Note: Descriptions are shown in the official language in which they were submitted.
~)65311
This invention relates to biocidally active organo-tin sucrose com-
pounds which are carboxylic acid esters of biocidally active organo-tin com-
pounds wlth sucrose.
A number of biocidally active organo-tin compounds have been
developed in recent years for a variety of pesticidal or herbicidal applica-
tions limited by their poor water solubility, low vapor pressure or both.
Accordingly, it is an ob~ect of one aspect of the present invention
to provide organo-tin compounds having pesticidal or herbicical activity to-
gether with improved water solubility.
An object of another aspect of this invention is to provide such
organo-tin compounds which may be used to provide agricultural compositions
useful in controlling the growth of undesired plant or animal pests.
An ob~ect of a further aspect of this invention is to provide such
organo-tin compounds which may be used to provide improved antifouling paints.
An object of an additional aspect of this invention is to provide
such organo-tin compounds which may be used to provide a composition and me-
thod for controlling mites.
An ob~ect of still another aspect of this invention is to provide
such organo-tin compounds which may be used to provide a composition and
method for controlling the growth of aquatic weeds.
Briefly, by a broad aspect o~ this invention, an organo-tin sucrose
compound is provided of the formula:
A - 2 -
10~53~.~
cOO-sucrose
x
LcooJ p ~H2~ n [S]mSnRlR2R3
in which the tetravalent tin atom has only three tin-carbon
bonds cnd wherein X is:
CH2- CH -
~ ~ ¦ or ¦¦ ;
m is O or l;
p is O when m is 1 and p is 1 when m is O;
n is O or an integer from 1 to 6 with the proviso
that, when m is 1, n is an integer from 1 to 6; and
at least two of Rl, R2 and R3 are each alkyl of
1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or
aliphatic aryl or aralkyl of 6 to 10 ring carbon atoms;
j when m is 1 or when m and n are both O, one of
¦ Rl, R2 and R3 is the acyl radical of an inorganic mineral
¦ acid or of a hydrocarbon; carboxylic or sulfonic acid; and
20 I when m is O or when m is 1 and n is said integer, all
Il of Rl, R2 and R3 have the above-indicated values.
,! ~
10~531~
According to another aspect of this invention an or~ano-
tin sucrose compound is provided having tne gen~rdl formula:
foo- sucrose
rl l
LcooJ p [CH2~-n-rS]m- SnRlR2R3
in which sucrose represents a sucrose residue, X repre-
sents
H2 ~ or CH -
, CH2 - CH -
m is O or 1, p is O when m is 1 and p is 1 when m is O;
n is O or an integer from 1 to 6 with the proviso that,
when m is 1, n is an integer from 1 to 6; and Rl,R2 and R3,
which may be the same as or different from one another, are
groups such that the tin atom has three tin-carbon bonds
and one bond which is not a tin-carbon bond. Thus, in the
case when n is O, p is 1 and n is O or in the case where
p is O, m is 1 and n is an integer, Rl,R2 and R3 all re-
present the same or different organic groups so that thetin atom forms its three tin-carbon bonds with carbon atoms
: of the groups Rl,R2 and R3. When n is an integer, m is O
and p is 1, however, two of Rl, R2 and R3 represent organic
groups as above and the other Rl,R2 and R3 represents an
inorganic moiety or an organic moiety, where the organic
group is attached to the tin atom by other than a tin-
carbon bond.
A
It
~O~S311
By variants of this invention, m = 0 and p = 1; or n = 0 or an in-
teger from 2 to 6; or n = 3 or 4; or n = 0.
By another variant, alkyl is butyl, and by a further variant,
cycloalkyl i9 cyclohexyl.
By still other variants, hydrocarbon aryl is phenyl, and hydrocar-
bon aralkyl is benzyl.
By another variant, at least two of Rl, R and R3 have the same
values, while in yet another variant, R = R = R ~
By still another variant, one of Rl, R and R3 is the aryl radical
of an inorganlc mineral acid.
By a still further variant, one of R , R and R is the acyl
radical of a hydrocarbon carboxylic sulfonic acid of 1 to 8 carbon atoms.
By a further variant, the acyl radical is p-toluene sulfonate.
