Note: Descriptions are shown in the official language in which they were submitted.
5~2 ~37
NEW UREA COMPOSITIONS OF MATTER
This invention relates to new chemical composi~ions of
matter and more specifically ~o new urea compounds of the for-
mulas:
C~ 3 ~H--C--N--cn2--C ~=
H C--C
CH3
or
,
~ H3 / ~IH2~n
CH3 O - \ C
~ H C - F - N
c~3
(I)
wherein R is lower aikyl9
n is 0 or 1 and ~ -
m is 0 or an integer fro~ 1 to 6~ .
The preferred compounds have ~he s~ructural formula:.
25 ~ N - C -N - C~2-C _ ~ (CH2)n
C11~3 0 \--C
~13C - C ~ / N
C~3 (II)
The compounds of ~he presen~ invention are particularly
useful as herbicides.
The ~erm "lower" 85 used herein designates a straight
or branched carbon chain of up to six carbon atomsO
'' ~
~ 9S ~ 2
.
The compounds of the present invention can be prepared
by reac*ing a compound of the formula:
r O-~=N~
~ N CH;
0
or
is ~ o=c nr~
N C ~ CH3
CH3
_ 2 (III)
wi~h two molar amounts of an amine of the formula:
" /~F
CH3 \o~
This reaction can be effected by heating a mixture of
ths isocyanate dimer and the amine in an inert reaction medium
such as toluene with warming and stirring until the reactants
dissolve. After this occurs, the product can be recovered by
standard procedures for the removal of th~ solvent and can be
further purified by standard procedures.
The isocyanate dimer of Formula III can be prepared by
reacting a compound of ~he formula:
.
s~
CH3 ~ NM2 CH3 ~ NH2
H3C - C ~ / N or ~H3 ~
(V)
with a molar excess of phosgsneO
This reaction can be performed by adding a slurry o~
solution of the compound of Formula V in a suitable organic
solvent, such as toluene, to a saturated solution of phosgene
in an organic solvent, such as toluene. The resulting mixture .
can be stirred at ambient temperatures for a period of from
about 4 to about 24 hoursO This reaction mixture can then be
purged with nitrogen gas to remove unreacted phosgene~ followed
by filtration, if the desired product forms as a precipita*e,
or by evaporation if the product is soluble therein. It can
be used as recovered or further purified.
; The following examples illustrate the preparations of
the compounds of the present invention,
EXAMPLE l
PREYARATION OF 5-t-Butylisoxazol-3-~
ISOCYANATE DIMER
A solution of phosgene (12~) in toluene (80 ml) was
charged into a glass reaction vessel equipped with a mechanical
stirrer. A slurry of 5-t-butyl-3-aminoisoxazole ~4 grams~ in
toluene ~20 ~1~ was added to the reaction vessel and the re-
sulting mixture was stirred for a period of about 16 hours
resulting in the formation of a precipita~e. The reaction
mixture was ~hen purged with nitrogen gas to remove unreacted
phosgene. The purged mixture was then filtered ~o recover
the desired product, 5-t-butylisoxazol-3-yl isocyanate dimer
as a solid.
