyl tearyl amine, can be convened to the quaternary by reaction with methyl chloride. The primary amine can also be ethoxylated o propexylatcd by reaction with ethylene oxide or propylene oxide before being quaternized. It will be understood that suchproceduresarewellknownintheart.
This invention is further illustrated by the following specific examples. From what has been said above, it will be understood that the products of the examples are in the form of isomeric mixtures.
Example I Phenylstearic acid, hydroxyphenylstearic acid, and tolylstearic acid were prepared from commercial grade olcic acid which contained a few percent of palrnitoleic acid by a Fricdel-Cratts reaction using aluminum chloride as the catalyst and benzene. phenol. and toluene, respectively, as the arylating agents. Thereafter, phenylstearonitrile was preplred on a continuous nitrile unit over bauxite catalyst at 280-300 C. from I127 g. phenylstearic acid. A crude yield of 833.5 g. of phenylstearonitrile was obtained comprising a mixture of isomers. predominantly, the C. to C and the C isomers with lesser proportions of other isomers.
Similarly. hydroxyphenylstearonitrile was obtained in 62% crude yield lrom the crude acid, and tolylstearonitrile was obtained in 87% crude yield from distilled tolylstearic acid.
Example ll Phenylstearonitrile (591 g.) prepared as described in Example I was reduced in it l-liter, Parr autoclave over 26?. (by wt.) alcohol washed Raney nickel catalyst in the presence of ammonia I p.s.i kill-40' C.) and hydrogen (800 psi total pressure at I25 (I for 4 5 hour The product was obtained as a light amber oil, 582.3 (97% mary amine, 99.9%.
crude yield). Pure phenyloctadecylamlne was obtained in 67% yield upon distillation at Nil-19070.3 mm.
Similarly, hydroxyphenyloctadecylamine was preplr d in 91.5% crude yield and 8l% distilled yield from distilled hydroxypherrylstearonitrile prepared as described in Example I. Tolyloctadecylamine was prepared in 97% crude yield from the distilled nitrile.
Example lll Phenyloctadecylaminc (50 3.. 0.l mole) prepared as described in Example ll and NaHCO, (25 g., 0.31 mole) in ml. isopropanol were treated with methyl chloride at -80/70 p.s.i. in a 300 cc. stirred autoclave for 3.5-4 hours. Carbon dioxide was removed by periodic venting of the reaction vessel. The reaction mixture was then diluted to an approximately 50% solution of quaternary in isopropanol.
A nal v.ri.r.- Percent amine.HCl. nil.
The product was a mixture of isomers of N,N,N-trimethyl-N-phenyloctadecylammonium chloride.
Similarly. the hydroxyphenyland tolyloctadecyl trimethylammonium chlorides were prepared from the reactants of Example ll.
Hydroxyphenyl derivative: 78.5% quaternary;
aminc.HCl
quaternary. 43.6; free amine, nil:
nil: free amine, 0.9%.
Tolyloctudccyl derivative: 64.3% quaternary;
amirre.HCl 2.8: Free amine, nil.
Example [V Tolylstearonitrile (806.8 g., 2.27 moles) was reduced in a two-liter Parr autoclave over 2% (by wt.) alcohol Raney nickel cataly t in he presence of ammonia (360 psi/' C.) and hydrogen (800 p.s.i. total pressure/ 135-135 C.) in five hours. The crude amine was obtained as an amber oil, 800 g. (98% crude yield).
Analyris.-Neut. equivalent, 362 (Calcd. 359.6); Primary amine, 881%; Secondary amine, 0.31 meg./g.
Distillation at 20l-202' C./0.7-l.0 mm. alorded a 68.8% yicld of tolyloctaoecylamine.
Amlysi.r.Neut. equivalent, 362 (Cllcd. 359.6); Primary amine, 98.8 k.
Example V Xylylstearonitrile (579.! g., 1.56 moles) was reduced in a one-liter Magnedash autoclave over 2% (by wt.) alcohol washed Raney nickel catalyst in the presence of ammonia (480 psi/I35 C.) and hydrogen (800 p.s.i. total pressure/B5440 C.) in eight hours. The crude was obtained as an amber oil, 576.4 g. (99% crude yre Ana1 r.ri.r.-l\'eut. equiialent. 366.0 Calcd. 375.7); Primary amine, 100.5%; Secondary amine, 3.l4%.
