Antifouling quaternary halide salts containing a triorganotin ether moiety

Disclosed are the usage, preparation, and evaluation of marine antifouling quaternary halide salts containing a cation portion which includes a trialkyltin ether moiety linked to a carbon atom at least two carbon atoms removed from the quaternized nitrogen atom. Taught as providing exceptional marine fouling inhibition are the quaternary salts of benzyl bromide and tertiary amines containing a tributylstannyl ether moiety at least two carbon atoms removed from the amino nitrogen atom with illustrated specific examples including the quaternary salts of benzyl bromide and 2-dimethylamino-2-methyl-1-propyl tributylstannyl ether, benzyl bromide and 1-dimethylamino-2-propyl tributylstannyl ether, benzyl bromide and 2-[N-pyrrolidinyl]ethyl tributylstannyl ether, and benzyl bromide and 2-diisopropylaminoethyl tributylstannyl ether. For antifouling purposes the quaternary salt is blended or dissolved in a resinous polymer component of a marine paint composition applied to an article's surface subsequently to be immersed in ocean water.

DISCLOSURE OF THE INVENTION 
This invention relates to the usage of, preparation of, and evaluation of 
marine antifoulants which include an organotin moiety. More particularly 
it concerns significantly useful particular marine antifouling agents 
which are quaternary halide salts having a cation portion characterized by 
a trialkyl tin moiety (especially tributyl tin moiety) linked by an ether 
linkage to a carbon atom at least two carbon atoms removed from a 
quaternized nitrogen atom of the cation. 
BACKGROUND 
Organotin compounds, especially the trialkyl and triaryltin compounds have 
been known to possess biocidal activity at least since about the 1940's 
and as early as 1958 there issued a German Pat. No. 1,042,975 concerning 
an organotin (triphenyltin chloride) contained in antifouling paint. Since 
that time knowledge about various organotins and varied organotin 
compounds for marine antifouling purposes has increased. Among the more 
prevalently advocated organotins for marine purposes are 
bis(tri-n-butyltin) oxide, bis(tri-n-butyltin) sulfide, and tri-n-butyltin 
fluoride with the following including illustrative teachings of them: for 
the first mentioned - Netherlands application Nos. 6,480,317 and 
6,511,311, British Pat. No. 1,001,639 (1960), and U.S. Pat. No. 3,227,563; 
for the second mentioned - British Pat. No. 917,629 (1963) and U.S. Pat. 
No. 3,234,032; and for the last mentioned - German Offen. No. 1,941,849 
(1970) and So. African Pat. No. 67 04,668. Biocidally active quaternary 
ammonium complexes are taught in U.S. Pat. No. 3,070,615; germicidal and 
fungicidal quaternary ammonium organotin halides are disclosed in U.S. 
Pat. No. 3,346,607; Japanese Pat. No. 10,102 (1966) teaches quaternary 
organotin compounds to inhibit growth of various organisms; quaternary 
ammonium-tin halide polymers are taught in U.S. Pat. No. 3,242,105; and 
U.S. Pat. Nos. 3,539,605 and 3,397,215 include teachings of preparing 
quaternary ammonium compounds whose anionic portion thereof may include 
any of a number of various metals. East German Pat. No. 63,490 and 
Japanese Pat. No. 6172 (1966) include teachings of organotin ether 
compounds containing a tertiary amine group. 
SUMMARY STATEMENT OF THE INVENTION 
In the present invention one prepares an antifouling quaternary halide salt 
containing a triorganotin ether moiety by a procedure which involves 
preparation of a triorganostannyl ether of a tertiary amine and then 
preparation of the quaternary salt from this ether. For preparation of the 
ether one takes an amino alcohol or phenol having a tertiary amino 
nitrogen spaced at least two carbon atoms from its hydroxyl functional 
group and a bis(triorganotin) oxide, preferably bis(tributyltin) oxide, in 
an aromatic hydrocarbon solvent, preferably benzene, and refluxes this 
mixture with water which forms during the reaction being removed so as to 
expedite completion of the reaction. The prepared triorganostannyl ether 
of the tertiary amine then is quaternized by reacting it with an aryl 
halide, preferably benzyl bromide, or C.sub.8 -C.sub.24 aliphatic 
hydrocarbon halide for a time requisite to provide quaternization. Heat is 
used to effect the quaternization and conveniently applied by refluxing an 
aromatic hydrocarbon liquid, preferably xylene, containing the reactants 
until the desired quaternary salt is produced. 
The quaternary salt of the invention is from quaternization of the aryl 
halide or the C.sub.8 -C.sub.24 aliphatic halide and a tertiary amine 
containing a triorganostannyl ether moiety whose etheral oxygen atom links 
a trioganotin radical to a carbon atom at least two carbon atoms removed 
from a tertiary amino nitrogen atom of the tertiary amine. Preferred is a 
quaternary salt of benzyl bromide or n-dodecyl bromide and a tertiary 
amine containing a tributylstannyl ether moiety whose etheral oxygen atom 
links a tributyltin radical to a carbon atom at least two carbon atoms 
removed from a tertiary amino nitrogen atom of the tertiary amine. 
Especially preferred is the quaternary salt of benzyl bromide and the 
tertiary amine containing the tributylstannyl ether moiety. 