By yet other specific variants, the compound is (n-butyl)3-
SnOCOC6H4COO-sucrose; (phenyl)3-SnOCOC6H4COO-sucrose; (cyclo-C6Hll)3-SnOCOC6
H4COO-sucro~el; ((n-butyl)3-SnOCOCH2CH2COO-sucrose; (phenyl)3-SnOCOCH2CH2COO-
sucrose; sucrose-ococ6H4coo(cH2)3sn~enyl)2Br; or (phenyl)3SnSCH2COO-SUcrse-
- 4 a -
~OtjS;~ll j `
The organo-tin co~pounds of aspects of this invention have shown bio-
cidal activity. Thus, amongst the compounds of aspects of this inven-
tion one can find fungicidal, algicidal, miticidal, herbi-
cidal and bactericidal activity. The activities are often,
per unit weight of tin, much higher than the activities
of currently used organo-tin compounds. In addition, the
presence of a sucrose residue appears to render the com~
pounds more water soluble than many currently used organo-
tin compounds.
The organo-tin sucrose compounds of aspects o~ this invention
and in particular those in which m and n are O, can be
prepared in good yields by relatively si ple and direct
reaction processes. The product is a mixture of compounds
which differ in the position of attachment of the oxygen
atom to the sucrose residue and in the number of tin-
containing groups attached to the sucrose residue. The
mixtures can be refined or purified to give a pure product
- but this is expensive an~ since this mixture appears to be
biocidally effective, the mixture is usually satisfactory.
The use of the single formula:
COO-sucrose
rl 1
LCool ~H~ nLS]m SnRlR2~3
herein is therefore to be construed as embracing the mix-
tures noted above.
~ 5-
106S311
The compounds in which m and n are both zero and
p is 1 are preferred since they are usually simpler to
prepare and have better bactericidal properties than
those in which m is O, n is an integer from 1 to 6 and
p is l, and so the sucrose residue is directly linked via
a tin-carbon bond to the tin atom. When n is an integer
and p is 1, it is preferred that n be from 2 to 6 and
most preferred that n be 3 or 4, since the intermediates
corresponding to the case where n is 3 or 4, and parti-
cularly 3, are readily available.
The nature of the groups Rl,R2 and R3 is,as noted~bove,dependent upon the requirement that the tin atom in
the organo-tin sucrose compound have three covalent tin-
carbon bonds. Organo-tin compounds where there are other
than three tin-carbon bonds appear to have less effective
biocidal properties.
Those of the groups Rl,R2 and R3 which are attached
by carbon-tin bonds to the tin atom are organic groups
such as alkyl, cycloalkyl groups, aryl and/or alkaryl
groups.
The alkyl group is desirably one which contains from
1 to 12 carbon atoms and it may be a straight or branched
alkyl group; more preferably, the alkyl group contains 1 to
8 carbon atoms and especially good results seem to be given
when the alkyl group contains 4 carbon atoms, e.g. an n-butyl
~06S3il
group so that if all three groups Rl,R2 and R3 represent
alkyl groups, together they contain about 12 carbon atoms
which seem to give best results. Suitable alkyl groups
include but are not limited to methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec.-butyl and tert.-butyl;
butyl is preferred. Contemplated alkyl equivalents are
alkyl groups bearing one or more substituents, e.g.,
halogen atoms or lower alkoxy, e.g. methoxyethyl, chloro-
methyl, methoxybutyl and bromoethyl.
The cycloalkyl group is desirably one containing
from 3 to 8 carbon atoms. Suitable cycloalkyl groups
include but are not limited to cyclopropyl, cyclobutyl,
cyclopentyl and cyclohexyl, optionally substituted, e.g.,
by alkyl or alkenyl of up to 4 carbon atoms to form cyclo-
alkylalkyl or cycloalkylalkenyl, e.g., cyclopropylmethyl;
cyclohexyl is preferred.
The aryl group is desirably a hydrocarbon aryl
group of 6 - 10 ring carbon atoms preferably phenyl or
naphthyl and especially phenyl. Aralkyl is aryl substi-
tued by lower alkyl as defined herein, preferably benzyl.
If one of the groups Rl,R2 and R3 is attached byother than a tin-carbon bond to the tin atom, that group
~an be in an inorganic moiety or an organic moiety where
the organic portion is linked through other than a carbon
atom to the tin atom, i.e. an acyl group.
106S311
In the case where one of R , R and R represents an inorganic acyl
moity, the acyl group is preferably of an inorganic mineral acid; suitable
examples include but are not limited tothe halogen atoms e.g. bromine or
chlorine atoms, an inorganic salt group e.g. a nitrate or phosphate, or one
valence of an oxygen or sulphur atom. In the case where one of R , R and R
represents an organic acyl moiety, the acyl group is preferably of a hydro-
carbon carboxylic or sulfonic acid of 1-15 carbon atoms, preferably alkanoly,
aroyl, alkanesulfonyl or arylsulfonye of 1-8 carbon atoms; suitable examples
include but are not limited to the acyl radicals of formic, acetric, propion-
ic and butyric acids; of methane, ethane, propane and butane sulfonic acid;and of benzene, toluene and xylene sulfonic acid. Preferred organic acyl
groups are the acetate and p-toluene sulfonate.
