Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2002-05-06
2004-04-27
Davis, Brian (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S292000, C564S293000, C564S294000, C514S642000, C254S390000
Reexamination Certificate
active
06727387
ABSTRACT:
BACKGROUND
This invention relates to novel quaternary ammonium salts useful in several applications, including phase-transfer catalysis, corrosion inhibition, inhibition of microbial growth, and development of antistatic agents.
Quaternary ammonium salts in which one of the groups attached to nitrogen is a tertiary alkyl group are known in the literature only for relatively small alkyl groups such as t-butyl or t-octyl. The quaternary salt formed from 1,1,3,3-tetramethylbutanamine is described in Journal of Organic Chemistry, vol. 40, pp. 531-2 (1975).
The problem addressed by this invention is to provide quaternary ammonium salts containing large branched alkyl groups, and methods for use of these salts as biocides, corrosion inhibitors and phase transfer catalysts.
STATEMENT OF INVENTION
This invention is directed to a compound of formula I:
wherein R
1
is C
1
-C
18
alkyl, C
1
-C
18
polyether alkyl, C
1
-C
18
alkenyl, C
1
-C
18
alkynyl, or C
7
-C
12
aralkyl; R
2
is C
1
-C
4
alkyl; R
3
is methyl or ethyl; R
4
, R
5
and R
6
are independently C
1
-C
21
alkyl, substituted C
1
-C
21
alkyl, C
1
-C
21
alkenyl or substituted C
1
-C
21
alkenyl; X
−n
is halide, hydroxide, tetrafluoroborate, phosphate or an organic anion having from 1 to 20 carbon atoms; and n is an integer from 1 to 5;
wherein at least one of R
4
, R
5
and R
6
is branched;
and wherein R
4
, R
5
and R
6
contain collectively at least nine carbon atoms.
DETAILED DESCRIPTION
An “alkyl” group is a saturated hydrocarbyl group having from one to twenty-one carbon atoms in a linear, branched or cyclic arrangement. A “polyether alkyl” group is an alkyl group comprising an oligomer of an alkyl epoxide, e.g., ethylene oxide or propylene oxide, where the oligomer optionally is end-capped with an alkyl or alkenyl group. An “alkenyl” group is an “alkyl” group in which at least one carbon-carbon single bond has been replaced with a double bond. Substituted alkyl and alkenyl groups are substituted with one or more hydroxy; halo; cyano; alkyl; alkoxy; carbalkoxy; carboxy; amino; alkylamino; or nitro groups, with substitution by one or more halo groups being possible on alkyl or alkoxy groups. An “alkynyl” group is an “alkyl” group in which at least one carbon-carbon single bond has been replaced with a triple bond. Preferably, alkyl, alkenyl and alkynyl groups are acyclic and unsubstituted. An “aryl” group is a substituent derived from an aromatic hydrocarbon compound. An aryl group has a total of from six to twenty ring atoms, and has one or more rings which are separate or fused. Substitution on aryl groups of one or more hydroxy; halo; cyano; alkoxy; alkyl; alkenyl; carbalkoxy; carboxy; or nitro groups is permitted, with substitution by one or more halo groups being possible on alkyl, alkenyl or alkoxy groups. An “aralkyl” group is an “alkyl” group substituted by an “aryl” group.
X
−n
is halide, hydroxide, tetrafluoroborate, phosphate, or an organic anion having from 1 to 20 carbon atoms. Organic anions are those containing carbon, with the exception of carbonate, bicarbonate, cyanide, cyanate and thiocyanate, preferably those containing carbon and hydrogen, including, for example, phosphonates, alkoxides, carboxylates, hydrocarbyl sulfates and sulfonates, and chelating carboxylic acids. X
−n
is the conjugate base of an acid H
m
X, having m acidic hydrogen atoms, where m≧n. Preferably, m is no greater than 10. Preferably, the pKa for removal of the most acidic hydrogen atom in the acid H
m
X is no greater than 17; more preferably the pKa for removal of the most acidic hydrogen atom in H
m
X is no greater than 9. Preferably, X
−n
is selected from the group consisting of halide; hydroxide; alkoxide; alkyl, aryl, aralkyl, alkenyl, and alkylamino carboxylates; alkyl and aryl sulfates; alkyl and aryl sulfonates; phosphates; phosphonates; alkyl, aryl, aralkyl, alkenyl, and alkylamino thiocarboxylates; chelating aliphatic carboxylic acids; and tetrafluoroborate. More preferably, X
−n
is selected from the group consisting of halide, alkyl sulfate, aliphatic phosphonate and chelating aliphatic carboxylic acids. Particularly preferred aliphatic phosphonates are the anions derived from aminotrimethylenephosphonic acid (ATMP), diethylenetriamine pentamethylenephosphonic acid (DETA), bis-hexamethylenetriamine-pentaphosphonic acid (BHMT) and hydroxyethylidene diphosphonic acid (HEDP). Particularly preferred chelating carboxylic acids include ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid.
