United States Patent 0
3,268,401
Patented August 23, 1966
1
2
3,268,401
synergistic with respect to seed protectant activity. The
according to the invention have been found to be highly
TRIARYLBORANE COMPLEX COMPOSITION AND
METHOD FOR SEED PROTECTION
Herman A. Birnbaum, Mendota Heights, and Harvey L.
buffering agent alone has no effective activity as a seed
protectant while the triarylborane complexes alone are
considerably less active against the damping off and seed
Anderson, Dellwood, Minn., assignors to Minnesota
Mining and Manufacturing Company, St. Paul, Minn.,
decay organisms of the soil and have greater negative
a corporation of Delaware
No Drawing. Filed June 15, 1964, Ser. No. 375,318
16 Claims. (Cl. 167-38)
This is a continuation-in-part of the copending applica
effects on the seeds themselves than do the compositions
of the invention. While the reasons for this synergistic
action are not fully understood, it may be that the seed
10
tion Serial No. 186,874 ?led on April 12, 1962.
This invention relates to the protection of seeds from
soil-borne organisms. In one aspect, the invention relates
to a process for the protection of seeds from soil-borne
safety is improved by decreasing the actual contact be
tween seed and the complex and the effectiveness of the
compositions against the soil-borne microorganisms is due
to the chemical stabilization of the active triarylborane
complexes by buffering them to a pH range in which
organisms. In another aspect, the invention relates to 15 they do not readily degrade. Regardless of the mecha
nism, which has no effect on the invention per se, the
compositions for the treatment of seeds to protect them
compositions of the invention have been found to be
from soil-borne microorganisms.
highly useful seed protect-ants.
Soil-borne organisms which cause decay of crop seeds,
The compositions of the invention are generally applied
damping off of young plants, etc. are responsible for large
scale agricultural losses.
To prevent ‘or reduce these 20 to the seeds at a rate of from about 0.03 to 1.0 ounce
losses, seeds are frequently treated with various chemicals
which are toxic to the organisms. Often, however, levels
of the triarylborane complex and from about 0.09 to 10
ounces of the buffering agent per 100 pounds of seed
of treatment su?icient to protect the seeds from the orga
although greater or lesser rates of application will oc
these complexes without adversely affecting their elfective
extending agents, solid wetting agents, stickers, and the
ness against the soil-borne organisms.
It is therefore an object of this invention to provide a
novel process for the protection of seeds.
It is another object of the invention to provide a new
and valuable class of seed protectant compositions.
It is another object of the invention to provide seed
protectant compositions with little or no phytotoxicity.
It is a further object of the present invention to provide
a process for the protection of seeds from soil-borne
OT-B, primary dioctyl sodium sulfosuccinate; “Renex”
35, polyoxyethylene tridecyl alcohol plus urea; “Triton
X-100” isooctylp‘henyl polyethoxyethanol; “Alkanol B”
sodium alkyl naphthalene sulfonate and fatty alcohol sul
casionally be desirable, depending upon the particular
nisms also adversely affect the seeds themselves (i.e. ex
hibit phytotoxicity). In many cases, a degree of phyto 25 seeds and ?eld conditions encountered. Ordinarily, but
not necessarily, the weight ratio of the triarylborane com
toxicity is tolerated in seed treatments in order to obtain
plex to the buffering agent Will be from about 1:3 to
the desired protection against the soil-borne organisms.
1:10.
Among the most effective seed treating agents are cer
The compositions according to the invention are pref
tain triarylborane complexes (see U.S. Patent 3,062,708).
erably applied to the seeds in solid (dust) formulations
It has been found however that these complexes by them
although slurry or liquid formulations can be used. The
selves or mixed with inert diluents, such as diatomaceous
solid formulations can consist entirely of the triarylborane
earth, clays, etc. are somewhat phytotoxic. It is there
complex-buffering agent composition or additives, such as
fore much to be desired to reduce the phytotoxicity of
like can be added. Thus, hydrated silica, diatomaceous
earth, etc. are suitable extending agents. Mixtures of
triarylborane complexes and/ or mixtures of the buffering
agents can also be utilized in particular seed treatment
compositions of the invention when desired. “Aerosol”
microorganisms.
fates; etc. are suitable solid wetting agents. Low volatility
It is a still further object of the invention to provide 45 solvents such as glycols, heavy mineral, vegetable or ?sh
oils are suitable stickers; etc. The solid (dust) composi
seeds coated with a composition which greatly reduces
tions of the invention can be applied directly by tumbling
the effect of soil-borne microorganisms on them.
them with weighed amounts of seed until the latter is
Other objects will become evident from the disclosure
uniformly and evenly coated with the desired amount of
which follows.