These residues R , R and R can be unsubstituted or can carry one
or two simple substituents, examples of which are lower alkyl groups, e.g.
methyl and ethyl groups, halogen atoms, e.g. chlorine atoms, lower alkoxy
groups, e.g. methoxy or ethoxy, or amino groups e.g. dimethylamino groups.
The group X is preferably:
~ or FH2 ~
.~ .
-- 8 --
106S31~
~since the compounds in which X is:
CH -
CH -
while being capable of being made in a fashion similar to
compounds where X is
~ or f~2-
tend to be more difficult to prepare since the products
are somewhat oily.
The compounds in which m is 1 and p is O can in
some circumstances be advantageous in that their synthesis
can be relatively simple.
The compounds in which n and m are zero and p is 1,
can be prepared by condensing sucrose with an anhydride
having the general formula:
/ CO
\CO /
in which X is as defined above
~o~S3~1
to give a sucrose ester of the general formula:
COO-sucrose
COOH
in which X and sucrose are as defined above, followed
by reacting the sucrose ester with an organo-tin hydroxide
or its corresponding oxide of the general formula:
RlR2R3SnOH or (RlR2R35n)20
in which Rl, R2 and R3 are as defined above.
In the first stage of this reaction, the two reagents can
be dissolved in an inert, aprotic solvent e.g. dimethyl
formamide, the resulting ester being apparently mixtures
including several 1:1 adducts and some 2:1 adducts together
with some free sucrose. In the second step of the reaction
which involves the use of the expensive organo-tin com-
pound, the reaction proceeds in high yields, often as high
as 85%.
To prepare the compounds in which n is an integer,
m is O and p is 1, the sucrose ester e.g. ¦ sucrose phtha-
late is initially prepared and then that ester is converted
to a metal salt, e.g. the sodium salt which is usually the
cheapest and most readily available, and reacted with an
organo-tin compound having the general formula:
Ph~ Sn [CH~ n Br
in which n is as defined above
and Ph represents a phenyl group,
.;.~
1~;5;~1
to give a compound of the formula:
COO-sucrose
COO ~H3 nsnph3
in which X, sucrose, n and Ph are as defined above.
In this compound, the bond between the tin atom
and a carbon atom of the aryl (phenyl) group is more sen-
sitive to attack by halogen atoms than the bond between the10
tin atom and the carbon atom of the linking alkylene group,
so that this compound can be converted by reaction with a
halogen, e-g.; bromine, in solution in, for example,
methyl alcohol, at low temperatures to give the following
compound according to the invention:
X COO-sucrose
( 2)nSnPh2Br.
This bromine substituted compound can be hydrolysed, if
desired, to eliminate the brominf atom and give the follow-
ing compound according to one aspect o~ this invention:
¦ /COO-sucrose
X \ ~ O.
COO (CH2 ) nSnPh2
in which X, Ph, sucrose and n are as defined above.
At
10653~1
Compounds in which m i9 1 and p is 0 can be prepared by reacting
an ester having the general formula:
R R R SnS(CH2) COOR
in which Rl, R2 and R3 are as defined above,
n i8 1-6 and R is an alkyl group e.~. methyl with sucrose.
The reaction can be conducted in a solvent e.g. dimethylformamide
by hesting in the presence of an alkali catalyst, e.g. potassium carbonate.
Some organo-tin sucrose compounds of aspects of this inv ention
have been found to have good miticidal activity, some to have fungicidal
activity, some to have algicidal activity, some to have herbicidal activity
and some to have bactericidal activity. The organo-tin sucrose compounds of
aspects of this invention are also safe to use in spraying onto crops either
in powder or liquid formulations because when exposed to sunlight or present
in soil, the compound is believed to decompose to a safe inorganic tin com-
pound and not to produce long-term pollution.
The biocidally active organo-tin sucrose compounds of aspects of
this invention can be used in essentially the same manner as corresponding
prior art compounds lacking the sucrose moiety in the molecule and variations
in the non-sucrose portion of the molecule appear to have generally the same
effect or biocidal activity a~ i8 known for the prior art compounds, e.g.,
see U.S. Patent No. 3,264,177.
i - 12 -
106S3~1
Preferred rates for application of the compounds of aspects of
this invention to foliage, stems and fruit of living plants
range from 0.01 to 106 kilograms of active ingre-
dient per hectare. More preferred rates are in the range
S of 1 to 10,000 kilograms per hectare and the most
preferred rates are in the range of 10 to 1,000 kilo-
grams per hectare. The optimum amount within this range
depends upon a number of variables which are well known to
those skilled in the art of plant protection. These vari-
ables include but are not limited to the disease to be con-
trolled, weather conditions expected, the type of crop,
stage of development of the crop and the interval between
applications. Applications within the range given may need
to be repeated one or many more times at intervals of 1 to
60 days.