For multivalent acids H
m
X, e.g., the aforementioned phosphonates, the conjugate base X
−n
can have n equal to 1, 2, 3, 4 or 5, up to the number of acidic hydrogen atoms m in the acid H
m
X. When the conjugate base is formed by neutralization of the acid H
m
X, the number of equivalents of base used to form the conjugate base will determine the value of n. To maintain charge balance, the number of quaternary ammonium ions in the compound will be equal to n. In a preferred embodiment of the invention, n is 1, i.e., X
−n
is X
−
. Preferably, X
−
is halide or alkyl sulfate, most preferably iodide or bromide.
Preferably, the quaternary salts of formula I are prepared from tertiary-alkyl primary or secondary amines. Preferably, R
4
, R
5
and R
6
in formula I all are alkyl groups. Preferably, formula I represents a mixture of compounds among which there are differences in the alkyl groups R
4
, R
5
and R
6
. Particularly preferred mixtures of tertiary-alkyl primary or secondary amines are Primene® BC-9 amine, Primene® 81-R amine, Primene® JM-T amine, or Primene® LA-2 amine, all of which are available from Rohm and Haas Company, Philadelphia, Pa. In each of the first three of these, which are tertiary-alkyl primary amines, the R
4
R
5
R
6
C— unit is a mixture of C
9
-C
10
, C
10
-C
15
, C
16
-C
22
hydrocarbons, respectively. Primene® LA-2 amine is derived from Primene® 81-R amine by alkylation of the amine with a single n-C
12
alkyl group. In each of the Primene® amines, at least one of the R
4
, R
5
and R
6
groups is branched. Preferably, R
1
is a C
1
-C
12
alkyl group.
In one embodiment of the invention, R
4
, R
5
and R
6
all are alkyl. Preferably, R
2
and R
3
are methyl and X
−
is halide, phosphonate or a chelating carboxylic acid. More preferably, R
1
, R
2
and R
3
all are methyl and X
−
is bromide or iodide. Preferably, R
4
, R
5
and R
6
contain collectively at least ten carbon atoms. More preferably, R
4
, R
5
and R
6
contain collectively at least twelve carbon atoms.
The present invention is further directed to a method for inhibiting the growth of microorganisms, including, but not limited to bacteria, fungi, algae and yeasts, by introducing a microbicidally effective amount of the compound to a locus that is subject to microbial attack. The amount of compound to be used depends on the application. Typically the amount of compound of Formula I incorporated into a locus is from 0.1 to 10,000 ppm, preferably from 0.5 to 5,000 ppm and more preferably from 1 to 1000 ppm.
Suitable loci include, for example: cooling towers; air washers; boilers; mineral slurries; wastewater treatment; ornamental fountains; marine structures, such as boats, ships, oil platforms, piers, pilings, docks, elastomeric rubbers and fish nets; marine antifouling coatings, such as marine paints and varnishes; reverse osmosis filtration; ultrafiltration; ballast water; evaporative condensers; heat exchangers; pulp and paper processing fluids; plastics; emulsions and dispersions; paints; latexes; coatings, such as varnishes; construction products, such as mastics, caulks, and sealants; construction adhesives, such as ceramic adhesives, carpet backing adhesives, and laminating adhesives; industrial or consumer adhesives; photographic chemicals; printing fluids; household products, such as bathroom disinfectants or sanitizers; cosmetics and toiletries; shampoos; soaps; detergents; industrial disinfectants or sanitizers, such as cold sterilants, hard surface di
Banavali Rajiv Monohar
Mukkamala Ravindranath
Crimaldi Kenneth
Davis Brian
Rohm and Haas Company
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