- EXANPLE 2
PREPARATION~ lisoxazol-3~x13 -3-Methyl-3
3S
-3
`
A mixture of S-t-butylisoxazol-3-yl isocyanate dimPr
(5 gTams) r N-(1,3-dioxolan-2-ylmethyl)methylamine (4 grams)
and toluene (100 ml) were charged into a glass reaction flask
equipped with a mechanical stirrer and thermometer. The reac-
tion mixture was then warmed with stirring until the reactantsdissolved. After this ~ime ~he reaction mixture was stripped
of solvent and the residue was recrystallized from ethyl ace-
tate ~o yield the desired product as a solid having a ~elting
point of 130 - 131C. Its elemental analysis was:
C H N
%
Theoretical 55.11 7.47 14.83
Found 54.36; 54~56 7L47; 7.4814.45; 14.52
EXA~PLE 3
PREPARATION OF 1-~5-t-But lisoxazol-3- 1)-3-Meth 1-3-
- Y y y _ _
(1,3-Dioxan-2-ylmethyl~ Urea
A mixture of 5-t-butylisoxazol-3-yl-isocyanate dimer
(5 grams), N-~1,3-dioxan-2-ylmethyl)methylamine ~4O5 grams)
and toluene ~100 ml) were charged into a glass reaction flask
equipped with a mechanical stirrer and thermometerO The reac-
tion mixture was then warmed with stirring until the reactants
dissolved. Hexane (50 ml~ was added ~o the reaction mixture
and the desired product was recovered as the precipitate having
a melting point of 171 - 173C. Its elemental analysis was:
C H N
~ ~
Theoretical 56~55 7.8 14.13
Found 55.79; 55.9S 7,8; 7.94 13.85; 13.96
Exemplary of the compounds within the scope of the
present invention that can be prepared by the procedures o
the preceding examples areo
1~3-t-butylisoxazol-5-yl)-3-me~hyl-3-~1,3~dioxolan 2 yl-
methyl) urea
1-~3~t-butylisoxazol-5-yl)-3-methyl~3-~1,3-dioxan-2-yl-
.4_
l' -
,t~
methyl~ urea
1-(5-t-butylisoxazol-3-yl~-3-methyl-3-(4,5-dime'chyl-193-
dioxolan-2-ylmethyl~ urea
1-(5-t-butylisoxazol-3-yl)-3-methyl-3-(4,5,6 triethyl-I,3-
dioxan-2-ylmethyl) urea
1-~3-t-butylisoxazol-5-yl)-3-methyl-3-(4-hexyl~ dioxolan
-2-ylmethyl) urea
1-(3-t-butylisoxazol-5-yl) 3-methyl-3-(5,6-dipentyl 1,3
dioxan-2-ylmethyl) urea
1-(5-t-butylisoxa~ol-3-yl)-3-methyl-3-(4-isopropyl-1,3-
dioxolan-2-ylmethyl) urea
1-(5-t-butylisoxazol-3-yl)-3-methyl-3-(4,5-dibutyl-1,3-
dioxan-2-ylmethyl) urea
1-(3-t-butylisoxazol-5-yl)-3-methyl-3-(5-pentyl-1,3-dioxo-
lan-2-ylmethyl) urea
- 1-(3-t-butylisoxazol-5-yl)-3-methyl-3-(4-methyl-5-ethyl-1,3-
dioxan-2-ylmethyl) urea
1-~5-t-butylisoxa~ol-3-yl)-3-methyl-3-(4-ethyl-5-propyl-
1,3-dioxolan-2-ylmethyl) urea
1-(5-t-butylisoxazol-3-yl)-3-methyl-3-(4-ethyl-576-diiso-
propyl-1,3-dioxan-2-ylmethyl) urea
1-(3-t-butylisoxazol-5-ylj-3-methyl-3-(4-hexyl-5-pentyl-1,3
-dioxolan-2-ylmethyl) urea
1-(3-t-butylisoxazol-5-yl)-3-methyl-3-(5-butyl-6-propyl-1,3-
dioxan-2-ylmethyl) urea
For practical use as herbicides, the compounds of this in-
vention are generally incorporated into herbicidal compositions
which comprise an inert carrier and a herbicidally toxic amount of
such a compound. Such herbicidal compositions, which can also be
called formulations, enable the active compound to be applied con-
veniently to the site of the weed infestation in any desired quan-
tity. These compositions can be solids such as dusts7 granules, or
wettable powders; or they can be liquids such as solutions, aerosols
or emulsifiable concentrates.
~5-
~ 3~ ~ ~
For example, dusts can be prepared by grinding and blending
the active compound with a solid inert carrier s~ch as the talcs,
clays, silicas, pyrophyllite and the like. Granular formulations
can be prepared by impregnating the compound, usually dissolved in
a suitable solvent, onto and into granulated carriers such as the
attapulgites or the vermiculites, usually of a particle size range
of from about 0.3 ~o 1~5 mm~ Wettable powders which can be dispersed
in water or oil to any desired concentration of the active compound
can be prepared by incorporating wetting agents in~o concentrated
dust compositions.