The compounds of aspect~ of this invention can be applied in
a variety of formulations, including wettable powders,
dusts, suspensions, emulsifiable concentrates, solutions,
granules, pellets, etc. Concentrates can also be prepared
for use by formulators in further processing near the point
of use. The formulations will include one or more bio-
cidally active compounds of aspects of this invention and can include
surface-active agents, solid or liquid diluents and other
materials as required to produce the desired formulation.
-13-
~5311
The surface-active agents act as wetting, dispersing
and emulsifying agents which assist dispersion of the active
material in the spray, and which improve wetting of waxy
foliage and the like by the spray. The surfactants can in-
clude the same anionic,nOn-ionic and cationic agents as have
been used heretofore in similar biocidal compositions. A
detailed list of such agents may be found in "Detergents
and Emulsifiers Annual," (John W. McCutcheon, Inc.).
Anionic and non-ionic surfactants are preferred.
kmong the anionic surfactants, preferred ones are alkali
and alkaline earth salts of alkylarylsulfonic acids, e.g.
decylbenzenesulfonates and alkylnaphthalenesulfonates,
dialkyl sodium sulfosuccinate esters, sodium lauryl sulfate,
sodium N-methyl-N-oleyltaurate, sodium dodecyldiphenyl
ether disulfonate, partial phosphate esters of alkyl and
alkylphenyl polyethyleneoxyethanols, and the oleic acid
ester of sodium isothionate. Preferred non-ionic surfac-
tants include alkylphenyl polyethylene glycol ethers, poly-
oxyethylene derivatives of sorbitan fatty esters and long-
chain alcohols and mercaptans, as well as polyoxyethyleneesters of fatty acids.
Preferred dispersants are alkali and alkaline earth
salts of lignosulfonic acids, salts of polymerized alkylaryl-
10~531i
sulfonates, e.g. those sold under the Trade Marks "caxad" and"Darvan" (sodium slats of polymerized alkyl napthaline sulfonic
acids, or of polymerized substitu-ted acyl alkyl sulfonic acid,
of R.T. Vanderbrit Co.) as well as methylcellulose, polyvinyl
alcohol and the like.
Surfactants are present in compositions of aspects of this invention
in amounts up to 20~ by weight based on the total weight of the resulting
composition. When larger amounts of surfactant are desired, as for improved
wetting of, spreating on or penetration into foliage, mixing in the spray
tank is usually preferable for convenience.
Powder and dust preparations can be made by blending the active in-
gredient, with or without surfactant, with finely divided solids, e.g. talcs,
natural clays, pyrophyllite, diatomaceous earth; flours e.g. walnut shell,
wheat, redwood, soya bean and cotton seed; or inorganic substances e.g. mag-
nesium carbonate, calcium carbonate, calcium phosphate, sodium silicoalumin-
ate, sulfur and the like. The choice of a particular diluent is based on
consideration of the physical and chemical properties required of the product,
the chemical and physical properties and concentration of the active ingredi-
ent, and the use for which the formulation is intended. The compositions
are made by thoroughly blending the active ingredient with the diluent and
other additives. Usually a grinding step, as in a hammer mill or fluid ener-
8Y mill, in included. The particles in dust and powder preparations are pre-
ferably less than 50 micron3 in average diameter. With compounds which are
highly water insoluble, improved activity may be obtained with still finer
grinding.
~'
~ - - 15 -
106S31~
Preferred wettable powder formulations will contain
40% or more active ingredient together with sufficient sur-
factant and inert dil~ent to permit dispersion in water for
spray application. Compositions intended for dust applica-
tion will generally contain less than 50~ active ingredient.
Powdered compositions can be converted to granulesby adding a liquid, treating mechanically, and usually
drying. Mechanical devices such as granulating pans, mixers
and extruders can be used. Compaction devices can be used
even without a liquid in the mixture. Water soluble binders,
e.g, inorganic salts, urea, ligninsulfonates, methyl cellulose,
other water soluble polymers and the like, can be included
in these particulate formulations in amounts up to 25%
by weight of the finished granule or pellet. Such materials~
also aid in disintegration of the pellet and release of the
active ingredient under field conditions. Alternatively, a
melt, solution or suspension of the active ingredient can be
sprayed on the surfact of preformed granules of clay, ver-
miculite, corn cob and the like. Surfactants may also be
included in formulations of the latter type.