Submerged portions of ships, boats, piers, buoys, water-intake pipes, and 
like articles in ocean waters as immersion time passes invariably become 
fouled by marine organisms to the detriment of the article's use. The 
quaternary salts of the invention possess useful biocidal properties, or 
at least significantly inhibit growth of marine organisms, and are 
especially useful as antifouling additives in compositions for coating 
articles used in water. As inhibitors of marine fouling, the invention's 
quaternary salts are quite exceptional. In evaluations to date each 
prepared quaternary salt of the invention has shown utility as a marine 
antifoulant. In comparison to tributyltin oxide as a standard for 
antifouling activity, preferred quaternary salts of benzyl bromide and the 
tertiary amine containing the tributylstannyl ether moiety have equaled or 
exceeded the standard's antifouling properties and our especially 
preferred quaternary salts have exhibited significantly superior 
inhibiting marine antifouling properties. For use as a marine antifoulant, 
the quaternary salt is included in a component of a coating composition 
which is applied to adhere to the article's surfaces subsequently 
subjected to ocean water immersion. Conventionally such coating 
compositions are marine paint compositions including a synthetic resinous 
polymer or the like as a principal constituent. The invention's quaternary 
salts mix readily with and/or dissolve in conventional marine paints 
containing synthetic resin polymers. The compatibility of blending and/or 
solubilization with the resinous polymer constituent arises from the 
highly organic nature of the quaternary salt. Except for its tin atom, 
divalent etheral oxygen atom, and quaternized nitrogen atom the quaternary 
salt is predominantly organic and composed of carbon and hydrogen atoms 
which largely determine oleophilic and hydrophylic solubilities and also 
blending compatibility with synthetic resin polymers. This highly organic 
nature of the quaternary salt gives the quaternary salt limited water 
solubility to provide effective antifouling resistance over lengthy 
periods of time as it slowly releases from a marine paint containing it. 
DETAILED STATEMENT OF THE INVENTION 
Included in the invention is a quaternary salt of an aryl halide or a 
C.sub.8 -C.sub.24 aliphatic hydrocarbon halide and a tertiary amine 
containing a triorganostannyl ether moiety whose etheral oxygen atom links 
a triorganotin radical to a carbon atom at least two carbon atoms removed 
from a tertiary amino nitrogen atom of the tertiary amine and which 
quaternary salt is of the formula 
##STR1## 
wherein X is Cl, Br, or I, and preferably is Br, each R is an alkyl 
radical of up to 12 carbon atoms with the sum total of the carbon atoms in 
the three not exceeding 24 and preferably totaling 12 carbon atoms and 
with no more than one of the three containing more than 4 C atoms and with 
each of the three not necessarily the same, but preferably the same R and 
preferably each being a butyl radical, 
R' is an aryl hydrocarbon radical, preferably the benzyl radical, or a 
C.sub.8 -C.sub.24 alkyl radical, preferably a straight chain alkyl 
radical, and especially preferably being C.sub.12, and 
Q is a quaternized moiety of a tertiary amine moiety selected from the 
group consisting of an aliphatic tertiary amine moiety of the structure 
##STR2## 
wherein n is a whole number integer of 2-5 and preferably is 2, and a 
methyl radical may replace a --H for up to and including two of the --H in 
the --(CH.sub.2).sub.n -- chain, and R" and R'" are C.sub.1 -C.sub.10 
alkyl radicals not necessarily the same, but preferably the same and 
especially preferably both methyl or ethyl radicals, 
a heterocyclic tertiary amine moiety of the structure 
##STR3## 
wherein 
##STR4## 
represents a pyrrolindinyl, morphilino, or piperazino ring, and n is a 
whole number integer of 2-5 and preferably is 2, 
a heterocyclic tertiary amine moiety with aromaticity of the structure 
##STR5## 
wherein n is a whole number integer of 2-5 and preferably is 2, and 
a tertiary amine structural moiety including an aromatic ring of the 
structure 
##STR6## 
wherein Z is the same or different and at least one Z is --NR.sub.2 or 
--(CH.sub.2).sub.n NR.sub.2 and any remaining Z is H, with R a C.sub.1 
-C.sub.24 alkyl radical, preferably methyl or ethyl, and n is a whole 
number integer of 1-5 and preferably is 1. 
To prepare a quaternary salt of the invention, one can initiate its 
preparation from a known starting material of an amino alcohol wherein the 
nitrogen is a tertiary amino nitrogen and is spaced at least two carbon 
atoms removed from a hydroxyl group. A large number organic compounds 
containing both a tertiary amine moiety and an hydroxyl moiety in their 
structure are known in the art with a number commercially available. In 
addition, the art makes available a variety of procedures for preparing 
additional hydroxyl-containing tertiary amine organic compounds, including 
for example, the methods of Blicke, "Organic Reactions", 1, 330(1942), and 
Cavitt, "J. Org. Chem." 27, 1211(1962). Illustrative but not inclusive of 
all useful starting reactants, are the following hydroxyl-containing 
tertiary amines; 3-diethylaminophenol; 2-dimethylaminomethyl phenol; 
2-diethylaminomethyl phenol; ortho-, meta, and para-dimethylaminophenol; 
ortho-, meta, and para-dimethylaminothiophenol; ortho-, meta-, and 
parahydroxy-N,N-dimethyl aniline; 2-(.beta.-hydroxyethyl) pyridine; 
2,4,6-tris(dimethylaminoethyl)phenol; 2-diethylaminoethanol; 
2-diethylaminopropanol; 2-diisopropylaminoethanol; 2-dibutylaminoethanol; 
2-dimethylaminoethanol; 3-dimethylaminopropanol; 
3-dimethylaminoisopropanol; 2-dimethylamino-2-methyl-1-propanol; 
2-diethyhexylaminoethanol; N(.beta. -hydroxyethyl)morpholine; 
N(.gamma.-hydroxypropyl)morpholine; 2,4-pyridinediol; 2,6-pyridinediol; 
N-(.beta.-hydroxyethyl)pyrrolidine; N-(.gamma.-hydroxylpropyl)pyrrolidine; 
N(.beta.-hydroxyethyl)piperazine; N-(.gamma.-hydroxylpropyl)piperazine; 
etc. 
With a starting material of an amino alcohol having its amino nitrogen 
spaced at least two carbon atoms removed from its hydroxyl group, one 
reacts therewith bis(tributyltin) oxide to prepare its corresponding 
organotin ether compound. A useful general procedure for this reaction is 
that in East German Pat. No. 63,490 (1968) for the preparation of the 
tributyltin ether of 1-phenyl-2-(diethylamino)ethanol and in Japanese Pat. 