In some cases the ac~i~e compounds are sufficiently soluble
in common organic solvents such as kerosene or xylene so that they
can be used directly as solutions in these solvents. Prequently,
solutions of herbicides can be dispersed under superatmospheric
pressure as aerosols. However, preferred liquid herbicidal compo-
sitions are emulsifiable concentrates, which comprise an active com-
pound according to this invention and as the inert carrier, a solvent
and an emulsifier. Such emulsifiable concentrates can be extended
with water and/or oil to any desired concentration of active compound
for application as sprays to the site of the weed infestation. The
emulsifiers most commonly used in these concentrates are nonionic or
mixtures of nonionic ~ith anionic surface active agents, With the
use of some emulsifier systems an inYerted emulsion (water in oil)
can be prepared for direct application to weed infestation.
A typical herbicidal composition according to this invention
is illustrated by the following example, in which the quantities
are in parts by weight,
EXAMPLE 4
PREPARATION OF A DUST
Product of Example 2 l0
Powdered Talc 90
The above ingredients are mixed in a mechanical grinder-
blender and are ground until a homogeneous 9 free-flowing dust of th~
desired particle size is obtal ed. This dust is suitable for direct
application to the site of the weed infestation.
The compounds of this invention can be applied as herbicides
in any manr,er recognized by the art. One method for the con~rol of
weeds comprises contacting the locus of said weeds with a herbicidal
composition comprising an inert carrier and, as an essential active
ingredient in a quantity which is herbicidally toxic to said weeds,
a compound of the present invention. The concentration o~ the new
compounds of this in~ention in the herbicidal compositions will ~ary
greatly with the type o~ fDrmulation and the purpose or which it is
designed, but generally the herbicidal compositions will comprise
~rom 0.05 to about 9~ percent by weight of the active compounds o~
this invention. In a preferred embodimen~ of this invention, the
herbicidal compositions will comprise from a~out 5 to about 75 percent
by weight of the active compound. The compositions can also comprise
such additional substances as other pesticides7 such as insecticides,
nematocides, fungicides and the like; stabili~ers, spreaders, deae~i-
vators, adhesives, stickers, fertilizers, activators, synergists and
the like.
The compounds of the present invention are also useful when
combined with other herbicides and/or defoliants~ dessicants, growth
inhibitors and the like in the heFbicidal compositions heretobefore
described. These other materials can comprise from about 5% to about
95~ of the active ingredients in the herbicidal compositions. Use of
combinations of these other herbicides and/or defoliants, dessicants,
etc. with the compounds of the present invention provide herbicidal com-
positlons of the individual herbicides. The other herbicides, de-
foliants, dessicants and the plant growth inhibitors, with which the
compounds of this invention can be used in the herbicidal compositions
to control weeds, can include chIorophenoxy herbicides such as 2,4-D,
2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4-CPB, 4-XPP7 2,4,5-TB,
2,4,5-TES 9 3,4,-DA, silvex and the like; carbama~e, herbicides
such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC and khe like;
thiocarbamate and dithiocarbamate herbicides such as DCECg methan
_~_
sodium, EPTC, di.allate, pEsc, perbula-te, ~ernolate and
the like; subs-ti-tuted urea herbicides such as norea,
disuron, dichloral urea, chloroxuron, cycluron, fenuron,
monuron, nonuron TCA, diuron, linuron, molinuron, neburon~
bu-turon; trime-turon and the like symmetrical triazine,
herbicides such as simazine, chlorazine, atraone, des-
me~ryne, norazine, ipazine, prometryn atrazine, trietazine,
simetone, prometone, propazine, ame-tryne and the like;
chloroacetamide herbicides such as alpha-chloro-Nrn-
dimethylacetamide, CDEAr CDAA~ alpha-chloro~N-i~opropyl-
acetamider 2-chloro-N-isopropyl-acetanilide, 4-(chloro-
acetyl)morpholine, l-(chloroacetyl)piperidine and the
like; chlorinated aliphatic acid herbicides such as TCA,
dalapon, 2,3-dichloropropropionic acid, 2,2,3-TP~ and
the. like; chlorinated benzoic acid and phenylace-tic acid
herbicides such as 2,3 r6-TBA1 2,3,5, 6-TBA, dicamba~
tricamba, amiben, fenac, PBA~ 2-methoxy-3,6-dichlorophenyl-
acetic acid, 3-methoxy-2l6-dichlorophenylace~ic acid,
2-methoxy-3,4,6-trichlorophenylacetic acid, 2j4-dichloro-
3-nitrobenzoic acid and the like; and such compounds as
aminotriazole, maleic hydrazide, phenyl mercuric acetate~
endothal, biuretl technical chlordanel dimethyl 2,3,5,6-
tetrachloroterephthalate, diquat, erbon, DNC, DNBP,
dichlorobenil, DPA, diphenamia, dipropalin, trifluraline,
solan, dicryl, merphos, DMPAI DSMA, MSMh, potassium azide~
acrolein, benefin, bensulide, AMS, bromacil, 2-(3,4-
dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine, 3,5-dione,
bromoxynil, cacodylic acid, DMA, DPMF, cypromid, DCB,
DCPA, dichlone, diphenatril, DMTT~ DNAP~ EBEPt EXD~
HCA, iosynil, IPX, isocril, potassium cyanate~ MAA, MAMA,
MCPES, MCPP, MH, molinate, NPA, OC~I paraquat, PCPf
picloram, DPA~ PCA, pyrichlor, sesone, terbac.il, terbutol,
TCBA, brominil, CP-50144, H-176-1, H-732, M-2091~ planavin,
dosium tetraborate, calcium cyanamid~ DEF, ethyl xanthogen
disulfide) sindone, sindone B, propanil and the li~e.
