Note: Descriptions are shown in the official language in which they were submitted.
~339Q~
The present invention relates to and has for its objects
the production of phosphoranyl derivatives containlng a nitrogen
atom as novel compounds which are useful as agricultural products
for plant growth regulation effec-ting growth promotion, growth
inhibition, and ma-turation dependent upon the concentration of the
present compound with respect to the plant. The compounds of the
present invention are ethylene-releasing and/or ethylene stimul-
ating agents, generally inducing the hormonal effects known for
ethylene as described in many texts
for example, ETHYLENE IN PLANT BIOLOGY, by F.B.
A~eles, Academic Press, Inc., 1973, particularly pages 103 through
215. Specific promotional effects include earlier bud break,
synchronization of fruit ripening and leaf drop, temporary increase
in tree sap or latex flow, breaking of dormancy in treated seeds,
bulbs, tubers and corns. Inhibitory effects include defoliation,
stunting and control of apical clominance. The compounds of the
present invention are particularly effective in the treatment of
tobacco, cotton, wheat, vegetables, fruit and rubber trees.
According to the present invention, there are provided
compounds indicated by analysis to possess the formula:
Rl
= ~ R
XR --P - O- - C -R
O ::`
H
wherein XR is a 2-haloethyl group such as ethyl terminally
substituted by fluorine, chlorine, bromine, or iodine; Rl, R2
and R are each independently hydrogen, phenyl which may be - `
substituted by alkyl containing 1-4 carbon atoms, alkyl of 1 to
12 carbon atoms optionally substituted with hydroxy and Rl can
also be alkenyl of 2 to~6 carbon atoms; or R and R3, together
with N and C can form a N-heterocyclic ring having from 3 to
~3391~6
5 carbon atoms in the ring, which ring may be saturated or
unsaturated; and the polymer of the above compound when Rl is
vinyl and R2 and R3 with N and C form said N-heterocyclic ring,
preferably a pyrrolidone ring, and the neutralized product of
said compound. This polymeric compound of the present invention
is believed to contain the unit:
¦ \ /
H- -CH2 - CH / O--- N+ = R2 3
XR / P \ ll
HO O C R n
where n is 1 to 5000 and additionally may contain units of the ~ -
unsubstituted N-vinyl heterocyclic ring and/or units of a
derivative of the above dimer which is monosubstituted with the
haloalkyl-dihydroxy phosphoryl group.
Of the complex compounds of this invention, those
forme~ from a 2-haloethyl phosphonic acid and a cyclic amide, ~`~
particularly a heterocyclic monoamide, are preferred. Most
preferred are the complexes of 2-haloethyl phosphonic acid and
N-methyl-2-pyrrolidone.
In the above formulae, it is to be understood that -~
the ionic charges can be neutralized to extinction and that
such neutralized compounds are also within the scope of this
invention.
The compounds of the present invention are
prepared by reacting a haloalkyl phosphonic acid, i.e.
corresponding to that moiety in the product desired, and an
amide, e.g. polyvinyl pyrrolidone or the amide
corresponding to the amide moiety of the product desired,
at a temperature from about the freezing temperature of the
reaction mixture to about 225C, preferably from about 0C
and about 200C under between about 10 psig and about 150
psig. In general the reaction involving the above-
described reactants is postulated as follows:
Il,,~OH ~ ~O N R~ -C3 - CH2
XR- P ~ + ~ -N-C~ R-P~ ll ~ 2
wherein X, R, Rl, R2 and R3 are as described in Formula I; b
has a value of between 2 and about 5500 when Rl is vinyl
and R2 and R3, with N, form a heterocyclic ring and
otherwise b is l; n is 1 and m is zero, except when a
heterocyclic polymeric reactant is employed. In the later
case, n has a value of 2-5000 and m is 1-5000 and the n and
m recurring units may be distributed in random or block
configuration in the polymeric product.
While the structures presented above have been
indicated by various analytical procedures, including
infrared anaylsis, elemental analysis, Hl, C13 and P31
nuclear magnetic resonance spectroscopy, titration
analysis and dissociation analysis, applicants do
" ~3~39~
not wish to be bound to any particular structure and
considers their invention to reside in any compound formed
from the reaction between a haloethylphosphonic acid and
the amides defined herein. It is further postulated that
the above described compound may be in equilibrium or
admixture with other complex or polymeric forms.
The phosphonic acid and amide reactants are
introduced into the reactor in a mole ratio of between
about 0.2:1 and about ~:1, preferably a mole r~atio of
between about 1:1 and about 3:1, based on phospho:amido
moieties. The reaction may be extremely rapid in the
absence of a diluent. However, the rate of reaction can be
reduced by employing a solvent for the reaction such as an
ether, ketone, chlorinated or nonchlorinated liquid
hydrocarbon, O-heterocyclic compound, water or any inert
liquid solvent or dispersant. Suitable solvents include
methyl ethyl ether~ diethyl ether, methyl ethyl ketone,
diethyl ketone, chloroform, carbon tetrachloride, benzene,
toluene, xylene, tetrahydrofuran, furfuryl, cyclohexane,
hexane, heptane, octane, etc. Most desirably, the reaction
is effected in the presence of a solvent in which the
product is insoluble. While the complex of the present
invention may partially dissociate in water when in very
dilute solutions of less than 2 moles of complex to 3 moles
of water, the complex is reformed upon evaporation of
water.