No. 6172 (1966) for the conversion of a number of amino alcohols into 
their organotin ether derivatives. In general one reacts about one mole of 
bis(tributyltin) oxide (TBTO) for each two moles of the amino alcohol or 
phenol, when the amino alcohol or phenol contains a single hydroxyl group 
for conversion to its monoether derivative. Where the amino alcohol or 
phenol contains a multiplicity of hydroxyl groups for reaction with 
tributyltin oxide to form an organotin polyether derivative, the molar 
ratio of TBTO to such tertiary amines containing a plurality of hydroxyl 
groups desirably is about 1 mole of TBTO for each 2 molar equivalents of 
hydroxyl groups to be etherified. Of course larger and smaller amounts of 
TBTO are useful, but incomplete formation of the ether derivative results 
with the use of smaller TBTO ratios and excess TBTO found with the product 
when employing larger TBTO ratios. Conveniently the reaction is carried 
forth in an aromatic hydrocarbon solvent, e.g. benzene, for the amino 
alcohol or phenol with refluxing of the solvent-reactant mixture and with 
the water formed by the reaction being azeotropically distilled therefrom. 
In some instances, it is possible to merely carefully heat while mixing 
the reactants without a solvent present, and to distill the water formed 
therefrom to provide the tributyltin ether derivative of the 
hydroxyl-containing tertiary amine starting material. Time for reaction 
can vary, but usually is between 10 and 116 hours. A convenient means to 
follow the extent of the reaction is to measure the amount of formed water 
removed from the reaction mixture. When solvent is used, it may be 
distilled or fractionated from the formed product. Generally a 
fractionation under reduced pressure of the formed product provides a 
product of adequate purity for characterization and confirmation of its 
structure and for utility in preparation of a quaternary salt of the 
invention. 
To prepare a quaternary salt of the invention, the tributyl tin ether 
derivative of the tertiary amine starting material is reacted, generally 
in about the equal molar amounts, with an aryl halide, e.g. benzyl 
bromide, or a long-chain (C.sub.8 -C.sub.24) aliphatic hydrocarbon halide, 
e.g. n-dodecyl bromide. Larger and smaller amounts of halide reactant can 
be used, but with incomplete quaternization of the tributyl tin ether 
derivative upon using the smaller amounts and with unreacted halide 
compound found with the formed quaternary salt upon using larger amounts. 
Conveniently the quaternization reaction is carried forth by heating the 
tributyl tin ether derivative and its quaternizing aryl or aliphatic 
halide with mixing in an aromatic hydrocarbon liquid, such as a xylene and 
preferably para-xylene, and generally with the mixture refluxed (about 
144.degree. C. for p-xylene) until quaternization is completed. Refluxing 
time for substantially complete quaternization can range from less than 
one day up to about one week or longer. Infrared spectral analysis and/or 
thin layer chromatographic analysis of the formed product or small 
portions thereof, after various time periods of refluxing, permits one 
readily to determine when quaternization is substantially completed. Of 
course one generally removes the hydrocarbon liquid, e.g. xylene, from the 
product before these analyses, with the xylene conveniently removed by 
vacuum distillation or like means. The formed quaternary salt product also 
is similarly stripped of its xylene or like hydrocarbon liquid. 
While the just described preparation methods specify benzene as a useful 
aromatic hydrocarbon solvent in preparation of the triorganotin ether 
derivative of the tertiary amine and p-xylene as a useful aromatic 
hydrocarbon liquid in preparation of the quaternary salt, other aromatic 
hydrocarbon solvents and liquids may be used. A number of aromatic 
hydrocarbon materials are useful for both preparations. Thus, in place of 
benzene one can use toluene or a xylene, and in place of xylene one can 
use benzene or toluene, for example. Likewise where the same aromatic 
hydrocarbon is useful for both preparations, one can proceed directly to 
quaternization of the triorganotin ether derivative without first 
separating the ether derivative from the aromatic hydrocarbon solvent in 
which it is prepared. 
For antifoulant utility, a quaternary salt of the invention is included as 
the antifouling constituent alone or in conjunction with other antifouling 
agents in conventional marine antifouling paint compositions which contain 
a resinous polymer in whole or as part as the binder component in their 
paint compositions. Generally one employs a synthetic vinyl polymer as the 
resinous binder, such as a vinyl chloride-vinyl acetate copolymer coating 
resin (e.g. VYHD vinyl resin of Union Carbide Corp.) However, the 
quaternary salt also may be blended with other conventionally employed 
resinous polymer binders, such as chlorinated rubber, rosin-vinyl polymer 
blends, and the like. Our quaternary salt blend readily with these 
conventional resinous binders. A quaternary salt is included in an amount 
effective to prevent fouling for the desired period of time and the 
resinous coating polymer is included in an amount effective to bind this 
amount of quaternary salt into a coating and adhere the coating to the 
article, conventionally to an underlying conventional marine primer 
coating which adheres directly to the article's surface for anti-corrosion 
protection thereof.

The invention now will be better understood with reference to the following 
specific examples: 
EXAMPLE A 
2-Dimethylaminomethyl phenol was prepared by the method of S. Cavitt, "J. 
Org. Chem.", 27, 1211 (1962). 61.0 gm salicylaldehyde, 127 gm 25% by wt 
dimethylamine in water and 1.2 gm 10% by wt palladium on charcoal are 
placed in a pressure bottle of a Parr hydrogenator and hydrogenated until 
41.7 lbs of hydrogen are taken up. The experiment is repeated and reaction 
mixtures combined. The catalyst is filtered off and the filtrate made 
acidic (pH 2), extracted with ether, and the ether discarded. The aqueous 
phase is adjusted to pH 8 with NaOH and extracted with ether. The aqueous 
phase is adjusted to pH 9 with NaOH and extracted with ether. The ether 
extracts are combined, dried over MgSO.sub.4, filtered, and evaporated on 
a rotating evaporator. There results 111.7 gm of an orange liquid (Percent 
crude yield - 75). This is fractionated at reduced pressure. The product 
is collected at 60.degree.-63.degree. C. at 0.5 mm to provide 99.1 gm of 
a yellow liquid (Percent yield - 65). 