In accordance with the above and other objects of the 50 chemical.
To prepare slurry or liquid seed treatment composi
invention, it has been found that seeds of crop plants
tions, the triarylborane complex and the buffering agent
(such as pea, corn, bean, oat, barley, cucumber, radish,
can be dissolved, along with a suitable surface active
?ax, tomato, etc. seeds) can be effectively protected
agent and possibly other additives if desired, in a solvent,
against soil-borne microorganisms and other destructive
biological agents present in soils by the application thereto
such as water, dimethylformamide, N-methyl pyrrolidone,
of a relatively small amount of a composition comprising
a complex of a triarylborane with a Lewis base having
a pKb less than about 10 in admixture with a ?nely divided
solid compound which buffers to a pH above about 6 in
its saturated solution. As used herein the buffer includes 60
acetone, methanol, tetrachloroethylene, methyl chloro
form, methylene chloride, chloroform, mineral oil and
not only compounds which resist any change in pH upon
addition of acid or alkali but also those which resist a
decrease of the pH to below about 6 but do not resist in
creases in pH.
The preferred buffers of the invention
buffer to a pH of from about 7.5 to 12.5.
The triarylborane complexes and the buffering agents
the like. The slurry or liquid seed treatment composition
can then be applied to the seeds using known techniques,
e.g. with a conventional slurry treater or by spraying or
tumbling onto the seeds.
Broadly speaking, the process for the preparation of
the triarylborane complexes comprises preparing an ether
solution of the triarylborane and introducing the desired
Lewis base. The complexes appear to form in mol-for
mol proportions, and ordinarily, there is immediate pre
3,268,401
3
4
cipitation of the ether-insoluble complex. The operation
Triphenylborane-pyridine _____________ _. 182-202“ C.
is carried out in the absence of air. Speci?c directions
Triphenylborane-3,S-dichloro-pyridine .___- 1l2—'l15° C.
for the preparation of the complexes of triphenylborane
Triphenylborane-bis(4-pyridyl) glycol ____. 173—181‘’ C.
are set forth in Berichte, vol. 57B, p. 813 if, 1924, while
other triarylboranes and their complexes are described
in the same Journal, vol. 61B, p. 271, 1928; vol. 6313, p.
Triphenylborane-v-picoline ___________ __ 135-—145° C.
Tn'phenylborane-imidazole ___________ __ 185-190" C.
Triphenylborane-sodium hydroxide ____ .. White solid,
934 if, 1930', and vol. 6413, p. 2112, 1931; and in An—
nalen, vol. 573, p. 195, 1951.
does not
melt below
300° C.
The triarylborane portions of the complexes are ex
empli?ed by triphenylborane, alkyl-substituted triphenyl
Tri(a-naphthyl)borane-ammonia ______ __
153—157° C.
boranes such as tri-p-tolyl borane and tri-p-xylyl borane,
halogen-substituted triphenylboranes such as tri-(p-?uoro
Tri(a-naphthyl)borane-diethylamine _____
Tri(u-naphthyl)borane-trimethylamine .___
Tri(p-?uorophenyl)borane-arnmonia _____
Tri(p-?uorophenyl)borane-triethylamine ._.
Tri(p-methoxyphenyl)borane-ammonia __.
170-175° C.
156—l58° C.
179 181° C.
110~115° C.
138-142” C.
phenyl) borane, alkoxy-substituted triphenylboranes such
as triphenetyl borane (i.e. tri-p-ethoxyphenyl borane) and
tri-(p-methoxyphenyl) borane, trinaphthyl borane, aryl
substituted triphenylboranes such as tri(p-biphenyl) bo
rane, aryloxy-substituted triphenylboranes such as itri(4
Tri(p-tolyl)borane-ammonia __________ _. 1143-156" C.
1The Duomeens are products of Armour and Company of
phenoxyphenyl) borane, arylthio-substituted triphenyl
Chicago, Illinois.
Chemically they are N~alkyl trimethylene
diamines. The alkyl group in Duomeen S is derived from
soya. fatty acid, in Duomeen 12 is derived from Cm fatty acid
and in Duomeen C is derived from coconut fatty acid.
boranes such as tri(4-phenylthiophen§,rl) borane and the
like. Triphenylborane is preferred in the‘ formation of 20
the complexes used in the invention because it is readily
'Among the buffering agents useful for purposes of the
prepared from chlorobenzene and bromobenzene, which
invention are the following: barium acetate, barium hy
are readily accessible, and is highly effective in the process
droxide, calcium acetate, calcium hydroxide, calcium sul
of the invention. A convenient method for the prepara
fate, lithium carbonate, lithium hydroxide, magnesium
tion of triphenylborane is the reaction of a metallic deriva 25 acetate, magnesium carbonate, magnesium phosphate,
tive of bromobenzene such as phenyl magnesium bromide
magnesium sulfate, nickel acetate, potassium acetate,
with boron tri?uoride, as described in Berichte, vol. 55B,
potassium bicarbonate, potassium carbonate, potassium
page 1261 (1922).
phosphate, potassium sulfate, sodium acetate, sodium bi
The term pKb is used herein in its conventional meaning,
carbonate, sodium carbonate, sodium phosphate, strontium
i.e. the negative logarithm of the ionization constant Kb. 30 acetate, strontium sulfate, zinc acetate, etc.