The reaction is carried out under anhydrous or
nonanhydrous conditions, preferably with agitation and is
completed within a period of not more than two hours to
provide from about 90% to about 100% conversion to product.
L33~
It is most preferred to dissolve each of the reactants in
the chosen solvent to provide a solution of the reactant
having between about 20 and about 60 weight percent
concentration therein. The respective reactant solutions
are then mixed in the reactor, desirably at ambient
temperature under atmospheric pressure. Formation of the
product may be indicated by the separation of an oil phase
which settles to the bottom of the reactor when a solvent
is selected in which the product is insoluble. After
reaction is complete, the upper solvent layer is withdrawn
and the oil recovered as a product of the process. When the
solvent is one in which the product is soluble, it can be
removed from the product by evaporation, stripping,
extraction or by any other convenient or conventional
method. However, it is to be understood that it may be
desirable to leave the product in solution to be used
directly as a plant growth regulating composition. In
general, the reaction is completed within a period of not
more than 2 hours, and more often within about 40 minutes.
When employed as agricultural aids, the products
of the present process, for economic considerations, are
usually combined with various inert carriers and extenders,
for example, they may be mixed with talc, clays and various
other conventional dry particulate solids to form pastes,
dusts, or heavy oily substances which may beneficially
adhere to the plant in climates of high rainfall.
Alternatively, the compounds of the present invention may
be extended with inert li~uid carriers which include
emulsions or solutions of any of the foregoing reaction
~1339~
solvents and solutions with mineral or vegetable oils or
they may be extended with water or aqueous solutions of
organic solvents. The concentrations of the present
compound in the carrier can vary between about 15 ppm and
about 150,000 ppm, preferably between about 25 ppm and
about 100,000 ppm depending upon the effect desired. The
resulting composition of active agent and ca~rier may be
applied to the plant at a rate of between about 0.1 and
about 100 Kg/hectare, preferably between about 0.5 and
abo~t 50 Kg/hectare of soil area for promotional effects
and higher amounts for inhibiting effects.
The complex compounds of the present invention can
be applied to plants as a particulate solid or as a liquid.
When liquid application is desired, the present compound
may be used as a preformed solution or the complex may be
formed on a plant part or plant situs subjected to
treatment, e.g. as when a solution of the
haloethylphosphonic acid and a solution of the amide are
applied as separate sprays so that the complex is formed on
the plant or plant situs when the ~respective solutions
contact each other. It is also to be understood that
various methods of application can be employed, such as
e.g. spraying, dipping, etc. as well as dry applications
which may entail dusting, broadcasting, or any other
convenient method of application.
It is also to be understood that the composition
containing the present compound or one of the treating
solutions may optionally conta.in other additives such as a
--8--
~133g~
surface active agent, a thickener, and/or other
agricultural chemicals such as, for example, an algicide, a
fungicide, an herbicide, an insecticide, a nematocide, a
disinfectant, or a plant growth regulant; or any mixture of
these. Preferably, when such mixtures are used, the added
agricultural agents are those which do not materially lower
the activity o~ the present complex. Exemplary of other
agricultrual agents which may be employed with the
compounds of the present invention include
tributylphosphortrithio -ate or -ite (DEF*or FOLEX);l,l-
dimethyl-4,4'-bipyridinium salts, e.g. the methyl sulfate
salt or halide salt (Paraquat~; sodium chlorate; an alkali
metal salt o~ cacodylic acid, e.g. the sodium salt BOLL's-
EYE, chlorinated isophthalonitriles, e.g. the
tetrachlorinated derivative, Daconi~; alkyl-l-
(butylcarbamoyl)-2-benzimidazole carbamate, e.g. the