2-(Dimethylaminomethyl)phenyltributylstannyl Ether is prepared as follows: 
59.6 gm (0.1 mole) bis(tributyltin) oxide and 30.0 gm (0.2 mole) 
2-dimethylaminomethyl phenol (as just prepared) are placed in 200 ml 
benzene. This is slowly heated to reflux in a system equipped with a 
Dean-Starke tube. After about 30 minutes water began to separate in the 
Dean-Starke tube. After 72 hours at reflux 1.9 ml of water had separated 
(theory 1.8 ml). A clear straw colored reaction mixture resulted and 
benzene is evaporated therefrom on a rotating evaporator to provide 87.7 
gm of a yellow liquid. This is fractionated at reduced pressure. The 
product collected at 165.degree.-168.degree. C. at 0.5 mm is 75.0 gm of a 
straw colored liquid (Percent yield - 82). Infrared spectral analysis 
provided bands characteristic of the desired product. 
Quaternization of 2-(dimethylaminomethyl)phenyl Tributylstannyl Ether. 50 
gm (0.113 mole) 2-(dimethylaminomethyl)phenyl tributylstannyl ether and 
500 ml xylene are placed together. Stirring is started and there is added 
dropwise over 20 minutes 28.5 gm (0.113 mole) 1-bromododecane in 50 ml 
xylene and heating is carried forth at reflux for a period of 72 hours. 
Then the solvent is stripped off on a rotating evaporator at reduced 
pressure (40 mm) to provide 86.7 gm of an orange, slightly viscous liquid. 
The infrared spectrum showed changes in certain bands attributable to 
formation of the quaternary salt. Remaining xylene was stripped off at 2 
mm to yield 76.3 gm of an orange, slightly viscous liquid. 
EXAMPLE B 
3-(Diethylamino)Phenyltributylstannyl Ether is prepared by placing 59.6 gm 
(0.1 mole) bis(tributyltin) oxide and 32.6 gm (0.2 mole) 
m-dimethylaminophenol in 200 ml of benzene. This is heated to reflux in a 
system that contains a Dean-Starke tube. After 30 minutes refluxing, water 
began to separate in the Dean-Starke tube, and after 72 hours a total of 
2.2 ml of water had collected (theory 1.8 ml). A brown reaction mixture 
resulted. This is treated with charcoal, filtered and the benzene 
evaporated off using a rotating evaporator to provide 87.8 gm of brown 
liquid. This is fractionated at reduced pressure to collect at 
181.degree.-183.degree. C. at 0.5 mm a desired product of 70.8 gm of a 
yellow, slightly viscous liquid (Percent yield - 78). Infrared spectral 
analysis shows this product to be the desired 
3-(diethylamino)phenyltributylstannyl ether. 
Quaternization of 3-(Diethylamino)Phenyl Tributylstannyl Ether is 
accomplished with 50.8 gm (0.112 mole) of 3-(diethylamino)phenyl 
tributylstannyl ether and 28.0 gm (0.112 mole) of 1-bromododecane in 400 
ml xylene. This is heated and stirred at reflux for 44 hours. A clear 
red-brown solution resulted. 300 ml of xylene is stripped off using a 
Claisen head to provide 113.5 gm of a red-brown, slightly viscous liquid. 
This is stripped at 2 mm with warming to remove the residual solvent. 
There remains 85.3 gm of a red-brown, slightly viscous liquid. Infrared 
spectral analysis shows this to be the desired quaternary salt. 
EXAMPLE C 
2-(2-Pyridyl)ethyl Tributylstannyl Ether is prepared from 59.6 gm (0.1 
mole) of bis(tributyltin) oxide and 24.6 gm (0.2 mole) 
2-(.beta.-hydroxyethyl)pyridine in 200 ml benzene. This is stirred and 
heated to reflux in a system that contains a Dean-Starke tube. After 30 
minutes refluxing water began to collect in the Dean-Starke tube and after 
refluxing 22 hours a total of 2.0 ml of water (theory 1.8 ml) had 
collected. This is evaporated on a rotating evaporator to provide 82.6 gm 
of straw colored liquid, which fractionated at reduced pressure. 66.4 gm. 
of a straw colored liquid are collected at 155.degree.-158.degree. C. at 
0.5 mm. (Percent yield - 80.6). Infrared spectral analysis shows this to 
be the desired ether. 
Quaternization of 2-(2-Pyridyl)ethyl Tributylstannyl Ether is accomplished 
with 51.0 gm (0.124 mole) 2-(2-pyridyl)ethyl tributylstannyl ether and 
31.0 gm (0.124 mole) 1-bromododecane in 400 ml xylene. This is stirred and 
heated at reflux for 24 hours. An orange-brown solution resulted. Most of 
the solvent is stripped off on a rotating evaporator to provide a 114.0 gm 
red-brown, slightly viscous liquid. This is stripped at 2 mm with warming 
to remove residual solvent. There remains 94.0 gm of a red-brown, slightly 
viscous liquid. Infrared spectral analysis shows this to be a mixture of 
the tin compounds, halide and the desired compound. Accordingly there are 
added 150 ml xylene. One then stirs and heats at reflux for 68 hours. The 
xylene solvent is stripped off as described above to provide 87.6 gm of a 
brown, slightly viscous liquid. Infrared spectral analysis shows this to 
be the quaternary salt. 
EXAMPLE D 2,4,6-tris(Dimethylaminomethyl)phenol is prepared in general by 
the procedure of Blicke, "Organic Reactions", 1, 330(1942). 47.0 gm (0.5 
mole) phenol and 360 gm 25% by wt dimethylamine in water are mixed 
together. Stirring was restarted with 150 gm 35% by formaldehyde in water 
added dropwise while maintaining reaction temperature at 
20.degree.-25.degree. C. Stirring was continued at 25.degree. C. for 1 
hour after the addition was complete. After heating at reflux (90.degree. 