Lewis base complexing agents suitable for use in the prep
The following examples illustrate methods and composi
aration of the complexes are, for example, ammonia (pKb
tions used in practicing this invention, but are not to be
4.74), methylamine (pKb 3.19), dodecylamine (pKb 3.7),
n-tetradecyl amine (pKb 3.8), ethylenediamine (pK,a
construed as limiting the scope thereof in respect of the
compositions or complexes to be employed, or the orga
4.07), hexamethylene diamine (pKb ca. 4), tetrahydro
furfuryl aminoethanol (pKb ca. 5), acetylacetone imide
(pKb ca. 5), benzy-lamine (PK;D 4.62), triethylenetetramine
The seed treatments of the invention are evaluated in the
(pKb ca. 3), N-alkyl propylene diamines such as 12-(N
tests and in ?eld tests. The details of the application of
nisms to be subjected to the compositions of the invention.
examples using Pythium soil and vermiculite greenhouse
dodecyl propylamine) (pK;J ca. 3), dimethylamine (pKb
3.31), di-n-propylamine (pKb 3.0), N-methylethanol
amine (pKb ca. 5), piperidine (pKb 2.79), piperazine
(pKi, 4.19), morpholine (pK~D ca. 5), trimcthylamine
(pKb 4.13), tri-n-propylamine (pKb 3.26), 3-dimethyl
aminopropylamine (pK;J ca. 4), tributylphosphine (pKb
the treatments and of the tests are as follows:
40
APPLICATION OF THE SEED PROTECTANT
COMPOSITIONS
Weighed amounts of the ?nely divided components of
ca. 3), phenyldiethyllphosphine (pKb ca. 4), phenyldipro 45 the seed protectants and of the seeds are tumbled together
until the seeds are uniformly and evenly coated. In cases
Where the triarylborane complexes are liquids, they are
mixed with and adsorbed by the solid components of the
pylphosphine (pKb 3.4), pyridine (pK,J 8.64), 3-bromo
pyridine (pKb 7.82), 'y-ethylpyridine (p-Kb ca. 8.6), 3-(4
pyridyl)-propanol-1 (pKb <8.6), 3,5-dichloro-pyridine
(pKb ca. 9) , bis(4-pyridyl)glycol (pKb ca. 8.6), nicotine
seed treatment before the seeds are added.
(pK-n 6.05), isonicotinic acid (pKb 021.10), n-butyl ni 50
PYTHIUM SOIL TEST
cotinate (p-Kb ca. 8.7), nicotinamide (pKb 8.64), isoni
This test' primarily measures the control of the Pythium
cotinic thionamide (pKlJ ca. 9), ?-picoline (pKb 7.96), 'y
organism by the seed treatment. Pythium is responsible
picoline (pKb 7.96), imidazole (pKb 4.37), metallic bases
including alkali and alkaline earth metal hydroxides, such
annually for important economic losses and its control
as sodium hydroxide (pKb <1), potassium hydroxide 55 per se is of great value. This test, in which the treated
seeds are subjected to soil which is heavily infested with
(pKh <1), and the like.
the microorganism, however, serves as a dependable gen
The following descriptions, including uncorrected melt
ing points where available, of a number of the complexes
will serve to characterize them and are generally illus
trative of the complexes useful in the invention.
eral screen for the evaluation of the general effectiveness
of seed protectant compositions against soil borne micro
60 organisms and other destructive biological agents present
in soils (e.g. Rhizoctonia, Pythium, Anthracnose, etc.).
M.P. or appearance
The treated seeds are planted in four-inch plastic pots
Triphenylborane-ammonia ____________ _. '179—183‘’ C.
Triphenylborane-methyl amine ________ _- 195-213“ C.
Triphenylborane-dodecyl amine _______ __ Tan grease.
containing soil heavily infested with Pythium. The pots
Triphenylborane-n-tetradecyl amine ____ _. Tan oil.
Triphenylborane-triethylenetetramine ____. 75-84" C.