methyl derivative, Benomyl; dialkylaminobenzenediazo
alkali metal sulfates, e.g. the dimethyl derivative, Dexon;
2,4-dinitro-6-alkylphenyl-crotonate, e.g. the actyl
derivative Karathane; ~anganese ethyl
bis(dithiocarbamate), e.g. Maneb or Manzate; 2,3-dihydro-
5-carboanilido-6-methyl-1,4-oxathiin-4,4-dioxide, (Plantvax~;
polychloronitrobenzenes, e.g. the pentachloroderivative
Terraclor*, 5-ethoxy-3-trichloromethyl-1,~,4-thiadiazole,
*
Terrazole; 5,6-dihydro-2-methyl-1, 4-oxathiin-3-carboxanilide,
Vitavax*; tetramethylthiuram disulfide, Arasan; N-(acyl-
tert.-amidoalkyl) anilides, such as Lasso; esters of
cyclopropane substituted carboxylic acids; alkylsulfinyl
substituted diphenylethers; alkyl-1,7.-dimethyl-3,5-
Trade Mark
g
~ 33~diphenyl pyrazolium salts and derivatives thereof; diethyl
amino-2,6-dinitro~4-trifluoromethylbenzene, and derivatives
such as the amino substituted derivative Cobex; dinit~oanilines;
trifluoromethyl-nitro-diphenyl ethers; halo-~-cyclicimido-
alkylene-substituted acetanilides; dichloro-nitrobenzoic
acid and derivatives thereof, e.g. Dinoben*; phosphonium
salts, such as Phosphon, halogenated benzoic acids, such
as 2,3,6-TBA or Benzac, 2,4-D and 2,4,5-T; aminodihalobenzoic
acids, such as Amiben; polychlorophenyl-nitro-phenylate
ethers, such as Modown; 6-benzyl-aminopurine (Benzyladenine);
arylazomalononitriles; dimethylformamide; methyl acetamide;
dimethylacetamide; 2-propyl-2-chloroethyl-trifluorodinitropropyl
toluidine (Basalin); N,N-bis (phosphonomethyl) glycine
(Glyphosine); 5-chloro-3-methyl-4-nitro-lH-pyrazole;
2-chloroethyltrimethyl ammonium chloride (Cycocel or
CCC); 2-(3-chlorophenoxy) propionic acid (3-CPA); 4-chloro-
phenoxyacetic acid (4-CPA); 3-(chlorophenyl)-1,1-dimethylurea
* . *
(Monuron); N-dodecyl guanidine acetate, (Dodine); urea;
2-haloethylphosphonic acid, e.g. ethephon; 3-amino-1,2,4-
triazole; cycloheximide; 2-(3-chlorophenoxy) propionamide;
maleic hydrazide (1,2-di-hydropyridazine-3,6-dione);
ammonium thiocyanate; the alkali metal salt of 2r3-dichloro-
2-methyl propionic acid, (e.g. the sodium salt Mendok);
3-(3,4-dichlorophenyl)-1,1-dimethylurea (Diuron);
6,7-dihydrodipyrido pyrazidinium dibromide (Diquat);
maleic hydrazide; 2,4-dinitro-6-sec-butyl-phenol (Dinoseb);
cycloheximide; N-2~4-dimethyl-5-(trifluoromethyl)-sulfonylamino
phenyl acetamide (Mefluidide); haloalkyl silanes; 6-~urfuryl-
aminopurine (Kinetin); 4-hydroxyethyl-hydrazine (BOH);
*
l-hydroxytriacontane; 3-indoleacetic acid (IAA); 3-indolebutyric
* *
acid (IBA); abscisic acid (ABA); l-naphthaleneacetic
acid (NAA); dieldrin-hexachloro-epoxy-octahydro-endodimethan-
naph~halene
Trade Mark
- 10 -
~ ~33~
* *
(Endrin); the 2,4-dichlorophenol ester of benzene (Genite);
N-~tetrachloroethyl) thio~ 4-cyclohexene-1,2-dicarboximide,
(Difolatan 4F); monosodium acid - methane arsonate (MSMA~;
trichlorophenyl-acetic acid alkali metal salt (Fenac);
2-naphtoxyacetic acid (BNOA*); the alkyl amine salt of
succinic acid or of 7-oxabicycloheptane-2,3-dicarboxylic
acid (Endothall); succinic acid~2,2-dimethyl hydrazine
(SADH or ~lar); gibberellic acid (Activol* or Gibrel~;
2,3,5-triiodobenzoic acid (TIBA*); iron chelate; sulfur;
nicotine sulphate; lead arsinate; self-emulsi~ying petroléum
oil; sodium selenate; zinc ethylene bisdithio-carbamate
(Zineb~; tetramethyl thiuramdisulfide (THIRAM); N-trichloromethyl-
thiotetrahydro-thalimide (Captan); mercaptobenzolthiozole
(Rotax); 1,1,1-trichloro-2,2-bis(chlorophenyl) ethane
(DDT); 2-(2,4,5-trichlorophenoxy) propionic acid ~Silvex*);
3,6-dichloro-o-anisic acid (Dicamba*); 2,2-dichloropropionic
acid (Dalapon); ~-chloro-4,6-bis(ethylamino) S-triazine
(Simazine); N,N-diallyl-2-chloroacetamide (CDAA); 2-chloroalkyl~
diethyl-dithio carbamate (CDE~*); dimethyltetrachloro
teraphthalate (DCPA or Dacthal); N,N-dimethyl-2,2-diphenyl
acetamide (Diphenamide); dimethyldithiocarbamate (Ferbam
*
or Ziram); malathion; actidione, zinc dimethyldithiocarbamate
*
(Ziram*); hexahydromethanoindene (Chlorodane); chlorinated
dimethanonaphthalene (~ieldrin or Aldrin); sodium N-methyldithio-
carbamate dihydrate (Vapam); 2,2-dichlorovinyl dimethyl
phosphate (Vapona* or DDVP); O-( 2,4-dichlorophenyl)-0-
methyl isopropyl phosphoramidothiate (Zytron); arsenic