Distillation at ISO-I96 C./0.070.l mm. aroma 75% yield of xylyloctadecylamine.
Analysin-Neut. equivalent, 374 (Calc'd 373.7); Pri- Example Vl amine,
5 6v 1 Example VII stirred, was chargedwith 25.0 (0.052 mole) NJ- A 500 ml. alas motor was elnr etl with 4: tr. (0.116 M W mole) of anisyloctadocylsmine, 19: 9232 mole) or 3 5?. u l 9 M M aodillm bicarbonate and 200 ml. or isopropanol. 'nie re- ""E C actor wit sealed and the reaction mixture heated to s 9 i ."E" 60-70 C. Gaseous methyl chloride was introduced at hour at 70785 50% 60-70 p.s.i.g. and the reaction mixture maintained at 60-; F mmurc was duima the '9 of 10' C./60-70 p.s.i.g. for six hours with periodic venting. d'mflhyl ""i"! P sodium chloridend om-um bicarbonate were After the addition was complete the reaction mixture was moved by finnflonmd unl-wpmpmohomfion N w refluxed at 105 C. for 1.5 hours. The resultant amber trimethyl N-anlayloctadccylammonlum chloride co nc ensalmon concentrated m i 60% acme M to about 40% avg j nary, being N-methyl-N,N-dl-(Beta-hydroxyethyD-N- Anaheim-Percent quaternary, 41.1; Free amine, trace; I tolylocmqecylammomum methyl sulfate Amineficl. 014%. Apalyrm-Percent quaternary, 59.4; Free amine, 4.1%;
Bump]: VH1 1 Amlnc sulfate, 2.2%. I
A 500 ml. glass reactor was charged with is g. (0.032 I Bump xm 1 m f naphmylocmecylamim. 10.1 2 mole) f A 500 ml. glass reactor was charged with 12.7 g. (0.027 sodium bicarbonate and 50 1 of isopropanoL h moie) of N,N-d l-(Beta-hydroxyethyl)tolyloctadecylatmne actor was sealed and the reaction mixture hand to 0 and 41.6 g. f lsopropanol. The reactor was sealed and 70 C methyl chloride was immduccd at 040 heated to 80 C. Gaseous methyl chloride was introduced and a reaction mixture maintained at 70- to about 50 p.si.g.an d the reaction mixture maintained at C./60-7O p.s.i.g. for 4.5 hours with periodic venting. 9 (3/4540 9 -8 houm'nlfi p p p Sodium chloride and excess sodium bicarbonate were re- Will-Ion of the 'y had followlnl 9 moved by filtration and the isopropanol solution of N,N,N- S quakmary 29-4; aminei L tritr-thyl N-naphthyloctadecylammonium chloride oon- Example XIV 'f y- 1W, l4; F m similarly, the ethoxylation product of 5 moles of eth- Aammc-flcli ylene oxide with tolyloctadecylamine was quatcrnized Example IX 30 using methyl chloride at 70-80 c./4s s0 p.s.i.g. to yield an isopropanol solution of the quaternary ammonium salt fig g gg having the following a. alysisz Percent quaternary, 28.0; m es) ot wrdium bicarbonate and $00 mlrof isopropanol. amine AmmeHcl' The reactor was sealed and the temperature of the reac- Example XV tion mixture was raised to 65-75 C. Gaseous methyl I chloride was introduced at 70-75 p.s.i.g. and the reaction z 2: i r of. 15 mm; of at 6545, 0/7045 six. for {our y ene on e Wt o y oc auecy amine was quatermzed. mauimm l The resulting quaternary ammonlum salt had the followteen hours with penodlc venting. Sodium chloride and exin anal Percent uamn 2] Fr cess sodium bicarbonate were removed by filtration and 40 q the isopropanol solution of N.N,N-trimethyl-N-xylylocta- Exam 1: x decylammonium chloride concentrated. p