Triphenylborane-duomeen S 1 _________ _. Red,l viscous
'
Triphenylborane-duomeen 12 1 ________ .__
Triphenylborane-duomeen C 1 _________ _.
Triphenylborane-dimethylamine _______ __
Triphenylborane-piperidine ___________ __
Triphenylborane-piperazine ___________ ._.
Triphenylborane-trimethylamine _______ _.
o1
.
Do.
Do.
157—166° C.
Ivory wax.
l70—175° C.
132-138“ C.
are held in a refrigerator at 45° F. to 50° F. for a period
65 of four days and are held for the remainder of the tests
at approximately 75° F. The moisture level is maintained
at about 25 percent of the water holding capacity of the
soil. The lower temperature provides optimum conditions
for the growth of the fungus organisms and relatively ad
verse conditions for the germination of the seeds while
the higher temperature favors the seed germination. The
results of this test are measured as percent emergence (the
percentage of the seeds planted which send shoots up
through the surface of the soil), average weight in grams
75 per pot of plants resulting from seeds planted in Pythium
3,268,401
5
6
soil (measured 17 days after planting) and height in inches
of the plants (measured 17 days after planting). The
(3) Triphenylborane-ammonia complex alone (5% of
essentially pure silicon dioxide added to- render the chem
ical physically adaptable to a seed treatment preparation)
average weight and height in inches are measured relative
to the portions of the plants above the soil level. Control
lots of untreated seeds are generally included.
(Lot F)
5
(4) Buffering agents alone (Lots G-I)
Inert diluents alone (Lots J-K)
( 5) No
(6)
treatment (Lot L)
VERMICUI.*1TE TEST
This test measures the effects of seed treatments on
In these tests 20 seeds are planted per pot and 5 rep
the seeds in the absence of the disease factor. Treated
licates (pots) are used for each individual treatment. One
and untreated seeds are planted in separate four-inch plas- 10 ounce ‘of seed treatment per bushel of seeds is used in
tic pots containing vermiculite of relatively small particle
every case.
Additive
Triphenyl
Lot
borane
ammonia
complex
(percent by
Pythium Soil
' Percent
Name
Percent
by
weight
weight)
vermiculite
Average
Emergence
plant
weight
per pot
Percent
Emergence
Average
plant
weight
per pot
25
Calcium hydroxide _______ __
75
95 .0
7 .2
96 .0
6 .3
25
Mangesium carbonate.
75
98 .7
7 .3
96 .0
5 .3
Ca Acétate 10
Bentonite 5%.
75
96.0
8.6
94.6
6.7
Diatomaceous
75
92 .3
5 .6
90 .6
3 .1
ICIMOHh
507
_
g
__
25
25
.
25
Kaolin _______ __
75
93 .3
5 .3
90 .6
3 .2
95
0
0
Silicon dioxide-__
Calcium hydroxide.
Magnesium carbonate.
5
100
100
90.7
30 .8‘
16 .7
4.8
0 .9
0.3
92.0
78 .6
69 .3
3.7
5 .8
6 .5
?a(OH)1z0570%_______
Ca Ac§me°m%_
100
38.7
0.8
85.3
6 1
‘100
24.0
0 6
70.7
2 9
g
0
__,..
Bentonite 5%_____
0
Diatomaceous eart
0
K21 1n ____________________ _-
size. The treatment and observation of the test pots are
' '
'
100
13 .7
0 2
92.0
6 1
33.3
0 6
89.3
4 4
These test results indicate that the seed protectant com
the same as in the Pythium soil test.
positions of the present invention (Lots A-C) are highly
35 effective against the test organism (Pythium) and have no
FIELD TEST
measurable phytotoxicity. The seed protestant composi
This test is run in mineral soil which is well infested
tions of the triphenylborane complex in admixture with
with a generalized population of damping otf and seed
an inert diluent and of the complex in essentially pure
decay organisms. Six replications of 100 seeds per treat
form (Lots D-F) exhibit signi?cant phytotoxicity both
ment are planted in randomized row plots 20-22 feet long. 40 in the percent emergence and in the average plant Weight
The crops are observed for percentages emergence.
in both Pythium and vermiculite tests and less effective
The pH values given relative to the buffering agents
activity against the test organism. The seed protectant
are those to which they buffer in their saturated aqueous
compositions containing none of the triphenylborane corn
plex exhibit little or no advantage over the untreated seeds.
solutions.
Example 1
In this example the relative e?’ects of the following
Example 2
In this example the relative effects of various treatments
45
treatments on Laxtons Progress pea seeds are compared:
on Laxtons Progress pea seeds are noted. The treatments
( 1) Triphenylborane-ammonia complex with buifering
include ( 1) various buffering agents alone, (2) the tri~
agents according to the invention (Lots A-C)
phenylborane-amm'onia complex alone and (3) composi
(2) Triphenylborane-ammonia complex with inert dil 50 tions according to the invention of triphenylborane-am
uents (Lots D-E)
monia with various buffering agents.