Solution formulations can be prepared in suitable
solvents. All solution formulations can be used for direct
low-volume applications. For such use, all that is required
is practical solubility and stability of the active ingredient
in the chosen solvent. An important sub-class of solution
~ 5'~
` ` . lA ~ ,~" `,
lO~S3~1
formulations is emulsifiable concentrates. For these, a
water-immisible solvent is required as well as surfactant
to help form and stabilize the final aqueous emulsion in
which the biocide is applied. It is preferred that the
active ingredient in solution formulations remain totally
dissolved at 0C or as low a storage temperature as can
reasonably be expected to occur for prolonged periods. In
order to insure this, co-solvents, which may be water-
miscible, may also be included in the formulations.
Suspension formulations can be made in water, organic
solvents or in mixtures of water and water-miscible organic
solvents in which the active ingredient has a solubility
under 0.1%. The preparations usually include, in
addition to the active ingredient and liquid carrier, suf-
facts, viscosity control agents and other moidfiers. They
are prepared by grinding the components in a sand mill,
roller mill or pebble mill, preferably until the average
particle size is under 20 microns. It is entirely practical,
and in some instances biologically advantageous, to grind
until a major proportion of active ingredient is 2 microns in
diameter or smaller. Hydrocarbon and other flammable carriers
should have boiling points above'~ 125C for safety in
handling. Suspensions in hydrocarbons are suitable for ex-
tension in spray oils and, by inclusion o~ a suitable emul-
sifying agent, may also be made sprayable from water.
10~5311
Organic liquids suitable for preparation of solutions, suspensionsand emulsifiable concentrates of the compounds of aspects of this invention
include alcohols, glycols, Cellosolves, (the Trade Mark for mono-and dialkyl
ethers of ethylene glycol and their derivatives, of Union Carbide Corporation),
carbitols, ethers, ketones, esters, sulfamides, amides, sulfoxides, sulfones,
paraffinic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons.
Choice of a liquid is dictated by the solubllity of the active compound to be
used and whether a suspension or solution is desired. The class of compounds
represeuted by broad aspects of the present invention is variable in solubili-
ty characteristics, so it is not possible to generalize in the use of particu-
lar solvents for particular purposes.
All compositions intended for spray use can contain minor amounts
of additives to reduce foam, inhibit corrosion, prevent claying, reduce cak-
ing, etc. a~ the conditions of uge may dictate. The conditions of need for
an use of of such additives are generally known in the art.
The compositions of a~pects of the invention can contain, in addi-
tion to the active ingredient of this invention, conventional insecticides,
miticide~, bactericides, nematicides, fungicides or other agricultural chemi-
cal~ e.g. fruit set agents, fruit thinning compounds, fertilizer ingredient~
ant the like, 50 that the compositions can serve useful purposes in addition
to the biocital activity of the compounds of aspects of this invention.
~hi - 18 -
1~65311
Examples of organo-tin sucrose compounds according to aspects of
this invention are given below in Table 1. Many of these com-
pounds have been tested for their biocidal activities and the
results are also given below:
TABLE 1
COMPOUND No
.
(n-butyl)3SnOCOC6H4COO-sucrose
(phenyl)3SnOCOC6H4COO-sucrose 2
(cyclo-c6Hll)3snococ6H4coo-sucrose 3
(n-butyl)3SnOCOCH2CH2COO-sucrose 4
(phenyl)3SnOCOCH2CH2COO-sucrose S
sucrose-OCOC6H4COO(CH2)3Sn(phenyl)2Br 6
(phenyl)3 SnSCH2COO - sucrose 7
The compounds were first tested against the fungi
which commonly grows on paint coatings, both inside and outside
buildings. There are 16 fungi which appear to be most fre-
quently found:
A~ternaria aZternata (syn. tenuis);AspergiZtus fZa~us;
AspergiZtus ver8ico Zor;
Aureobasidium puZZuZans;
CZadosporium herbarum;
;, .
--19--
~065311
Cur~u~ria geicutata;
DendryphieZZa 6aZ*na;
Pus~rium o~yspor~m;
PaeciZomyce~ ~ariot*i;
Penic*ZZium e~pansum;
PeniciZZiu~ purpurogenum;
PestaZotia ~acrotricha;
Phoma vioZacea;
Stachybotry~ atra;
StemphyZium dentriticum; and
Trichoderma ~iride.
'. The compounds of aspects of this invention were tested for
their effectiveness against these 16 fungi by dissolving
the compounds in turn in Cellosolve (Trade Mark for ethylene glylcol mono-
ethyl ether) and incorporating the solution into a Czapek-
Dox agar medium at 100, 10 and 1 ppm by weight. After
- hardening7 the agar plate was inoculated with spore sus-
pensions of the 16 fungi and incubated at 25C for ten days.