.,~ _ ~ _
~ mab/ ~
~$~
Such herbicides can also be used in the methods and
composition of this invention in the form of their salts, esters,
amides, and otheT derivatives whenever applicable to ~he par-
ticular patent compound.
Weeds are undesirable plants growing where they are
not wanted, having no economic value, and interfering with the
production of cultivated crops, with the growing of ornamental
plants, or with the welfare of livestock. Many ~ypes of weeds
are known, including annuals such as pigweed9 lambsquarter,
foxtail, crabgrass, wild mustard, field pennycress, ryegrass,
goose grass, chickweed, wild oats, velvet leaf, purselane,
barnyard grass, smartweeds, knotweed~ cocklebur, wild buckwheat,
kochia, medic corn cockle, ragweed, sowthistle, coffee-weed,
croton, cuphea, dodder9 fumitory, groundsel~ hemp nettle,
knowel, spurge, spurry, emex, jungle rice, pondweed, dog
fennel, carpetweed, morning glory, bedstraw, ducksalad and
naîad; biennials such as wild carrot, matricaria, wild barley,
campion, chamomile, burdock, mullein, roundleaved mallow,
; bull thistle, hounds-tongue, moth mullein and purple star
thistle; or perennials such as white cockle, perennial rye-grass,
quackgrass, Johnson grass, Canada thistle, hedge bindweed,
Bermuda grass, sheep sorrel, curly dock, nutgrass, field chick-
weed, dandelion, campanula, field bindweed, Russian knapweed,
mewquite, toadflax, yarrow, as~er, gromwell, horsetail, iron-
weed, sesbania, bulrush, cattail and wintercrass,
Similarly, such weeds can be classified as broadleaf or
grassy weeds. It is economically desirable to control the
growth of such weeds without damaging beneficial plants or
livestock.
The new compounds of ~his invention are particularly
valuable for weed control because ~hey are toxic to many speci s
and groups of weeds while they are relatively non~oxic ~o many
beneficial plants. The exact amount of compound required will
_g_
depend on a variety of factors, including the hardiness of the
particular weed species, weather9 type of soil, method of
application, the kind of beneficial plants in the same area,
and the like. Thus, while the application of up to only about
one or two ounces of active compound per acre may be sufficient
for good control of a light infestation of weeds growing under
adverse conditions, the application of ten pounds or more of
active compound per acre may be required for good control of
a dense infestation of hardy perennial weeds growing under
favorable conaitions.
The herbicidal toxicity of the new compounds of this
invention can be illustrated by many of the es~ablished testing
techniques known to the art, such as pre- and post emergence
testing. ~
The herbicidal activity of the compounds of this
invention was demonstrated by experiments carried out for the
pre-emergence control of a variety of weeds. In these experi-
ments small plastic greenhouse pots filled with dry soil were
seeded with the various weed seeds. Twenty-four hours or less
after the seeding, the pots were sprayed with water until the
soil was wet and the test compounds formulated as aqueous
emulsions of acetone so:Lutions containing emulsifiers were
sprayed at the indicated concen~rations on the surface of
the soil.