Seed Treatment Composition
Test Results
‘
Triphenyl-
Amount
of seed
Percent
borane-
Percent
treatment
emer-
ammonla
Buffering agent
by weight
(oz./bu.)
gence
complex (per-
Name
pH
cent by weight)
___
'
Barium Acetate ____ __
_
Magnesium Carbonate. .
_
Magnesium Sulfate_
Calcium Hydroxide
Calcium Acetate. __
Potassium Carbona
Potassium Bicarbonat
Potassium Phosphate
Potassium Bicarbonat
-
.
‘
6—7
12.5 ___________ _.
soil
ulite
1.0
73
73
56
1. 0
0
100
41
100
1. 0
0
97
>7
100
1. 0
0
95
~7
12. 4
100
100
1.0
1. 0
0
0
98
95
100
1. 0
O
98
11. 6
~8. 5
>9
~8. 5
6. 35
100
100
100
87. 5
1.0
1. O
1.0
1. 0
0
0
O
83
93
97
97
80
>9
87. 5
' - 0. 5
72
1.0
97
73
> 0.5
68
85
*
76
Magnesium Carbonate ______ __
>7
87. 5
1.0
83
98
Calcium Hydroxide _________ -_
12. 4
87. 5
0. 5
1. 0
65
83
93
82
>
25.0.
gence
vermic
0. 5
'
Potassium Phosphate _______ ._
'
0
N7
emer
Pythium
100
'
Potassium Sulfate ___________ _.
Percent
0. 5
_____do
Calcium Acetate ____________ _.
12. 4
6. 35
.
75.0
87. 5
.
72
85
1. 0
85
72
0. 5
92
87
1. 0
86
88
0.5
88
85
3,268,410
Example 3
I
In this example Pythium soil tests and vermiculite tests
'
v
Buffering Agent
are utilized to compare the growing characteristics of
-
~
P
'
Laxt'ons Progress pea seeds treated with compositions of 5
Name
the invention consisting of various buffering agents and
the triphenylborane-ammonia complex with those of untreated pea seeds of the same type.
‘
'
PH
A
The seed treatment
'
Te?“ Results
- -
P
ercent
t
ercen
Emergence Emergence
Pythium
5°11
Verrnie
“me
,
compositions are 121/2 percent triphenylborane-ammonia
ggég’éf‘i-IIIII
g
g?
2%
complex, 75 percent buffering agent and 121/; percent
Magnesium Phosphate _________ ._
~7
79
88
?nely divided silica, the latter being added as an aid in 10 lg?gggglllénfcglggggj3:333:33;
:3
2%
3%
17.2
.
$2
__
>11
73
‘
__
(1.21%
it
2%
15 Calcium Sulfate ________________ __
6.25
65
35
compounding
‘
the mixture.
The rate ‘of
. seed treatment in
itrgntiumj
1 mm ar
Slléfatet
0H3 ______________
8 ________ __ __
_-
all cases is 0.5 ounce per bushel of seeds.
Lithium Hydroxide ________ __
.
>
Buffermg Agent
Test Results
Name
Percent
8211*“ 1133i“ ------ "
0111111
(36
a e __________ __
.
90
Percent
pH
Emergence
Emergence
_
Pythium
Vermie-
Soil
ulite
,
20
goutrol
(Ugtregtedtseeds) ________________
__
otassium at 0113. e __________ __
11.6
0
85
£7319
Potassium Bicarbonate _________ _-
~8. 5
79
90
*1§§‘f,§§§;t-e-_-_-_j:::
313
53
g;
Potassium Siniate ______________ -_
~7
s1
90
233113 §§*;‘f;§§;f§.-e~_;:;:;;;;;
£12
godium Acetate ________________ __
>9.0
‘321% £$ISIIIJI§§ZIIIIITf
:3
Barium Acetate ................ _-
6-7
Example 4
The following table presents data from tests run on
Laxtons Progress pea seeds treated with a variety of com
3? 25 positions according to the invention, both the triaryl
73
86
90
borane complex and the bu?t'ering agent being varied.
33
The seed protect-ant compositions of this example all
90
contain 25 percent of the triarylborane complex and 75
percent of the bu?ering agent.
Seed Treatment Composition
Triarylborane Complex
Test Results
‘Amount
Buffering Agent
of seed
-
pKb= oi
Lewis
Name
Name
Pythium Soil
0z.,fbu.
pH
Base
Control. . none
_________________________ _ _65l__4_-_.?__&r_---Ci
---- __ "-51
_______ “in
.