trioxide mixtures (Sodite); posphomolybdic acid (PMA);
0,0-diethyl-0(2-isopropyl-6-methyl-~-pyrimidinyl)
*
Trade Mark
~33~3Q~
*
phosphorothioate (Diazinon), 1,1-bis(chloxophenyl)-2,2,2-
trichloroethanol (Kelthane); 2,2-bis(p-methoxyphenyl)-
l,l,l-trichloroethane (Methoxychlor or DMDT); 2,4,4',5-
tetrachlorodiphenylsulfone (Tedion); O,O-diethyl-O- (and
S-)-2-(ethylthio) ethyl phosphorothioates (Systox); isopropyl-
N-(3-chlorophenyl) carbamate (chloro-IPC or CIPC); sodium
2,4-dichloro-phenoxyethylsulfate (SES or Sesone); Bordeaux
mixture; preparations containing streptomycin (Agrimycin);
N-trichloromethylthiophthalimide (Phaltan); ethyl mercuric
chloride mixtures (Ceresan); 3,5-dimethyl-2H-1,3,5-tetrahydro-
thiadiazine-2-thione (Mylone); l-naphthyl-N-methylcarbamate
(Carbaryl~; l-dimethyl-carbamoyl-5-methyl-3-pyrazolyl
dimethylcarbamate (Dimethilane); O,O-dimethyl S-(N-methylcarbamoyl
methyl) phosphorodithioate (Dimethoate); 3-(3,4-dichlorophenyl)
-l-methoxy-l-methylurea (Linutron); 2-chloro-4,6-bis(ethylamino)-
S-triazine (Simazine~; l,l,l-trifluoro-2,6-dinitro-N,
* *
N-dipropyl-p-toluidine (Treflan or Trifluralin); 4~dimethylamino-
3,5-xylyl N-methylcarbamate (Zectran*); ferric dimethyl
dithiocarbamate (Ferbam); N-I-naphthyl phthalamic acid
(NPA); S-propyl-butylethyl thiocarba~ate (PEBC); disodium
methane arsenate (sodar*); calcium acid methyl arsinate
(calar); ~-benzenehydrochloride (Lindane*); diethyl-S-
diethylaminoethyl phosphorthiolate (Amiton or Amitrole);
rotenone; pyrethrum; the acaricide of 2,4,5,4'-te~ra- :
chlorodiphenyl sulfone (Tedion); l,l-dimethyl-piperidinium
salts, e.g. Metiquat chlorlde and Terpal; the anionic
salts of allyltrimethylammonium-, bromoethyltrimethylammonium-,
isopropyltrimethylammon:ium-! N-chloroethyl-N,N-dimethyl-
hydrazonium-, N-bromoethyl-NjN-dimethylhydrazonium-,
N-isopropyl-N,N-dimethyl-hydrazonium-, N-allyl-N,N-dimethyl-
Trade Mark
- 12 -
~33g~6i
hydrazonium- and N,N-dimethylmorpholinium- cations N-methyl
pyrrolidone and mixtures of any of the foregoing and many
more plant growth regulators and agricultural agents. Each
of the above active adjuvants is individually effective at
a range of rates, depending upon the particular substance,
the particular use and the type of plant or soil and other
growing conditions. Generally, these substances are employed
individually at rates of between 0.001 and about 40 lbs. per
acre. The same rate of application can be employed in the
present invention when such chemically active additives are
administered separately. When employed in admixture with
the compounds of the present invention, or with either of ;
separate solutions of the amide of the present complex or
the haloalkylphosphonic acid solution, the known agent is
preferably incorporated in an amount between about 0.01
weight percent and about 60 weight percent, based on the
weight of the total composition. It is generally preferred
that the known agricultural agent be used in an amount
within its established rate range for individual use as
sole agent, although because of the combined effect at-
tributable to the present compounds, lesser amounts within
the established rate range or amounts below the established
rate range are appropriate. Thus, amounts below the median
of the established rate range generally give good results
in combina~ion with the present complexes, particularly the
chloroethylphosphonic acid/methylpyrrolidone complex.
The compounds and/or compositions of the present
invention can be empolyed on many plants including
gymnosperms and angiosperms, of monocotyledonous and
~.-
- 13 -
~ ,
; ~
; ~1 3 ~
dicotyledonous types. Species of these embrace vegetables,
fruits, grasses, bushes, trees, ornamentals and the like.
Examples of plant life which can be treated with the
present compounds alone or in admixture include fruit trees
such as apple, peach, apricot, tangerine, pear, cherry,
grapefruit, orange, lemon, lime, plum, persimmon, banana,
guava, nectarine, oLive, papaya, date, fig, as well as
fruits thereof and other trees such as oak, hazel, beach,
pecan, almond, rubber, cork, pine, elm, spruce, fir, cedar,
yew, eucalyptus, magnolia, dogwood, palm, walnut, wiIlow,
avacado, chestnut, hawthorn, maple, mango, and the like.