After spraying, the soil containers were placed in the
greenhouse and provided with supplementary heat as required
and daily or more frequently watering. The plants were main-
tained under these conditions for a period of from 14 ~o 21
days, at which time the condition of the plants and the degrees
of injury to the plants was rated on a scale of from 0 to 10,
as follows: 1 = no injury, lp2 = slight injury, 3,4 = moderate
injury3 556 = moderately severe injury~ 7,8,9 ~ seYere injury,
and 10 = deathO The effectiveness of these compounds is demon
-10-
stra~ed by the following data:
14 DAYS AFTER TREATMPNT
,_ ,. .
Produ_t of Ex mple 2
RATE OF
APPLICATION
~Lbs/Acre) 1 0.5 0.25 0.125
Wild Mustard 10 1 10 5
Bindweed 8 5 S 4
Pigweed 8 0 0 0
Velvet Leaf 8 0 0 0
Morning Glory 10 10 8 8
Yellow Foxtail 7 3 3 0
Barnyard Grass 9 0 0 0
Johnson Grass 8 8 7 8
Quack Grass 3 1 0 0
Wild Oats 7 4 3
Crabgrass 9 9 8 8
Sprangletop 9 9 8 5
Cheat grass 0 0 0 0
Sugar Beet 10 0 10 10
Soybean 7 3 2 2
Cotton NE 0 0 0
Pinto Bean 0 0 0 0
Alfalfa 10 10 10 5
Wheat . 5
Rice 10 8 7 7
Sorghum 8 7 2 2
Corn 6 S 3 0
Oats 5 7 0 0
21 DAYS AFTER TREATMENT
.. ~
Product of Example_2
-
RATE OF
APPLICATION
(Lbs/Acre) 1 0.5 0.25 0.125
Wild Mustard 10 3 10 7
BiDdweed 10 O O 0
Pigweed 10 10 10 O
Velvet l.eaf 10 2 9
Morning Glory10 10 l0 7
Yellow Foxtail 10 O 0 0
Barnyard Grass l0 0 0 O
Johnson Grass 9 8 5 3
Quack Grass 5 8 0 0
Wild Oats lO 10 8 0
Crabgrass l0 10 8 O
Sprangletop 10 10 9 O
Cheat Grass 8 8
Sugar Beet 10 10 10 10
Soybean 10 3 2 0
Cot~on NE 0 O O
PintG Bean 9 10 0 O
Alfalfa 10 10 10 0
Wheat l0 lO 5 0
Rice 10 10 4 2
Sorghum 8 8 1 0
Corn 7 ~
9ats 10 10 1 O
-12~ ,
~ 3~ ~
~:~ .,
14 DAYS AFTER TREATMENT
~ . . . . .
Product of Example 3
RATE OP
APPLICATION
(Lbs/Acre) 4 2 1 0.5 0025 0.125
Yellow Nutsedge 3 1 1 - - -
Wild Mustard 10 10 10 10 7 2
Bindweed - . - 10 10 10 3
Pigweed 6 5 7 10 10 0
Jimsonweed 3 4 2 10 7 6
Velvet Leaf 3 10 10 9 9
Morning Glory 4 4 4 10 8 2
Yellow Foxtail 4 4 2 1 0 0
Barnyard Grass10 8 3 0 0 0
Johnson Grass 3 6 2 0 Q 0
Quack Grass - - 3 2 3 0
Wild Oa~s 5 . 7 7 0 0 0
Crabgrass 10 7 5 0 0 0
Sprangletop - - 9 1 O 0
Cheat Grass 3 0 0 8 0 O
Sugar Beet - - 10 10 10 10
Soybean - o 3 0 0 . 0
Cotton - - 10 10 10 9
Pinto Bean - - 1 0 0 0
Alfalfa - - 10 10 10 10
Wheat - - 10 10 0 0
Rice - - 0 0 0 0
Sorghum -~ - 2 0 0 0
Corn ~ o 2 . 0 0 0
Oats O O 7 o
-13-
PRE-EMERGENCE HERBICIDE TEST DATA
21 DAYS AFTER TREATMENT
Product of_Example 3
RATE OF
APPLICATION
(LbsJAcre) 4 2 1 0.5 0.25 0.125
Yellow Nutsedge 3 2 2 - - -
Wild Mustard 10 10 10 10 10 10
Bindweed - - 10 10 10 7
Pigweed 7 8 8 10 10 0
Jimsonweed 10 10 5 10 10 10
Velvet Leaf 10 10 10 10 10 10