011.1111
31 0x1 e.____
.
‘?aB'Pyndme ------------ --~---- 8-64 {____dn
%
Do ______________________ __
8. 64
Magnesium Sulfate .... __
~7
1
Do ______________________ __
8. 6.4.
>7
1
¢3B-Dodecy1amine ___________ _-
' 3. 7
Magnesium Carbonate. _
_
Calcium Hydroxide---"
Bis—¢3B-Piperazine __________ __
4.19
-___.do __________ _; _____ __
Calcium Acetate: _____ __
vermiculite
treatment,
Plant
Ht. in
Percent
Emerg-
Plant
Ht.‘ in
ence
Inches
ence
Inches
72
74
111.5
.5
1,5
385
93
1.8
1.
20
1. 7
28
' 1. 0
93
1%
47
1.0
98
1.7
%
38
53
94
1. 2
1.2
1. 5
95
95
90
1. 8
1.8
1. 8
IA
92
1. 5
93
1.5
95
1.4
95
1.9
ye
68
1. 5
90
1.9
1
31
0. 8
90
1. 6
1.0
12. 4
‘
1
12.4
1
¢3B'NaOH __________________ __
<1
¢3BeMethyl Ethanolamine-____
ca. 5
Calcium Hydroxide".--
12. 4
1y2
375
.54
Do ______________________ __
ca. 5
Potassium Bicarbonate-_
~8. 5
1
83
1. 1
62
n
87
1.3
82
2. 79
Calcium Hydroxlde_____
12. 4
1
95
1. 5
98
1.8
1A
97
1. 5
98
1.8
93
1.5
95
1.8
IA
95
1.5
90
1.7
87
1. 5
85
1. 5
%
90
1. 5
96
'
6. 35
Percent
Emerg-
_
¢3B-Piperidine ______________ __
¢;B-Diethylene Triamine .... __
.
ca. 3
_-___d0 _________________ _.
ca. 3
Barium Acetate ....... __
e
Do ______________________ __
12.4
1
6-7
1
'
Do ______________________ __
ca. 3
Potassium Acetate ____ -_
10‘
1
¢3B~Trirnethylamine ________ __
Do ______________________ __
4. 13
Calcium Hydroxide".-.
12. 4
1
4. 13
Potassium Phosphate.--
9
1
¢3B~Amm0nia _______________ _.
4. 74
Calcium Hydroxide".-.
12. 4
l
%>,
%
%
%
87
1. 2
.
93
92
1.2
90
1.5
1. 7
1. 4
1.5
90
1. 3
98
as
1.8
89
1.3
1.3
68
96
1, 2
92
1. 3
92
1. 6
85
89
89
1.3
1.3
93
l. 6
1.5
1.3
,
3,268,401
19
Similar advantages over untreated seeds are obtained
when treating compositions in accord with the invention
containing tri(ot-naphthyl) borane- ammonia, '[I‘i(oc
naphthyl) borane-diethylamine, tri(a-naphthyl) borane
trimethylamine, tri(p-?uoropheny1) borane-ammonia,
tri(p-?uoropheny1) borane-triethylarnine, tri(p-methoxy
phenyl) borane-ammonia, tri(p-tolyl) borane-ammonia,
tri(p-bipheny1) borane-ammonia, tri(4-phenylthiophenyl)
borane-ammonia, tri(4-phenoxypheny1) borane-ammonia,
etc., are used.
Example 5
A number of other ‘compositions according to the
invention are evaluated in. this example on Laxtons
Progress pea seeds.
Test Results
Amount
_
of seed
Seed Treatment Composition (percent by weight)
Pythium Soil
tz-eatligierit
oz.
Percent
Aver.
Percent
Aver.
ence
wt./pot 1
ence
wt./pot 1
Emerg-
~
Plant
7
Control, none
Calcium Hydroxide (75), Magnesium Carbonate (10),
Calcium Acetate (10), Bentonite (5) .... __
Do__.
Do____
___-
1
%
y.
,
__
qsgBtrimethylamine (25), Calcium Hydroxide (75)
vermiculite
u.