Analynlr.Pcroent uaternary, 83.7; Free amine, A 500 ml. glass r tor was charged with 48.1 (0.1 032%;A mm mole) of di-(pbenylundecyhamine. 9.24 g. (0.11 mole) E h x of sodium bicarbomte and 200 ml. of isopropanol. Rte 9 reactor was sealed and 1b.; temperature raised to 70 C. A 500 ml. glass reactor was charged with 47.2 g. (0.117 Gaseous methyl chloride was introduced at 70 p.s.i. and mole) of phenyldooosanylamine, 22.0 g. (0.247 mole) of the reaction mixture maintained at 60-70 C./60-70 sodium bicarbonate and 60.0 ml. of isopropanol. The rep.s.i.g. for four hours with periodic venting. Sodium chloactor was sealed and heated to 70-75 C. Gaseous methyl ride and excess sodium bicarbonate were removed by lilchloride was introduced to 60-70 p.s.i.g. and the reaction tration and the N,N-dimethyl-N,N-di(phenylundecyl)ammixture maintained at 70-75 C./60-70 psig. for {our monium chloride was obtained as an isopropanol solution boots with periodic venting. Sodium chloride and excess having the following analysis: Percent quaternary, 33.3; sodium bicarbonate were removed by filtration and the Free amine, 0.34%; Amine.HCl, 0.05%. isopropanoi solution of N.N,N-trimethyl-N-phenyldoco- Exam 1: XVI xanylammonlum chloride was obtained as a yellow liquid p ving the following analysis: Percent quaternary, 48.7; A 500 glass W85 Charged with $0 8- [u mint, il; AmineHCL il, mole) of di-(phenyldocosyl)amine, 5.85 g. (0.07 mole) of sodium bicarbonate and 200 ml. of isopro anol. The o- Example x1 actor was sealed and the temperature raised to 70' C. A 500 ml. glass reactor was charged with 50.0 g. (0.203 Gaseous methyl chloride was introduced at 70 p.s.i.g. and mole) of phenylundecylamine, 37.9 g. (0.45 mole) of the reaction mixture maintained at 60-7 C./60-70 sodium bicarbonate and 50 g. oi isopropanol. The reactor p.s.i.g. for four hours with periodic venting. Sodium chlowas sealed and heated to 70-75 C. Gaseous methyl chloride and excess sodium bicarbonate were removed by ride was introduced to 70 p.s.l.g. and the reaction mixture filtration and the N,N dimcthyl-N.N 1t(phenyldocosyl) maintained at 70-75 C./60-70 p.s.l.g. for 2.5 hours with ammonium chloride was obtained as an isopropanol soluperiodic venting. Sodium chloride and excess sodium bi' lion having the following analysis: Percent quaternary,
carbonate were removed by filtration and the isopropanol 26.4; Free amine, 0.2%; AmineHCl. 2.99%. solution 0! N.N.N-trimethyl-N-phenylundecylammonium Exam e vm chloride was obtained as a clear colorless liquid having p the following analysis: Percent quaternary, 57.0; Free A tWOJiler fluloclfl" will! 445 8- amine, nil, AmineJ-lCl, nil. (0.614 mole) of di-(lolyloctadccyl)amine, 60.0 g (0.674 E I. X" mole) of sodium bicarbonate. and 500 ml. of isopropanol. The reactor was scaled and thc tennt-rature raised to A 200 ml. 3-neck round bottom flask, equlpped with an C. Gaseous methyl chloride was i' troduccJ at 75 p.s.i.g. addition funnel, thermometer, reflux condenser and msg- 75 and the reaction mixture maintained at 70-80 C./ 70-80 7 p.s.i.g. for six hours with periodic venting. Sodium chlw ride and excess sodium bicarbonate were removed by &1- tration and the iaopropanol solutionot quaternary was concentrated under reduced pressure. The resultant prodquaternary, 88.9;
: Example XX A 500 ml, glass reactor was charged with 40.8 g. (0.119 mole) of N,N di(Beta hydroxyethyl)phenylundecylamine, 2.5 g. (5% by wt.) of sodium bicarbonate and about 100 ml. of isopropanol. The reactor was sealed and the mixture heated to 70' C. Gaseous methyl chloride was introduced to 75 p.s.i.g. and the reaction mixture maintaineo at 75-80' C./70-75 p.s.i.g. for five hours with periodic venting. The sodium chloride and excess sodium bicarbonate was removed by filtration yielding an isopropanol solution of the quaternary ammonium salt.