Spore germination was then counted; the results are listed
in Table 2 together with the results for tributyltin oxide
used as a control.
. -20-
1()653~1
TA~LE 2
Compound Number of fungi showing inhibition of spore
germination (max.16)
s 1 l ~1
10 ~
.
oxide ..
* inactive against
- As can be seen from Table 2, most of the compounds
show very high activities. The high activity at the 1 ppm
level of some of the compounds is remarkable considering
the much lower tin content of these co.mpounds compared
with standard organo-tin biocides, e.g. the tributyltin
oxide.
.Compounds 1 and 5 were tested for fungicidal activity
in a polyvinyl acetate copolymer emulsion paint having the
following composition:
-21-
10~5311
Tloxide RCR (the Trade Mark of a brand of
titanium dioxide) . . .. . . . . . . . . . . . . . . . 34.2
sodium hexametaphosphate
(4% solution) . . . . . . . . . . . . ~ . . . . . . . 1.3
Celadol M450 (4Z solution)
(Trade Mark ~ . . . . . . . 8.5
water . . . . . . . . . . . . . . . . . . . . . . . . 25.6
Vinamul N6815
(Trade Mark ~ . . . . . . . 30.4
Various concentrations of the two compounds as well as various
concentrations of Amical 48 (Trade Mark for a commercial fungicidal) as a con-
trol were incorporated into this emulsion paint at the pigment dispersion10
stage. The emulsions, including a further control emulsion containing no
fungicide, were brushed onto plaster covered glass boiling tubes and allowed
to dry. One set of painted tubes was tested as made while a second set was
tested after 200 hours of artificial weathering according to British Standard
BS 3900,F3.
Fungicidal testing was started by inoculating coated tubes with a
suspension of mixed fungal spores in 0.01% Tween 80 solution (Trade Mark for
a polyoxyethyle derivative of fatty acid partial esters of sorbital anhydrides
of Altas Chemical Industries) containing not less than 10 spores/ml.
The fungal species employed were:
Alternaria alternata,
Aureobasidium pullulans,
Cladosporium herbarum,
Paecilomyces variotii,
Penicillium expansum, and
Stemphylium dendriticum.
- 22 -
106S3~1
Inoculated tubes were kept under conditions designed
to promote controlled condensation on paint surfaces and
incubated for four weeks. Fungal growth present on painted
tubes after this time was assessed by examination through
a stereoscopic ~icroscope and rated on a 0-5 scale where
0 = no growth and 5 = overall growth.
In addition, all emulsions were stored for four weeks
at 37C and then examined for color, odor and rheology
defects.
10 All of the emulsions appear to have satisfactory
storage properties; no adverse color, odor and rheology
changes were apparent after storage. The results of the
fungicidal tests are listed in Table 3.
TABLE 3
.
CompoundAmount Fungal Growth Assessment
(ppm) as made after 200 h. artificial
weathering
20 controlnone 4 3-4
Amical 48* 0.25 1
Amical 48 0.5 0
Amical 48 1.0 0 0
. .
' ~ ~ ~
_. _
-23-
1065311
Another established application of organo-tin com-
pounds is in anti-fouling paints; the marine alga Enteromorpha
is considered to be mainly involved in the fouling of ships'
hulls.l Compounds of aspects of the invention were tested against
Enteromorpha in sea water modified with algal nutrients at
concentrations of 1 to 0.1 ppm; the results are listed in
Table 4.
TABLE 4
1 0 .
~ ;
+ = effective - = not effective
2S As can be seen from the above,many of the organo-tin
sucrose compounds of aspects of this invention are remarkably active
algicides. For comparative purposes, the minimum concentration
A~
lO~S311
at which the commercially used tributyltin oxide and tributyl-
tin fluoride are effective in these tests is 0. 3 ppm. The
algicidally active sucrose compounds in Table 4 are therefore
at least thre~ times more active, even though these sucrose
compounds have considerably less than half the tin content
of the commercial biocides as shown in Table 5. At a U.S. price
in early March, 1977 of over S10,000 per ton for tin, the
economic savings of higher activity per tin atom can be sig-
nificant.
TABLE 5
Compound % Sn
.
tributyltin oxide 39.8
tributyltin fluoride 38.4
(butyl)35nOCOC6H4COO-sucrose 15.2
(phenyl)3SnOCOC6H4COO-sucrose 14.1
Current technology produces anti-fouling paints with
prolonged biocidal effectiveness by incorporation of the
biocide into a polymer to ensure very slow release of the
- active material. The poly-functional nature of the sucrose
compounds of aspects of this invention ives them the ability to be
readily incorporated into polymers.