1
Emerg~
0.18
Plant
85
3. 28
0
0
88
3. 31
0
0
92
3. 92
0
0
0
0
0
0
92
98
92
3. 54
3.67
2. 77
88
3.85
95
5.47
Do__ _
%
95
4.68
92
4. 24
Do __________________________________ __
M
88
4. 08
87
¢;B-ammonia (25), Magnesium Carbonate (
D ___
D0____
1
%
M
_
¢3B-ammonia (10), Calcium Hydroxide (65), Magne
3. 72
85
3. 31
98
4. 76
83
70
3. 42
2.46
95
92
4. 48
3. 91
4. 44
sium Carbonate (10), Calcium Acetate (10), Benton
ite (5)_._
‘
'
1
D0--D0___
75
2. 77
97
%
85
3. 83
98
M
85
5. 53
92
85
3. 43
97
4. 60
%
92v
4. 88
93
2.77
%
92
5.00
97
3.57
88
-_
qSgB-ammonia (15), Calcium Hydroxide (60), Magnesium Carbonate (10), Calcium Acetate (10), Bentonite (5)____
0___
3. 67
.
3. 74
.
1
____ __
Do__._
oaB-ammom'a (20), Calcium Hydroxide (55), Magne
sium Carbonate (10), Calcium Acetate (10), Benton
ite (5)___
Do__-
1
v
Do__.
___-
_
___.
3. 22
95
3. 33
%
97
6. 52
98
3. 23
M
97
7.19
97
3.89
98
98
97
3. 59
3.17
3. 31
qSaB‘ammonia (25), Calcium Hydroxide (50), Magne-
.
sium Carbonate (10), Calcium Acetate (10), Benton
ite (5)____
D0--.
Do__.
1
%
)4
90
92
100
4. 48
5. 12
5. 87
1 There are three plants per pot. The value reported is the total weight in grams of the tops (i.e. the portion
above the soil or vermiculite level) of all three plants.
Example 6
The following tests are on Golden Cross Bantam
sweet corn seeds.
Seed Treatment Composition
Triphenyl-
Test Results
Buffering Agent
borane
ammonia
complex (percent
Name
pH
by weight)
,
_
Percent
Amount
of seed
Percent
treatment
emerg-
(oz./bu.)
ence
soil
___
12.5 ___________ __
Barium acetate ______________ ._
6-7
87. 5
1
12.5 ___________ ._
Potassium Carbonate _______ -.
11.6
87. 5
1
‘
‘A
%
$6
%
12.5 ___________ __
Magnesium Carbonate ______ ..
12.5 ___________ __
Magnesium Sulfate __________ ._
>7
~7
87.5
87.5
1
1
%
$4
1A
M
12.5 ___________ __
Potassium Sulfate ___________ _.
~7
87. 5
1
12.5 ___________ __
87. 5
1
50 __________________ ..d0 ...................... -_
12. 4
12. 4
75
50
95
92
92
92
95
82
68
93
93
83
80
65
88
88
~8. 5
25 __________________ __do ______________________ ._
82
95
42
Potassium Bicarbonate ______ __
87. 5
72
72
72
1%
14
87.5
12. 4
93
93
90
88
>9
Calcium Hydroxide _________ __
90
66
83
. 95
88
, 90
87
86
Potassium Phosphate _______ __
12.5 ___________ __
92
70
90
95
87
93
87.5
’
96
82
88
6.4
12.5 ___________ __
8
92
1A
M
1
%
M
1
Calcium Acetate.-. ________ -.
-.
ence
vermic
ulite '
90
~
12.5 ___________ __
emerg_ .
pythium
by weight
Control, none--- Control, none-
Percent
92
85
92
92
83
92
95
95
82
73
%
54
90
89
93
72
%
14
95
88
72
93
%
%
1
1
‘A
M
1
93
89
87
92
70
80
3,268,401
11
12
Example 7
divided compound butters to a pH of from about 7.5
to 12.5.
The following are ?eld tests which demonstrate the
13. A composition comprising a complex of a triaryl
value of the compositions of the invention on various
borane selected from the class consisting of triphenyl
crops under normal conditions of use.
Seed
Seed treatment composition
Corn (Golden Cross Bantam sweet corn). _ _ _ _
None, control- _ _
_
Dosage
Test results
(oz.{100 lb.
of seed)
(percent
emergence)
._
o
25% @Bamrnonia, 75% calcium hydroxide ________ _.
Cucumber (SMR-12) pickling cucumber)“ ___ None, control-"
_
Do
25% ‘NB-ammonia, 75% calcium hydroxide ________ __
Do
25% qseB-ammonia, 2.156% calcium hydroxide, 37%%
magnesium carbonate.
Cotton (Machine delinted Stoneville No. 7) ___ None, control--_
_____
.
Do
25% qsgB‘ammonia, 75% calcium hydroxide ________ __
Do
‘Do
___
_____
do
_-__.
25% ¢3B~ammonia, 37%% calcium hydroxide, 336%
magnesium carbonate.