Examples of vegetable plants sultably treated with the
present compounds or their admixtures include asparagus,
beans, brussel-sprouts, carrots, cauliflower, celery,
cucumber, squash, lentil, lettuce, onion, peas, peanut,
peppers, potatoes, pumpkin, soybean,~ spinach, tomato,
broccoli, kale, beets, and the like. Examples of grains
and grasses which may be treated with the present compounds
or their admixtures include barley, rye, oats, wheat, rice,
corn, bluegrass, etc. Ornamentals suitably treated include
rhododendron, roses, azelea, tulip, carnation,
chrysanthemum, dahlia, hyacinth, geranium, impatien, iris,
lily, poinsetta, snapdragon, fuch~ia, gladiola, etc. Other
crops suitably treated with the present compounds or their
admixtures include pineapple, melon, grapes, hops, berries,
such as cranberries, strawberries, raspberries,
blueberries, blackberries and~ currants, coffee plants,
sugar cane, flax, cotton, tobacco plants and the like.
-14-
The compo~nds of the present invention induce the
effects generally associated with ethylene activity, such
as control of apical dominance and promotion of branching,
bud initiation and enlargement, callus induction, increased
resistance to cold, color and ripening promotion, breaking
dormancy, inhibition of stem elongation; increased
flowering and fruit set, advance or harvesting, resistance
to lodging, disease resistance, loosening of fruit and
nuts, dehiscence, promotion of rooting and rhizome
development, seed development, increased yield in crops and
other effects more fully discussed on pages 103 through 233
of Ethylene in Plant Biology by Frederick B. Abeles,
published by the Academic Press, 1~73.
By way of illustration, in the treatment of cotton
plants to provide increased yield on single harvest and
synchronization of boll opening and leaf drop, application
of certain complexes, e.g. the acid/N-methyl pyrrolidone
complexes (from about L000 ppm to about 15,000 ppm in a
carrier) is preferabl~ effected at least 30 days after
square set; although it is to be understood that
application can be made at any time after the square set up
through initial boll break without any damage to the plant
or plant fiber and still provide beneficial effect.
The present compound in the composition is applied
to the crop at a temperature desirably within the range of
from about 65F. to about 95F.; although application at
higher or lower temperatures does not result in crop
damage, but merely alters the period or plant response,
which is extended at lower temperatures and shortened at
higher temperatures. Normally, the results of the present
application are evident within 5 to 14 days after treatment
depending upon the concentration of the active ingredients
and the temperature conditions extant. For example, with
low level applications, results have been observed within 8
to 12 days; whereas at high level applications, results
have been evident within 5 to 7 days. It has been found
that field temperatures of about 95F. and above generally
do not require dosage levels above 3,000 ppm of the present
compound, although higher dosage levels can be employed
without damage to the plant or cotton fiber.
The advantages realized from the application of
the above N-methyl pyrrolidone complexes for preharvest
treatment of cotton are enumerated as follows:
l. Providing a multipurpose composition for
effecting boll ripening, boll dehiscence and
leaf defoliation so as to avoid the need for
multiple chemical applications.
2. Increasing the rate of boll dehiscence so as
to provide more uniformly opened bolls for
first harvest collection and synchroniæing
defoliation so that it is effected after the
bolls are fully developed and opening or
opened.
3. Producing metabolic effects in increased
dehiscence which exceeds the sum of the
effects obtained with either the amide or the
phosphonic acid from which the present
complex compounds are formed.
-16-
3~i
4. Advancing early dehiscence of bolls
containing mature fibers while having
substantially no effect on the completely
matured breaking bolls so as to increase the
proportion of recoverable cotton in a slngle,
first harvest and to minimi~e and/or obviate
the necessity of a second harvest.
5. Providing cotton fiber of inherent high
quality and, in certain cases, improving the
quality of cotton fiber.
6. Reducing plant temperature sensitivity and
resistance to low temperature dehiscence.
7. Permitting later planting of crop and/or
earlier harvesting.
8. Providlng economic and labor saving harvest
of cotton crops.
The present compounds are stable, complexes,
most of which are insoluble in diethyl ether and some~are `~ -
insoluble in water. All are ethylene releasing compounds
and/or have profound ethylene stimulating capability when
~in contact with plant tissue.
The fact that the present compounds are distinct
complexed compounds is shown by their~infrared spectra, in
which a shlft of~the amlde~carbonyl band from~low to high ; -
wave length is indicative of complex formation, i.e. that
:
.
,~
~,
`'':
` .'''' "
- 17
!,~ ~ ,,
there has been a change in the carbonyl structure. The
infrared data for the complexes prepared in this study are
given in Table I.
Further indication of the complex structure was
provided by the base titration of the complexes in
nonaqueous media. Table III reports the difference in Kal
and Ka2 for the complexes versus ethephon. In Table II, a
normal base titration gives the relative amount of ethephon
in such complex on both a weight and molar basis. Further
support for the complex structures was obtained from
elemental analysis.
Another determination for the indicated structure
of the complexes was made utilizing Hl and P31 nuclear
magnetic resonance spectroscopy. Carbon 13 relaxation time
(C-13, Tl) measurements indicated that the complex has a
lifetime such that the present complex is characterized as
a coordination or association complex as opposed to a
collisional complex.
Finally, as a check on the character of the
carbonyl group in the present compléxes, carbon 13 analysis
was made to provide a comparison between the carbonyls of
the complexed and non-complexed compounds. These
measurements indicated a downward shift for the complex
which supports the structure as described herein.