-25-
, l ,
`` iO6S311
The anti-bactericidal properties of organo-tin
sucrose compounds of aspects of this invention were tested by growing
the bacteria both on agar plates and in a liquid culture;
the results are given in Table 6.
S
TABLE 6
CompoundEscherichi Saccharomyces Micrococcus
C li cerevisiae dentifrificans
Conc. Inhib. Conc. Inhib. Conc. Inhib.
(ppm) (~) (ppm) (%) (ppm~ (%)
1 2 84 100 8 100 0.25 100
15 1 83 23 8 ~ ~ 100
As can be seen above, only very low concentrations
of the compounds are required to supress the growth of
~ M.denitrificans. ~he minimùm concentration for inhibition
may he even less, since 0.25 ppm was the lowest concentra-
tion tested.
Some compounds of a8pects of this invention, especially compounts
1 and 3, have been found to be effective miticides. ~hey
were tested by the leaf dip method as set out in Table 7
and compared with conventional miticides much as Dibrom
and Tedion. As can be seen from these results, Compounds
1 and 3 were highly effective.
A~i
-26-
T.~ L~ ? 10~3~1
Organism Compound Dose Percentage
. (ppm)Effectiveness
2 Spot Mite 3 40 100
(Tetranychus
urticae Koch) 1 40 100
Dibrom 10 39
Mite Egss 3 40 100
(Tetranychus
urticae Koch) 1 40 96
Tedion 2.5 100
.
Compounds 1, 2 and 3 ~ of aspects of this invention were tested
for their effect against various weeds and crops both for
pre-emergence and post-emergence effects. It was found that -
compound 3 had no noticeable effect at a dose of 33
gm cm~2; this indicates a lack of phytotoxicity which is
important for the use of the compounds as miticide on vege-
tation. Compounds 1 and 2, on the other hand, were found
20to have certain selective effects on weeds and crops and so
appear useful as selective herbidies. For example, com-
pounds 1 and 2 have no effect on rice, but do have a high
degree of toxicity to, for example, wild oats.
Compounds 1 and 2 haYe also been found to exercise
a useful degree of control over the growth of aquatic weeds
when present in water at a dose of 2 ppm. They are at
least as effective as copper sulphate against aquatic weeds
and are also potentially less toxic to aquatic animals, for
example, fish, than copper sulphate.
106S3~1
Without further elaboration, it is believed that
one skilled in the art can, using the preceding description,
utilize the present invention to its fullest extent. The
following preferred specific embodiments are, therefore, to
be construed as merely illustrative.
In the following Examples, the temperatures are set forth uncor-
rected in degrees Celsius; unless otherwise indicated, all
parts and percentages are by weight. The values obtained
in elemental analyses are within commonly accepted limited
of error. All new products give the expected parent peaks
in the mass spectra, and the expected absorption peaks in
NMR and IR.
Example 1
A. Preparation of phthalic half ester of sucrose
An excess of phthalic anhydride was heated with
sucrose in solution in dimethylformamide at a temperature
of 60C for S hours. The reaction proceded as in the fol-
lowing reaction scheme:
[~ O + sucrose ~ o- sucro=e
--28--
106S311
Titration of the resulting ester compound I with stan-
dard alkali showed that the ester had the composition of one
acid group/molecule.
Analysis
Calculated for 1:1 adduct: C 48.98~; H 5.3~;
Found: C 46.6%; H 4.8%;
Characteristic features of I.R
.
OH region 3400 cm~l,
-ICl- 1710 cm~l.
o
B. Preparation of organo-tin compound
The ester I prepared above was reacted with triphenyl-
tin hydroxide or bis(triphenyltin) oxide in solution in-
benzene at 50~C for 3/4 of an hour to give the compound in15
a yield of 83~ by weight, based on the weight of starting
organo-tin compound:
~ C - O-sucrose
11 L
~11--0-SnPH3.
Analysis
Calculated: C 54.4%; H 4.7%;
Found: C 54.6~; H 4.8%.
-29-
106S311
Characteristic features of I.R.
-OH region 3350 cm~l,
(a) 1730 cm~l
-6- (typical of organic esters),
O
(b)
-C- 1640 cm~l,
ll (typical of carboxylate
O group attached to tin),
Ph 730, 695 cm~l.