Analytic-Percent quaternary, 33.1; Free amine,
Example XXI A 500 ml. glass reactor was charged with 37.1 g. (0.072 mole) of N.N-di(Bcta-hydroxyethyl)phcnvldocosylamine, 5.0 g. (0.059 mole) of sodium bicarbonate and about 100 ml. of isopropanol. The reactor was scaled and the mixture heated to 75' C. Gaseous methyl chloride was introduced at 0 p.s.i.g. and the reaction mixture maintained at 75-80' C./70-75 p.s.i.g. for five hours with periodic venting. The sodium chloride and excess sodium bicarbonate were removed by filtration, yielding an isopropaaol solution of the quaternary ammonium salt.
Andysta-Percent quaternary, 31.2; Free amine, 1.5%;Amine-HCLnil.
Example XXII A twotrter Parr autoclave was charged with 761.0 g. (2 6 moles) of toty1tallowamine," 512.9 g. (5.7 moles) and 150 ml. of isopropanol. The reactor was sealed and the mixture heated to 65-75 C. Gaseous methyl chloride I introduced at 70-75 p.s.i.g. and the reaction mixture maintained at 65-75 C./ 70-75 p.s.i.g. for about eleven hours. Socium chloride and excess sodium bicarbonate were removed by filtration with the aid of additional isopropanol. The isopropanol solution containing the N,N.N- trimethyl-N-tolyltallow" ammonium chloride was then concentrated to the maximum concentration at which it still remained AnalysiL-Petoent quaternary, 73.8; Free amine, 0.25%;Amioe-HC1, nil.
Example XXlll A 500 ml. glass reactor was charged with 69.2 g. (0.1 mole) of di-(xylyloctadecyl)amine, 10.9 g. (0.13 mole) of sodium bicarbonate and 95 ml. of isopropanol. The reactor was sealed and the temperature raised to 80' C. Gaseous methyl chloride was introduced at 85 p.s.l.g. and the reaction mixture maintained at 80-85 C./85-90 p.s.i.g. for three hours with periodic venting. Sodium chloride and excess sodium bicarbonate were removed by filtration and the N,N-dime hyl-N.N-dl-(xylyloctndecyll ammonium chloride was obtained as an isupropanol solution having the following analysis Percent quaternary.
, 40.5.; Free amine; 1.24%; Amine-HG], (Ll-7%.
Example XXIV A 500 ml. glass reactor was charged with 34.9 g. (0.063 mole) of N,N-di.- (alpha-methyl Beta hydroxyethyl)- phenylbehenylamine, 2.0 g. of sodium bicarbonate and 35 g. of iaopropnnol. The reactor was sealed and the mixture heated to 75" C. Gaseous methyl chloride was introduced to 75 p.s.i.g. and the reaction mixture maintained at .5-80' C./701-75 p.s.i.g. for ten hours with periodic venting. Sodium chloride and excess sodium bicarbonate was removed byfiltration, yielding an isopropanol solution of the quaternary ammonium salt.
Analyrrr.-Percent quaternary, 34.2; Free amine, l4.l%;- Amine-HCl, nil.
We claim:
l. Quaternary ammonium compounds represented by the formula whe'ein R, is selected from the group consisting of alkyl radicals having from 1 to 3 carbon atoms, and
R, is selected from the group consisting of alkyl radicals having from 1 to 3 carbon atoms, (CH,CH,0),H, and
CIIa cmnomr and R, is selected from the group consisting of alkyl radicals having from I to carbon atoms, and
(Illa (Cu,cuo .u
wherein p and w are integers from 1 to 40 and the sum of p and w is less than R. is selected from phenyl, naphthyl, and phenyl substituted with from 1 to 2 groups selected from methyl. hydrosy, and methoxy; r and y areintegersfromotr l9andthesumotxandyisan integertromS to I9;Aisananion;andnisaninteger from 1 to2,saidcompoundscomprisingisomericmixtures with respect to the position of R to the alkyl chain.
2. The compounds of claim I whe'ein Il It, and R, are each methyl.
3. The compounds of claim I wherein R is methyl. R. is -(CH;CH,O),H, and R, is -(CH;CH.O).H wherein pandwareintegersfrom 1 toZOandthesumofpand w is less than 30.
4. The compounds of claim 1 wherein R is methyl, R3 is wherein p and w are integers from I to 20 and the sum of p and w is less than 30.