C.) for 2 hours the solution was red-orange. 100 gm sodium chloride was 
added portionwise and reflux continued for 30 minutes. The layers were 
separated while the reaction mixture was still hot. The organic phase was 
taken into benzene and dried over MgSO.sub.4. The drying agent was 
filtered off and the benzene evaporated on a rotating evaporator to 
provide 130.3 gm of a red-orange liquid (Percent crude yield - 98). This 
was distilled at reduced pressure and to collect at 
131.degree.-135.degree. C. at 0.5 mm a product of 110.0 gm of yellow 
liquid (Percent yield - 83). 2,4,6-tri-(Dimethylaminomethyl)phenyl 
Tributylstannyl Ether is prepared from 59.6 gm (0.1 mole) bis(tributyltin) 
oxide and 53.0 gm (0.2 mole) 2,4,6-tri-(dimethylaminomethyl)phenol in 200 
ml benzene. This is stirred and heated to reflux in a system that contains 
a Dean-Starke tube. After refluxing 72 hours only 1.0 ml of water had 
collected in Dean-Starke tube. The benzene is stripped off on a rotating 
evaporator and 200 ml of toluene are added. An additional 72 hours of 
refluxing are carried forth during which time an additional 0.5 ml of 
water was collected. The solvent was stripped off on a rotating evaporator 
to provide 117.8 gm of a orange liquid. This was fractionated at reduced 
pressure, 205.degree. C. at 2 mm to 216.degree. C. at 6 mm, to collect the 
desired product, 42.2 gm of yellow, slightly viscous liquid (Percent yield 
- 38). Note: Distillation was stopped early in this preparation because 
product was decomposing in the reaction vessel. 
Quaternization of 2,4,6-tris-(dimethylaminomethyl Phenyl Tributylstannyl 
Ether is accomplished as follows: 37.0 gm (0.067 mole) 
2,4,6-tris-(dimethylaminomethyl)phenyl tributylstannyl ether and 33.4 gm 
(0.134 mole) 1-bromododecane are placed in 150 ml xylene. The resulting 
mixture is stirred and heated at reflux for 48 hours. After several hours 
a tan solid began to separate and after 48 hours a brown reaction mixture 
with some tan solid resulted. The solid is filtered off, washed with 
xylene and dried to give 121.1 gm of tan solid. Infrared spectral analysis 
showed this to be amino-hydrobromide with no aromatic character. The 
solvent was stripped from the filtrate at 6 mm to provide 34.4 gm of 
viscous, brown liquid which solidified to a waxy solid. Infrared spectral 
analysis showed this to be the quaternary salt. 
EXAMPLE E 
N,N-Di-(2-Ethylhexylamino)ethyl Tributylstannyl Ether is prepared from 59.6 
gm (0.1 mole) bis(tributyltin) oxide and 57.0 gm (0.2 mole) 
N,N-Di-(2-ethylhexyl)ethanolamine in 200 ml benzene. This is stirred and 
heated to reflux in a system that contains a Dean-Starke tube. After 
refluxing for 22 hours a total of 1.8 ml of water (theory 1.8 ml) had 
collected in the Dean-Starke tube. The solvent is stripped off on a 
rotating evaporator to provide 117.0 gm of orange liquid. Upon 
fractionating at reduced pressure, 80.0 gm of the desired product, a 
yellow liquid, was collected at 195.degree.-199.degree. C. at 0.5 mm 
(Percent yield - 70). Infrared spectral analysis showed this to be the 
desired ether. 
Quaternization of N,N-di-(2-ethylhexylamino)ethyl tributylstannyl ether is 
accomplished as follows: 27.2 gm (0.0445 mole) 
N,N-di-(ethylhexylamino)ethyl tributylstannyl ether and 7.4 gm (0.0445 
mole) benzyl bromide in 150 ml xylene are stirred and refluxed for a total 
of 116 hours. An orange reaction mixture resulted. Most of the solvent is 
stripped off on a rotating evaporator. Residual solvent is stripped off at 
6 mm using a Claisen head to provide 38.0 gm of orange-brown liquid. 
Infrared spectral analysis showed this to be largely the desired 
quaternary salt with the possibility of some unreacted starting materials 
being present. 
EXAMPLE F 
N,N-Diethylaminoethyl Tributyltin Ether is prepared from 59.6 gm (0.1 mole) 
bis(tributyltin) oxide and 23.4 gm (0.2 mole) N,N-diethylethanolamine in 
200 ml benzene. This is stirred and heated to reflux in a system which 
contains a Dean-Starke tube. After 30 minutes water began to collect in 
the Dean-Starke tube and after 22 hours at reflux 1.8 ml of water (theory 
1.8 ml) had collected. The solvent is stripped off on a rotating 
evaporator to provide 81.1 gm of a straw colored liquid. Upon 
fractionating at reduced pressure there is collected the desired product, 
65.5 gm of water-white liquid, at 135.degree.-139.degree. C. at 0.7 mm 
(Percent yield - 80). Infrared spectral analysis shows this to be the 
desired ether. 
Quaternization of N,N-diethylaminoethyl Tributylstannyl Ether is 
accomplished as follows: 52.8 gm (0.130 mole) N,N-diethylaminoethyl 
tributylstannyl ether and 21.7 gm (0.127 mole) benzyl bromide in 150 ml 
xylene are stirred and heated at reflux for 48 hours. A clear red-orange 
reaction mixture forms. The solvent is stripped off on a rotating 
evaporator to provide 88.9 gm of red-orange liquid. Thin layer 
chromatography (TLC) indicated that the reaction was not yet complete. 
Whereupon there are added to 150 ml xylene and refluxing carried forth for 
an additional 68 hours. The xylene then is stripped as described above to 
provide 69.2 gm of orange-brown liquid. Infrared spectral analysis showed 
this to be the desired quaternary salt. 
EXAMPLE G 
2(N-Morphilino)ethyl Tributylstannyl Ether is prepared from 59.6 gm (0.1 
mole) bis(tributyltin) oxide and 26.2 gm (0.2 mole) 
N(.beta.-hydroxyethyl)morpholine in 200 ml benzene. This is stirred and 
heated to reflux in a system which contains a Dean-Starke tube. After 30 
minutes refluxing water began to collect in the Dean-Starke tube and after 
refluxing for 22 hours 1.8 ml of water (theory 1.8 ml) had collected. The 
benzene is evaporated on a rotating evaporator to provide 84.4 gm of clear 
yellow liquid. This is fractionated at reduced pressure with the desired 
product, 65.6 gm of water-white liquid, collected between 156.degree. C. 
at 0.5 mm to 165.degree. C. at 0.7 mm (Percent yield - 79.2). Infrared 
spectral analysis shows this to be the desired ether. 