Example 2
The ester I prepared in part A of Example 1 was re-
acted with bis(tri-_-butyltin) oxide in solution in benzene
. at 40 to 50C for 3/4 of an hour to give the product:
1l
(a) O;sucrose
~ C O-Sn(butyl)3
Analysis
Calculated: C 49.29%; H 6.7%;
Found: C 50.78%; H 7.00%.
-30-
106S31~
Characteristic features of I.R.
OH region 3350 cm~l,
(a) 1725 cm-l,
- lCI-
O
(b)
-C- 1630 cm~l.
o
Example 3
The phthalic half ester of sucrose prepared as
described in part A of Example 1 was treated with sodium
hydroxide to give the sodium salt and the latter was re-
acted with excess Ph3Sn(CH2)3Br in dimethylformamide at
50C for 3 days to give the compound:
C O-sucrose
II
C (CH2 ) 3SnPh3
11
Analysis
Calculated: C 54.95%; H 5.2%;
Found: C 54.6%; H 5.2%.
-31-
10~5311
Characteristic features of I.R.
OH region 3350 cm~l,
1720 cm~l.
O
Ph 925, 690 cm~l.
This compound II was then dissolved in methyl alcohol
and reacted at 50C with bromine to giYe the compound:
11
CO-sucrose
~h III
ICl --- O(CH2)3lnBr
O Ph
AnalysiS
Calculated: C 47.5%; H 4.64%;
Found: C 46.8%; H 5.29%.
Characteristic features of I.R.
OH region 3350 cm~l.
~C- 1720 cm~l.
O
Ph 730, 695 cm~l.
(ObserYed reduction in comparatiYe intensity of phenyl
absorption to carbonyl absorbtion).
This compound III can be hydrolysed, if so desired, to
give the compound:
-32-
1065311
_ , _
~ O(Ch~)33n 1 -O
Example 4
A. Preparation of succinate half ester of sucrose
This material was prepared in a manner similar to
that described in part A of Example 1 for the phthalate
half ester, i.e. a 5:1 mixture of succinic anhydride:
sucrose was heated at 60C in dimethyl formamide for
5 hours:
~0
CH2 C O
11
I O + sucrose - > HOOCCH2CH2 -C - O-sucrose.
CH2 C~
~O
Titration of the product indicated that it had a composition
intermediate between a 1:1 and 1:2 structure.
B. Preparation of organotin derivatives of the succinate
O
Il 11
~ he compound: ~u3SnOCCH2CH2C-O-sucrose was prepared
using reaction conditions similar to those described for the
phthalate derivative, the compound being obtain in a yield
106S31~
of 75% by weight based on the weight of the startins organo-
tin compound.
Analysis
Calculated for 1:1 compound: C 46.96%; H 7.10~;
Found: C 45.95%; H 7.20%.
Characteristic features of I.R.
C=O at 1730 cm~l 1640 cm~
OH 3400 cm~l
Example 5
Ili1
In a similar manner, the compound: Ph3SnOCCH2CH2CO-sucrose
was prepared in a yield of 84%.
Analysis C34H4QO14Sn
Calculated; C 51.6%; H 5.1%;
Found: C 51.4~; H 4.7%.
Characteristic features of I.R.
C=O 1730 cm~l, 1640 cm~
OH 3400 cm~l
Ph 690 cm~l, 730 cm~l.
Example 6
Other Derivatives of Phthalate Half Ester
In a similar manner, the tricyclohexyl tin derivative:
ll
C O-sucrose
O - o-sn(c6Hll)
was prepared in a yield of 80%.
-34-
10~;5311
Analysis C38H5814Sn
Calculated: C 53.2%; H 6.6%;
Found: C 53.1%; H 6.6%.
Characteristic features of I.R.
C=O at 1730 cm~l, 1640 cm~
OH at 3400 cm-l.
Example 7
Methyl-S-triphenylstannylthioglycollate
(2.0 g, 4.4 mmole) was dissolved in 15 ml dimethylformamide
and heated with sucrose (4.5 g, 13.2 mmole) in 45 ml
dimethylformamide and potassium carbonate (0.04 g) at
50~55C for two hours.
The solution was poured into cyclohexane and the
lower layer washed with several portions of cyclohexane
until the majority of the dimethylformamide had been removed.
The resulting semi-solid was extracted with chloroform and
the solvent removed, The purification procedure (cyclohexane
wash, chloroform extraction)was repeated to leave 1.2 g
solid which was found to consist of some unreacted sucrose
and a mixture of substituted products.
- Analysis C32H58O12SSn:
Calculated: C 50.20%; H 4.97%;
Found: C 51.42%; H 5.58%.
-35-
10~531~
The preceding examples can be repeated with similar
success by substituting the generically or specifically
described components and/or operating conditions of this
invention for those used in the preceding examples.
36