Having thus generally described the invention,
reference is now directed to the following examples which
serve to illustrate preferred embodiments but which are not
to be construed as limiting to the scope of the invention
as set forth hereinabove and in the appended claims. In
-18-
1~339q~
the examples all amounts and proportions are by weight
unless otherwise indicated.
The preparation for each of the compounds shown
below is reported in the Example designated by number. The
same numbers are used throughout in analyses and testing to
identify and illustrate utility of the indicated compound.
*Indicated H ~ ~+ RR3
Compound: ~
Example No. Rl R2 R3
2 CH3 CH3 H
4 CH3 CH3 CH3
S H CH3 CH3
B ! 6 H H CH3
9 H , H C3H~
--19--
~ 33~; R
*;Indicated ~I H~O~ / o ~ N ~ R5
Bl Compound~ H2CH2 /P O -- C
H-O
Example No. Rl R5
1 CH3 (CH2)3
3 H (CH2)3
7 CH3 -CH=CH-CH=CH-
8 CH3 (CH2)4
~ CH3 (CH2)4
11 HOCH2CH2 (CH2)3
12 (CH3)2CH- (CH2) 3
13 C6Hll (CH2)3
14 (CH3)3c- (CH2)3
. CH3(CH2)11- (CH2) 3
16 Polyvinylpyrrolidone (K30) Complex (CH2)3
*In the above, the "indicated compound" is that which is
indicated by analysis and is therefore assumed; however, it
is to be understood that the following Examples and Tables
are no~ limited to this assumed structure but are directed
to the complex compound of whatever structure results from
the reaction between 2-chloroethylphosphoniic a~id, o~
indicated homolog, and the amide having the R , R and R
groups shown above.
EXAMPLE 1
A solution containing 2.97 grams (0.03 mole) of
N-methyl-2-pyrrolidone in 7.13 grams (10 ml) diethyl ether
was added, with stirring, to a solution containing 4.32
grams (0.03 mole) of 2-chloroethylphosphonic acid in 7.13
grams (10 ml) diethyl ether in a 250 ml glass Erlenmeyer
flask equipped with a drying tube to maintain anhydrous
conditions and a magnetic stirring bar to maintain gentle
-20~
~33~
agitation. The reaction was effected at ambient
temperature and atmospheric pressure. Withln 10 minutes
6.48 grams of the zwitter ionic complex purported to have
the structure shown above separated as a yellowish oil
(88.7% yield).
The oil was recovered and dried in a rotary
evaporator for 0.5 hours at 50C at 2 mm. The complex was
subjected without further purification, to combustion
analysis.
Calculated: C,34.53; H,6.16; N,5.75.
Found: C,33.98; H,6.45; N,5.74.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 2
A solution containing 3.65 grams (0.05 mole) of
N,N-dimethyl formamide in 7.13 grams (10 ml) diethyl ether
was added, with stirring, to a solution containing 7.23
grams (O.OS mole) of 2-chloroethylphosphonic acid in 7.13
grams (10 ml) diethyl ether in a 250 ml glass Erlenmeyer
flask equipped with a drying tube to maintain anhydrous
conditions and a magnetic stirring bar to maintain gentle
agitation. The reaction was effected at ambient
temperature and atmospheric pressure. Within 10 minutes
9.2 srams of the zwitter ionic complex purported to have
the structure shown above separated as a yellowish oil
(84.6% yield). The oil was recovered and dried in a rotary
evaporator for 0.5 hours at 50 C at 20 mm. The complex was
subjected, without further purification, to combustion
analysis.
; ~33~
Calculated: C,27.59; H,5.98; N,6.44.
Found: C,24.05; H,5.36; N,5.19.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 3
A solution containing 4.25 grams (0.05 mole) of 2-
pyrrolidone in 7.13 gram (10 ml)diethyl ether was added,
with stirring, to a solution containing 7.23 grams (0.05
mole) of 2-chloroethylphosphonic acid in 7.13 grams (10 ml)
diethyl ether in a 250 ml glass Erlenmeyer flask equipped
with a drying tube and a magnetic stirring bar. The
reaction was effected at ambient temperature and
atmospheric pressure. After a few minutes 10.0 grams the
zwitter ionic complex purported to have the structure shown
` above separated as a yellowish oil (87.2% yield). The oil
was recovered and dried in a rotary evaporator for 0.5
hours at 50C at 20 mm. The complex ~as subjected, without
further purification, to combustion analysis:
Calculated: C,31.27; H,5.66; N,6.10.
Found: C,30.53; H,5.74; N,5.79.
The balance of the product in the ether phase could be
isolated and recoved by evaporation of the diethyl ether
solvent.
~L133~
EXAMPLE 4
A solution containing 4.35 grams (0.05 mole) of
N,N-dimethyl acetamide in 7.13 grams (10 ml) diethyl ether
was added, with stirring, to a solution containing 7.23
grams (0.05 mole) of 2-chloroethyphosphonic acid in 7.13
grams (10 ml) diethyl ether in a 250 ml glass Erlenmeyer
flask equipped with a drying tube and a magnetic stirring
bar. The reaction was effected at ambient temperature and
atmospheric pressure. After a few minutes 10.4 grams of a
zwitter ionic complex purported to have the structure shown
above separated as a yellowish oil (89.8~ yield). The oil
was recovered and dried in a rotary evaporator for 0.5
hours at 50C at 20 mm. The complex was subjected, without
further purification, to combustion analysis:
Calculated: C,31.10; H,6.48; N,6.05.