Quaternization of 2-(N-morphilino)Ethyl Tributylstannyl Ether is 
accomplished as follows: 47.2 gm (0.112 moles) 2-(N-morphilino)ethyl 
tributylstannyl ether and 19.1 gm (0.112 moles) benzyl bromide in 150 ml 
xylene are stirred and heated at reflux for 138 hours. A clear bright red 
reaction mixture resulted. The xylene solvent is stripped off at 6 mm to 
provide 63.2 gm of red-brown liquid. Infrared spectral analysis showed 
this to be the quaternary salt. 
EXAMPLE H 
3-Dimethylamino-1-Propyl Tributylstannyl Ether is prepared from 59.6 gm 
(0.1 mole) bis(tributyltin) oxide and 20.6 gm (0.2 mole) 
3-dimethylamino-1-propanol in 200 ml benzene. This is stirred and heated 
to reflux in a system that contains a Dean-Starke tube. After 30 minutes 
refluxing water began to collect in the Dean-Starke tube and after 
refluxing for 22 hours a total of 1.9 ml of water (theory 1.8 ml) had 
collected. The benzene is stripped off on a rotating evaporator to provide 
77.1 gm of straw colored liquid. This is fractionated at reduced pressure, 
with 53.0 gm water-white liquid (Percent yield - 67.6) being collected at 
135.degree.-139.degree. C. at 0.7 mm. Infrared spectral analysis shows 
this to be the desired ether. 
Quaternization of 3-Dimethylamino-1-Propyl Tributylstannyl Ether is carried 
forth as follows: 44.4 gm (0.113 mole) 3-dimethylamino-1-propyl 
tributylstannyl ether and 19.4 gm (0.113 mole) benzyl bromide in 150 ml 
xylene are stirred and heated at reflux for 114 hours. A clear tan 
solution results which contained a small amount of a gummy solid. The 
solvent is stripped off at 6 mm to provide 61.1 gm of brown liquid with 
some solid. Infrared spectral analysis showed the liquid to be the 
quaternary salt. 
EXAMPLE I 
2-Dimethylamino-2-Methyl-1-Propyl Tributylstannyl Ether is prepared from 
59.6 gm (0.1 mole) bis(tributyltin) oxide and 23.4 gm (0.2 mole) 
2-dimethylamino-2-methyl-1-propanol in 200 ml benzene. This is stirred and 
heated to reflux in a system that contains a Dean-Starke tube. After 30 
minutes water began to collect in the Dean-Starke tube and after 46 hours 
only 1.6 ml of water (theory 1.8 ml) had collected. Solvent is stripped 
off on a rotating evaporator to provide 78.3 gm of straw colored liquid. 
This is fractionated at reduced pressure to collect the desired product, 
52.7 gm of water-white liquid (Percent yield - 65), at 
132.degree.-137.degree. C. at 0.5 mm. Infrared spectral analysis shows 
this to be the desired ether. 
Quaternization of 2-(dimethylamino)-2-Methyl-1-Propyl Tributylstannyl Ether 
is accomplished with 40.7 gm (0.10 mole) 
2-(dimethylamino)-2-methyl-1-propyl tributylstannyl ether and 17.1 gm 
(0.10 mole) benzyl bromide in 150 ml xylene. This is stirred and heated at 
reflux for 72 hours. A clear yellow-tan solution resulted. The solvent is 
stripped off at 6 mm to provide 56.2 gm of tan slightly viscous liquid. 
Infrared spectral analysis shows this to be the quaternary salt. 
EXAMPLE J 
N,N-Dibutylaminoethyl Tributylstannyl Ether is prepared from 59.6 gm (0.1 
mole) bis(tributyltin) oxide and 34.6 gm (0.2 mole) 
N,N-dibutylethanolamine in 200 ml benzene. This is stirred and heated to 
reflux in a system that contains a Dean-Starke tube. After 30 minutes 
water began to collect in the Dean-Starke tube and after refluxing for a 
period of 22 hours a total of 1.8 ml of water (theory 1.8 ml) had 
collected. A rotating evaporator is used to remove the benzene and to 
provide 95.1 gm of red-orange liquid. This is fractionated at reduced 
pressure with collection at 163.degree.-166.degree. C. at 0.7 mm of 73.1 
gm of yellow liquid (Percent yield - 79). Infrared spectral analysis shows 
this to be the desired ether. 
Quaternization of N,N-Dibutylaminoethyl Tributylstannyl Ether is 
accomplished with 46.2 gm (0.1 mole) N,N-dibutylaminoethyl tributylstannyl 
ether and 17.1 gm (0.1 mole) benzyl bromide in 150 ml xylene. This is 
stirred and heated at reflux for 126 hours. A clear orange solution 
resulted. 100 ml of solvent is stripped off using a Claisen head at 
atmospheric pressure. Residual solvent is stripped off at 6-8 mm to 
provide 60.7 gm of red-orange liquid. Infrared spectral analysis shows 
this to be the quaternary salt. 
EXAMPLE K 
2-[N-Pyrollidinyl]ethyl Tributylstannyl Ether is prepared from 65.0 gm 
(.109 mole) bis(tributyltin) oxide and 25.0 gm (.217 mole) 
N-(.beta.-hydroxyethyl)pyrolidine in 200 ml benzene. This is stirred and 
heated to reflux in a system that contains a Dean-Starke tube. After 
refluxing 20 hours, a total of 2.0 ml of water (theory 1.96 ml) had 
collected in the Dean-Starke tube. The solvent is stripped off on a 
rotating evaporator to provide 94.0 gm of yellow liquid. This is 
fractionated at reduced pressure with collection at 
150.degree.-154.degree. C. at 0.3 mm of water-white liquid (Percent yield 
- 63). Infrared spectral analysis shows this liquid to be the desired 
ether. 