Peas (Alderman) ____________________________ __
None, control"-
..
l
2
6
56. 2
1%
24. 0
31. 7
3
35.2
3
36, 5
_
64. 6
Do ___________________________________ __ None,
25% d¢3B
control___
ammonia, 75% calcium hydroxide ________ _.
é _-
25%dqsgBxammonia,
__.._ ?
75%
____
calcium
_..
hydroxide ________ __
11 2
25% ¢3B ammonia, 37%% calcium hydroxide, 37%%
$6
~
66. 8
77. 3
29. 0
50. 5
31
40
magnesium carbonate.
Sorghum (Midland) _____________________ _______
None, control_
_
_
22
Do ______________________________________ __
25% anti-ammonia, 75% calcium hydroxide ________ __
%
32
Do
25% (MB-ammonia, 3i'%% calcium hydroxide, 335%
magnesium carbonate.
%
31
borane, alkyl-substituted triphenyl-borane, halogen-sub
What is claimed is:
stituted triphenylborane, alkoxy-substituted triphenyl
1. The method of protecting seeds from soil dwelling
organisms which comprises applying to said seeds before 30 borane, trinaphthyl borane, tri (p-biphenyl) borane, tri
(47phenoxyphenyl) .borane and tri-(4-phenylthiophenyl)
planting a composition comprising a complex of a triaryl
borane with a Lewis base having a pKb less than about
borane selected from the class consisting of triphenyl
borane, alkyl-substituted triphenylborane, halogen-sub
stituted triphenylborane, alkoxy-su'bstituted triphenyl
borane, trinaphthyl bo-rane, tri-(p-biphenyl) borane, tri
10 intimately intermixed with a ?nely divided solid com
pound which buffers to a .pH above about 6 in its saturated
aqueous solution.
(4~phenoxyphenyl) borane and tri-(4-phenylthiophenyl)
14. A composition comprising a complex of triphenyl
borane with a Lewis base having a pKb less than about
10 intimately intermixed with a ?nely divided solid com
pound which bu?ers to a pH above about 6 in its saturated
aqueous solution.
15. A composition comprising a complex of a tria-ryl
borane selected from the class consisting of triphenyi
borane with a Lewis base having a pKb less than about
10 intimately intermixed with a ?nely divided solid com
pound which buifers to pH above about 6 in its saturated
aqueous solution.
' 2. A method according to claim 1 wherein the Lewis
'base is pyridine.
3. A method according to claim 1 wherein the Lewis
base is dodecylamine.
borane, alkyl-substituted triphenylborane, halogen-sub
stituted triphenylborane, alkoxy-substituted triphenyl
borane, trinaphthylborane, tri-(p-biphenyl) borane, tri
(4-phenoxyphenyl) borane and tri-(4-phenylthiophenyl)
'
4. A method according to claim ‘1 wherein the Lewis
base is piperizine.
borane with ammonia intimately intermixed with a ?nely
divided solid compound which bu?’ers to a pH above
about 6 in its saturated aqueous solution.
'6. A method according to claim 1 wherein the Lewis
'16. A composition comprising a complex of a triaryl
base is piperidine.
'
‘
50
borane selected from the class consisting of triphenyl
v7. A method according to claim 1 wherein the Lewis
5. A method according toclaim ‘1 wherein the Lewis
base is anethylethanolamine. .
:
'
rborane, alkyl-substituted triphenylborane, halogen-sub
base is diethylenetriamine.
8. A method according to claim I wherein the ‘Lewis
base is trimethylamine.
_
stituted 'triphenylborane, alkoxy-substituted triphenyl
borane, trinaphthyl'borane, tri-(p-biphenyl) borane, tri
(4-phenoxyphenyl) borane and tri-(4-phenylthi-ophenyl)
_
‘9. A method according to- claim 1 wherein the ?nely
divided solid compound is magnesium carbonate. ,
borane with a Lewis base having a pKb less than about
_,
10 intimatel'y'iutermixed with ?nely divided solid calcium
hydroxide.
organisms which comprises applying to said seeds before
planting a composition comprising a complex of triphenyl
References Cited by the Examiner
‘borane with a Lewis base having a pKb less than about 60
' 10. The method ‘of protecting seeds from soil dwelling
” j UNITED STATES PATENTS
10 intimately intermixed with a ?nely divided solid com
pound which buffers to a pH above about 6 in its saturated
'aqueous solution.
3,062,708
3,140,977v
"
- 11. The method according to claim 10 wherein said
Lewis base is ammonia.
'
12. A method according to claim 1 wherein the ?nely
65
JULIAN
11/1962
7/1964
Updegra?? _________ __ l67—30
Duyfjes et a1 _______ __ 167~—30
LEVITT, Primary Examiner.
GEORGE A‘. vMENTIS. Assistant Examiner.