Morning Glory 10 10 10 10 10 10
Yellow Poxtail 10 10 10 1 0 0
Barnyard Grass 10 10 8 1 0 0
Johnson Grass 7 8 7 2 0 0
Quack Grass - - 10 10 7 0
Wild Oats 10 10 10 1 1 0
Crabgrass 10 10 10 0 0 0
Sprangletop - - 10 7 0 0
Cheat grass 10 9 4 g 0 0
Sugar Beet - - 10 10 10 10
Soybea~ - - 10 10 4
Cotton - - 10 10 10 10
Pinto Bea~ - - 10 8 7 0
Alfalfa - - 10 10 10 10
Whea~ . - - 10 10 3
Rice - - .10 0 0 0
Sorghum - - - 10 1 0
Corn - - 10 3 0
Oats - - 10 4 0 0
~14-
5~ ~
The herbicidal activi~y of the compounds of this
invention was also demonstrated by.experiments carried ~ut
for the post-emergence control of a variety of we~ds, In
these experimen~s the compounds to be tested were fo~mula~ed
as aqueous emulsions and sprayed at the indicated dosage on
the foliage of the various weed species ~hat have attained
prescribed size. After spraying, the plants were placed in
a greenhouse and watered daily or more frequently. Water
was not applied to. the foilage of the treated plants. The
severity of the injury was determined 14 days after treat-
ment and was rated on the scale of from 0 to 10 heretobefore
described. The effectiveness of these compounds is de~on-
strated by the following data:
POST-EMERGENCE HERBICIDE TEST DATA
.. _ . .. _ ,, .. w...... _
Pr ct of Exam
RATE OF
APPLICATION
~Lbs/Acre) 1 0.5 0.25 0.125
Wild Mustard 10 10 10 10
Bindweed 10 10 10 10
Pigweed - - 10 10
Jimsonweed 10 10 10 10
Velvet Leaf 10 .10 10 10
Morning Glory 10 10 10 10
Yellow Foxtail 8 9 5 o
Barnyard Grass 10 10 0 0
Johnson Grass 10 10 1 0
Quack Grass 10 10 10 0
Wild Oats 10 10 10 2
Crabgrass ~10 8 0 0
Sprangletop 10 10 10
Cheat Grass 10 8 0
Sugar Beets 10 10 10 10
-15-
Cot~on 10 10 10 10
SoybeaDs lD 10 7 6
Pin~o Beans - 10 10 10 7
Alfalfa 10 10 10 10
Sorghum 10 3 0 0
Wheat 10 10 10 5
Rice 10 10 10
Corn 10 7 0 0
Oats 10 10 9
POST-EMERG~NCE HERBICIDE T.EST DATA
RATE OF
APPLICATION
~Lbs~Acre) 4 2 l 0.50.250.125 0.062 0.032
Yellow Nutsedge 10 7 .8 10 10 lO - -
Wild Mus~ard 10 10 10 - - 10 0 0
Bindweed 10 7 7 10 7 0 0 0
Pigweed 10 10 10 10 10 10 - -
Jimsonweed 10 10 10 10 10 10 0 0
Velvet Leaf - - - - 0 0 0
Morning Glory10 10 10 10 10 10 0 0
Yellow Foxtail7 10 9 10 0 0
Barnyard Crass10 10 7 10 10 0 0 0
Johnson Grass10 8 10 10 0 0 0 0
Quack Grass - - 7 7 0 0
Wild Oats 10 10.10 1 0 0
Crabgrass 10 10 10 5 0 0 - -
Sprangletop - - 10 7 0 0 - -
Cheat Grass - - 3 1 0 0 - -
Sugar Beets - 10 10 10 10
Cotton - - 10 10 10 10 - -
Soybeans 10 l0 10 9 l 1 0 0
Pinto Beans - - 10 l0 10 . 0 ~ -
Alfalfa - - 10 10 10 10 ~ - .
~. ,
-16-
.
f~
Sorghum - -10 1 O 0 o .
Whea~ 13 10 O 0
Ri ce - o0 O O 0
Corn - -10 1 1 0 - ~ ,
Oats - -10 5 0 0 - -
.
.
7- ,