Found: C,28.27; H,6.19; N,5.18.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EX~MPLE 5
A solution containing 3.65 grams (0.05 mole) of N-
methyl acetamide in 7.13 grams (10 ml) diethyl ether was
added, with stirring, to a solution containing 7.23 grams
(0.05 mole) of 2-chloroethylphosphonic acid in 7.13 grams
(10 ml) diethyl ether in a 250 ml glass Erlenmeyer flask
equipped with a drying tube and a magnetic stirring bar.
The reaction was effected at ambient temperature and atmos-
pheric pressure. After a few minutes 10.4 grams of the
-23-
; 1~3391q~
zwitter ionic complex separated as a yellowish oil (95.6%
yield). The oil was recovered and dried in a rotary
evaporator for 0.5 hours at 50C at 20 mm. The complex was
subjected, without further purification, to combustion
analysis:
Calculated: C,27.59; H,5.98; N,6.44.
Found: C,26.87; H,6.02; N,5.95.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 6
A solution containing 2.95 grams (0.05 mole) of
acetamide in 7.13 grams (10 ml) diethyl ether was added,
with stirring, to a solution containing 7.23 grams (0.05
mole) of 2-chloroethylphosphonic acid in 7.13 grams (10 ml)
diethyl ether in a 250 ml glass Erlenmeyer flask equipped
with a drying tube and a magentic stirring bar. The
reaction was effected at amhient temperature and
atmospheric pressure. After a few minutes 10.0 grams of
the zwitter ionic complex purported to have the structure
shown above separated as a yellowish oil (98.2% yield).
The oil was recovered and dxied in a rotary evaporator for
0.5 hours at 50C. at 20 mm. The complex was subjected,
without further purification, to combustion analysis:
Calculated: C,23.59; H,5.40: N,6.88.
Found: ~ ~,23.22; H,5.59; N,6.74.
-24-
~ 339~
The balance of the product in .he ether phzse could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 7
-
A solution containing 3.09 grams (0.028 mole) of
N-methyl-2-pyridone in 7.13 grams (10 ml) diethyl ether was
added, with stirring, to a solution containing 4.32 grams
(0.03 mole) of 2-chloroethylphosphonic acid in 7.13 grams
(10 ml) diethyl ether in a 250 ml glass Erlenmeyer flask
equipped with a drying tube and a magnetic stirring bar.
The reaction was effected at ambient temperature and
atmospheric pressure. After a few minutes 6.30 grams of
the zwitter ionic complex purported to have the structure
shown above separated as a yellowish oil (87.6% yield).
The oil was recovered and dried in a rotary evaporator for
0~5 hours at 50C at 20 mm. The complex was subjected,
without further purification, to combustion analysis:
Calculated: C,36.44; H,5_23; N,5.19.
Found: C,37.87, H,5.13; N,5.52.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 8
A solution containing 3.39 grams (0.03 mole)of
N-methyl-2-piperidone in 7.13 grams (10 ml) diethyl ether
-25-
1~33~
was added, with stirring, to a solution containing 4.32
gram (0.03 mole) of 2-chloroethylphosphonic acid in 7.13
grams (10 ml) diethyl ether in a 250 ml ylass Erlenmeyer
flask equipped with a drying tube and a magnetic stirring
bar~ The reaction was effected at ambient temperature
and atmospheric pressure. After a few minutes 5.7 grams of
the zwitter ionic complex purported to have the structure
shown above separated as a yellowish oil (73.7~ yield).
The oil was recovered and dried in a rotary evaporator for
0.5 hours at 50C at 20 mm. The complex was subjected,
without further purification, to combustion analysis:
Calculated: C,34.63; H,6.64; N,4.80.
Found: C,37.28; H,6.60; N,5.44.
The balance of the product in the ether phase could be
isolated and recovered by evaporation of the diethyl ether
solvent.
EXAMPLE 9
A solution containing 4.35 grams (0.05 mole) of
N-propyl-formamide in 7.13 grams (10 ml) diethyl ether is
added, with stirring, to a solution containing 7.23 grams
(0.05 mole) of 2-chloroethylphosphonic acid in 7.13 grams
(10 ml) diethyl ether in a 250 ml glass Erlenmeyer flask
equipped with a drying tube and a magnetic stirring bar.
The reaction is effected at ambient temperature and
atmospheric pressure. After a few minutes 10.0 grams of
the zwitter ionic complex puEported to have the structure
shown above separates as a yellowish oil (88.0% yield).
-26-
~ ~a ~ 7!~
The oil was recovered and dried in a rotary evaporator for
0.5 hours at 50C at 20 mm. The balance of the product in
the ether phase could be isolated and recovered by
evaporation of the diethyl ether solvent.