Quaternization of 2-(N-pyrrolidinyl)Ethyl Tributystannyl Ether is 
accomplished as follows: 38.8 gm (0.096 moles) 2-(N-pyrrolidiny)ether 
tributylstannyl ether and 16.4 gm (0.096 moles) benzyl bromide in 150 ml 
xylene are heated and stirred at reflux temperature for 120 hours. A clear 
red-brown material resulted. 100 ml solvent are stripped off at 
atmospheric pressure using a Claisen head. Residual solvent is stripped 
off at 6-8 mm to provide 57.0 gm of brown liquid. Infrared spectral 
analysis shows this to be the quaternary salt. 
EXAMPLE L 
1-Dimethylamino-2-Propyl Tributylstannyl Ether is prepared from 89.4 gm 
(0.15 mole) bis(tributyltin) oxide and 30.9 gm (0.3 mole) 
1-dimethylamino-2-propanol in 200 ml benzene. This is stirred and heated 
to reflux in a system that contains a Dean-Starke tube. After refluxing 23 
hours a total of 2.6 ml of water (theory 2.7 ml) had collected in the 
Dean-Starke tube. The solvent is stripped off on a rotating evaporator to 
provide 111.0 gm of yellow liquid. This is fractionated at reduced 
pressure with collection at 167.degree.-175.degree. C. at 0.5 mm of 63.4 
gm of straw colored liquid. (Percent yield - 54). Infrared spectral 
analysis shows this liquid to be the desired ether. 
Quaternization of 1-Dimethylamino-2-Propyl Tributylstannyl Ether is 
accomplished with 47.8 gm (0.122 mole) 1-dimethylamino-2-propyl 
tributylstannyl ether and 20.9 gm (0.122 mole) benzyl bromide in 150 ml 
xylene. This is stirred and heated at reflux for 120 hours. A clear yellow 
solution resulted. 100 ml of solvent is stripped off at atmospheric 
pressure using a Claisen head. Residual solvent is stripped off at 6-8 mm 
to provide 69.1 gm of yellow-orange liquid. Infrared spectral analysis 
shows this to be probably the quaternary salt. However, the possibility of 
it merely being a mixture cannot be ruled out. 
EXAMPLE M 
2-(N-Piperazino)ethyl Tributylstannyl Ether is prepared from 59.6 gm (0.1 
mole) bis(tributyltin) oxide and 26.0 gm (0.2 mole) 
N-(.beta.-hydroxyethyl)piperazine in 200 ml benzene. This is stirred and 
heated to reflux in a system that contains a Dean-Starke tube. After 30 
minutes refluxing water began to collect in the Dean-Starke tube and after 
22 hours of refluxing a total of 1.8 ml of water (theory 1.8 ml) had 
collected. Solvent is stripped off on a rotating evaporator to provide 
84.3 gm of yellow liquid. This is fractionated at reduced pressure and 
35.9 gm of a water-white desired product (Percent yield - 43) was 
collected at 160.degree.-167.degree. C. at 0.5 mm. Infrared spectral 
analysis shows this product to be the desired ether. 
Quaternization of 2-(N-piperazino)Ethyl Tributylstannyl Ether is 
accomplished with 29.0 gm (0.07 mole) 2-(N-piperazino)ethyl 
tributylstannyl ether and 12.0 gm (0.07 mole) benzyl bromide in 150 ml 
xylene. This is stirred and heated at reflux for 120 hours. A clear 
red-brown reaction mixture resulted. 100 ml solvent are stripped off at 
atmospheric pressure using a Claisen head. Residual solvent is stripped 
off at 6 mm to provide 41.9 gm of brown liquid. Infrared spectral analysis 
shows this to be the desired quaternary salt. 
EXAMPLE N 
2-Diisopropylaminoethyl Tributylstannyl Ether is prepared from 89.4 gm 
(0.15 mole) bis(tributyltin) oxide and 43.5 gm (0.30 mole) 
2-diisopropylaminoethanol in 200 ml benzene. This is stirred and heated to 
reflux in a system that contains a Dean-Starke tube. After refluxing for 
23 hours a total of 2.6 ml of water (theory 2.7 ml) had collected in the 
Dean-Starke tube. Solvent is stripped off on a rotating evaporator to 
provide 134.3 gm of orange liquid. This is fractionated at reduced 
pressure with collection at 147.degree.-155.degree. C. at 0.4 mm of 87.6 
gm of straw liquid (Percent theory - 73). Infrared spectral analysis shows 
this liquid to be the desired ether. 
Quaternization of 2-(di-isopropylamino)Ethyl Tributylstannyl Ether is 
accomplished with 54.0 gm (0.12 mole) 2-(di-isopropylamino)ethyl 
tributylstannyl ether and 20.6 gm (0.12 mole) benzyl bromide in 150 ml 
xylene. This is stirred and heated at reflux for 120 hours. A clear 
yellow-orange solution resulted. 100 ml solvent are stripped off at 
atmospheric pressure using a Claisen head. Residual solvent is stripped 
off at 6-8 mm to provide 74.4 gm of yellow-orange liquid. Infrared 
spectral analysis shows this to be the desired quaternary salt. 
Each of the quaternary salts prepared in preceding Examples A through N, in 
addition to produce structural confirmation by infrared spectral analysis, 
were examined by thin layer chromatography (TLC) using methanol and 
chloroform as developers. In all instances there was evidence of only a 
slight amount, or less, of unreacted starting materials present in the 
quaternary salt products. 
ANTIFOULING EVALUATIONS 
Each of the precedingly prepared quaternary salts of Examples A through N 
were evaluated from antifouling activity in the Atlantic Ocean natural 
seawater near Miami Beach, Florida, United States of America. 
The preparation, exposure, and evaluation of test panels for these 
evaluations were as follows: Each quaternary salt was hand mixed in a 1 to 
9 ratio by weight with a commercially available polyvinylacetae - acrylic 
copolymer latex (e.g. No. 2345, National Starch Company). 1.5 grams of 
this quaternary salt/latex mixture then was spread uniformly over a 
centrally located 5 inch diameter circle onto a rigid polyvinylchloride 
test panel and dried. One test panel having a white background and another 
panel having a black background were prepared for each evaluated 
quaternary salt. The white-background panel facing up was immersed in the 
sea water at a depth of about 4 inches. The black-background panel facing 
down was immersed in the sea water at a depth of about 61 inches. 