5. The compounds of claim I wherein R, is
6. The compounds of claim 5 wherein R, and R, are each methyl.
7. The compounds of claim 1 wherein R is phenyl.
8. The compounds of claim I uher r'n R. is xylyl 9. The compounds of claim 1 herein R. i\ hytlmnphenyl.
10. The compounds 01 claim I wherein A is selected 9 from the group consisting of Cl--, 50.", OH, NO; and Br.
11. I'hecompouadsolclaim l whereinxisn integer fromOtollmdyisanintegerfrom-ttolSandthe tumofxmdyialS.
1:. The compounds cl claim 11 wherein 1m, pbenyl, 5
and A is selected from the group consisting of Cl, S0,, OH-, NO; and Br.
13. The compounds of claim 12 wherein R1. R and R, are each methyl and A is Cl".
14. The compounds of claim ll when-in R is hydroxyphenyl, and A is selected from the group consisting of C1, 50,-, OH", NO; and Br'.
15. The compounds of claim 14 wherein R R3 and R, are each methyl, and R is hydxoxyphenyl.
10 CHARLES B. PARKER, Primary Examiner. S. T. LAWRENCE, III, Assistant Examiner.
US. Cl. X.R. l5 252-8.6, 8.8, 311.5; 260-413, 465, 570.8, 999
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625891A (en) * 1968-04-18 1971-12-07 Armour Ind Chem Co Wash cycle fabric softeners and method of preparing and using same
US3807983A (en) * 1971-04-02 1974-04-30 Akzona Inc Quaternary ammonium aquatic herbicides
US4485048A (en) * 1982-08-09 1984-11-27 Akzona Incorporated Ethoxylated quaternary benzyl compounds
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111965B1 (en) * 1982-12-23 1989-07-26 THE PROCTER & GAMBLE COMPANY Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
CN115124428A (en) * 2022-07-20 2022-09-30 山东鑫泰水处理技术股份有限公司 Composite bactericide containing dialkyl methyl benzyl quaternary ammonium salt and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH214904A (en) * 1941-12-03 1941-05-31 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
CA558966A (en) * 1958-06-17 E. Chiddix Max Quaternary ammonium salts
US3026169A (en) * 1960-03-23 1962-03-20 American Enka Corp Manufacture of viscose rayon

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH217133A (en) * 1938-11-25 1941-09-30 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
CH217132A (en) * 1938-11-25 1941-09-30 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
CH217137A (en) * 1938-11-25 1941-09-30 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
CH217136A (en) * 1938-11-25 1941-09-30 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
US2520275A (en) * 1946-12-28 1950-08-29 Onyx Oil & Chemical Company Aromatic diquaternary ammonium compounds
US2519999A (en) * 1949-06-29 1950-08-22 Rohm & Haas Dialkoxyxylylene-bisquaternary salts
GB789794A (en) * 1955-10-10 1958-01-29 Continental Oil Co Improvements in or relating to preparation of quaternary ammonium halides
US3037910A (en) * 1958-04-18 1962-06-05 Burroughs Wellcome Co Process for treatment of hypertension
US3050521A (en) * 1959-04-03 1962-08-21 Rohm & Haas N-alkylbenzyl-n-dodecenyl quaternary ammonium salts
US3205169A (en) * 1961-07-14 1965-09-07 Nalco Chemical Co Compositions for breaking emulsions or inhibiting formation thereof and processes utilizing same
US3283005A (en) * 1963-04-29 1966-11-01 Armour & Co p-xylylene bis quaternary ammonium compounds
US3311659A (en) * 1963-11-21 1967-03-28 Rayette Faberge Process for preparing higher fatty alkyl diloweralkyl benzyl ammonium halides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA558966A (en) * 1958-06-17 E. Chiddix Max Quaternary ammonium salts
CH214904A (en) * 1941-12-03 1941-05-31 Geigy Ag J R Process for the production of a water-soluble, higher molecular weight, α-substituted benzylamine derivative.
US3026169A (en) * 1960-03-23 1962-03-20 American Enka Corp Manufacture of viscose rayon

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625891A (en) * 1968-04-18 1971-12-07 Armour Ind Chem Co Wash cycle fabric softeners and method of preparing and using same
US3807983A (en) * 1971-04-02 1974-04-30 Akzona Inc Quaternary ammonium aquatic herbicides
US4485048A (en) * 1982-08-09 1984-11-27 Akzona Incorporated Ethoxylated quaternary benzyl compounds
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions

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