Immersion exposures were continued for six weeks before the condition of 
the panels was evaluated. Panels at about 4 inch depth were rated for 
resistance to algal growth on a comparative scale of 0 to 10 equals no 
growth and 0 equals completely fouled. Panels at about 61 inch depth were 
rated for resistance to hard fouling on a similar comparative scale of 0 
to 10 where 10 equals no fouling and 0 equals complete fouling. It was 
also noted whether the hard fouling was of barnacles, tunicates, 
encrusting, bryozoana oysters, hydroids, or tube worms or amphipods. 
Ratings were made of both the painted circular areas and the background 
areas of the panels. 
In addition to preparation, exposure, and evaluation of the panels 
involving the quaternary salts and unpainted control areas of those 
panels, two control systems were included and evaluated for comparison 
purposes. Like white- and black-faced test panels were prepared with 
centrally located 5-in. dia. circular coatings only of the latex, as a 
negative control. Like white- and black-faced test panels also were 
prepared with centrally located 5-in. dia. circular coatings thereon of 
1.5 grams of a 1 to 9 ratio by weight of bis(tributyltin) oxide (TBTO) to 
the latex. These served as a positive control as the TBTO is a known 
toxicant for marine organisms. 
Data of the just described evaluations are presented in the following TABLE 
I. 
TABLE I 
__________________________________________________________________________ 
PANEL ANTIFOULING ACTIVITY EVALUATION 
Activity Rating.sup.(a) 
Material Upper (facing up) 
Lower (facing down) 
Evaluated Covered Area 
Uncovered Area 
Covered Area 
Uncovered Area 
__________________________________________________________________________ 
Ex. A Quaternary Salt 
3 0 9f 4,a,b,c,d,e,f 
Ex. B Quaternary Salt 
3 2 9f 0,a,b,c,d,e,f 
Ex. C Quaternary Salt 
2 0 9f 2,a,b,c,d,e,f 
Ex. D Quaternary Salt 
0 0 9f 2,a,b,c,d,e,f 
Ex. E Quaternary Salt 
6 2 8f 2,a,b,c,d,e,f 
Ex. F Quaternary Salt 
5 2 9f 2,a,b,c,d,e,f 
Ex. G Quaternary Salt 
10 4 8f 2,a,b,c,d,e,f 
Ex. H Quaternary Salt 
5 2 10 2,a,b,c,d,e,f 
Ex. I Quaternary Salt 
10 6 9 4,a,d,f 
Ex. J Quaternary Salt 
8 2 9 2,a,b,c,d,e,f 
Ex. K Quaternary Salt 
10 6 9 2,a,b,c,d,e,f 
Ex. L Quaternary Salt 
10 4 9 2,a,b,c,d,e,f 
Ex. M Quaternary Salt 
5 2 9f 2,a,b,c,d,e,f 
Ex. N Quaternary Salt 
10 4 9 2,a,b,c,d,e,f 
TBTO (Positive Control) 
5 3 9 2,a,b,c,d,e,f 
Latex only (Negative Control) 
0 0 0 0,a,b,c,d,e,f 
__________________________________________________________________________ 
.sup.(a) Activity was rated on a scale of 0 to 10 where 10 = no fouling 
and 0 = completely fouled. Hard fouling was further noted as (a) 
barnacles, (b) tunicates, (c) encrusting bryozoans, (d) oysters, (e) 
hydroids, (f) tube worms and ampliphods. 
From the foregoing evaluations, overall performance rankings can be given 
to the various evaluated quaternary salts and controls by considering the 
sums of the 0-10 ratings for the covered areas on the upper and lower 
immersed panels. This summing of observed performance ratings gives equal 
service value to resistance to soft fouling (i.e. as by algae) and to hard 
fouling (as by hard-shell and other marine organisms). In such an overall 
comparative performance ranking for comparison purposes a sum total for 
the two 0-10 ratings equaling 20 warrants a ranking of "outstanding", a 
sum total of 19 is ranked as "excellent", a sum total of 18 is ranked as 
"good", a sum total of 17-16 is ranked as "fair", a sum total of 15-10 is 
ranked as "poor", a sum total of 9-1 is ranked as "very poor", and a sum 
total of 0 is ranked as "ineffective". Under this performance ranking 
system, the quaternary salts of I, L, K, and N are ranked as excellent 
with these each being especially preferred materials for practice of the 
invention; the quaternary salt of Example G receives a ranking of good and 
the quaternary salt of Example J receives a ranking of fair with these two 
salts being preferred materials for practice of the invention; the 
quaternary salts of Examples E, F, H, and M rank as poor, yet still 
perform closely equivalent to the TBTO control material, and the 
quaternary salts of Examples A, B, C, and D rank from poor to very poor, 
yet do exhibit useful antifouling activity. Of note is that the negative 
control of latex only under this ranking system ranks as ineffective. None 
of the quaternary salts, whose performances were evaluated were noted to 
exhibit any "throwing power" in protecting uncoated area of the test 
panel. 
While certain specific and illustrative embodiments have been described so 
as to teach the invention with great specificity, it will be obvious 
therefrom that various changes and modifications may be made therefrom 
without departing from the true spirit and scope of the invention. For 
example, while the organo-portion of the organotin moiety has been 
illustrated by example by butyl radicals and on a broader scope taught as 
being of certain alkyl radicals, it will be apparent that these alkyl 
radicals can be replaced in whole or part by phenyl radicals, such as by 
the triphenyltin moiety being substituted for the tributyltin moiety to 
provide other embodiments of the invention. Likewise, while our quaternary 
salts have been specifically taught and illustrated with their ether 
linkage being bivalent oxygen, it will be apparent that the ether linkage 
could be a bivalent sulfur and specifically a thioether with corresponding 
changes of oxygen to sulfur in reactants for preparation of the quaternary 
salts. All these just mentioned and other changes and modifications will 
be apparent to the art. Of course the particular usages of, preparations 
of, and quaternary salts of these changes and modifications will not 
necessarily each be the equivalents of and equal to and may in some 
instances be inferior and in other instances superior to those taught in 
the present disclosure with the present invention limited only to the 
extent as set forth in the appended claims.