EX~PLE 10
A solution containing 3.50 grams (0.02 mole) of N-
(o-tolyl)-2-pyrrolidone in 7.13 grams (10 ml) diethyl ether
was added, with stirring, to a solution containing 2.88
grams (0.02 mole) of 2-chloroethylphosphonic acid in 7.13
grams (10 ml) diethyl ether in a 250 ml glass Erlenmeyer
flask equipped with a drying tube and a magnetic stirring
bar. The reaction was effected at ambient temperature and
atmospheric pressure. After a few minutes 5.30 grams of
the zwitter ionic complex purported to have the structure
shown above separated as a yellowish oil (81.4% yield).
The oil was recovered and dried in a rotary evaporator for
0.5 hours at 50C at 20 mm. The balance of the product in
the ether phase could be isolate~ and recovered by
evaporation of the diethyl ether solvent.
EXAMPLE 11
A slurry of 3.87 grams (0.03 mole) of N-(2-hydroxy-
ethyl)-2-pyrrolidone was added, with stirring, to 4.32
grams (0.03 mole) of 2-chloroethylphosphonic acid in a 250
ml glass Erlenmeyer flask. Th~e reaction was effected at
ambient temperature and atmospheric pressure. After 30
minutes 8.19 grams of the zwitter ionic complex indicated
to have the structure shown above formed as a homogeneous
yellowish oil (100% recovery).
-27-
,: . . . ... .
~L~.339~
EXAMPLE 12
A solution containing 2.54 grams (0.02 mole) of
N-(isopropyl)-2-pyrrolidone in 7.13 grams (10 ml) diethyl
ether was added, with stirring, to a solution containing
2.88 grams (0.02 mole) of 2-chloroethylphosphonic acid in
7.13 grams (10 ml) diethyl ether in a 250 ml glass
Erlenmeyer flask equipped with a drying tube and a magnetic
stirring bar. The reaction was effected at ambient
temperature and atmospheric pressure. After 20 minutes the
ether solvent was removed by evaporation and 5.40 grams of
the zwitter ionic complex purported to have the structure
shown above was recovered as a yellow oil and the oil dried
in a rotary evaporator for 0.5 hours at 50C at 20 mm (100%
recovery).
EXAMPLE 13
_
A solution containing 5.01 grams (0.03 mole) of
N-cyclohexyl-2-pyrrolidone in 7.13 g~ams (10 ml) diethyl
ether was added, with s~irring, to a soluticn containing
4.32 grams (0.03 mole) of 2-chloroethylphosphonic acid in
7.13 grams (10 ml) diethyl ether in a 250 ml glass
Erlenmeyer flask equipped with a drying tube and a magnetic
stirring bar. The reaction was effected at ambient
temperature and atmospheric pressure. After 30 minutes the
ether solvent was removed by evaporation at reduced
pressure and 9.30 grams ~f the zwitter ionic complex
purported to have the structure shown above was recovered
as a water insoluble, yellowish oil. The oil was recovered
and dried in a rotary evaporator for 0~5 hours at 50C at 20
mm (100% recovery).
-28-
~33g~6
EXAMPLE 14
A solution containing 2.82 grams (0.02 mole) of
N-(tert-butyl)-~-pyrrolidone in 7.13 grams (10 ml) diethyl
ether ~as added, with stirring, to a solution containing
2.88 grams (0.02 mole) of 2-chloroethylphosphonic acid in
7.13 grams (10 ml) diethyl ether in a 250 ml glass
Erlenmeyer flask equipped with a drying tube and a magnetic
stirring bar. The reaction was effected at ambient
temperature and atmospheric pressure. After 20 minutes the
ether solvent was evaporated at reduced pressure, and 5.40
grams of the zwitter ionic complex purported to have the
structure shown above was recovered as a water insoluble
yellowish oil. The oil was recovered and dried in a rotary
evaporator for 0.5 hours at 50C at 20 mm. (100%
recovery).
EXAMPLE 15
A solution containlng 2.54 grams (O.Ol mole) of
N-dodecyl-2-pyrrolidone in 3.57 grams (5 ml) diethyl ether
was added, with stirringr to a solution containing 1.44
grams (0.01 mole) of 2-chloroethylphosphonic acid in 3.57
grams (5 mlj diethyl ether in a 250 ml glass Erlenmeyer
flask equipped with a drying tube and a magnetic stirring
bar. The reaction was effected at ambient temperature and
atmospheric pressure~ After 20 minutes the ether solvent
was evaporated at reduced pressure and 3.40 grams of the
zwitter ionic complex purported to have the structure shown
above recovered as a water insoluble, yellowish oil. The
oil was recovered and dried in a rotary evaporator for 0.5
hours at 50C at 20 mm. (100% recovery).
-29-
1~339l~
EXAMPLE 16
A solution containing 16.5 grams (0.15 mole) of
polyvinylpyrrolidone (K30) in 54.6 grams of water was
added, with stirring, to 28.9 grams of GAF technical grade
2-chloroethylphosphonic acid, containing 21.65 grams (0.15
mole) of 2-chloroethyl phosphonic acid, in a 250 ml glass
Erlenmeyer flask. The reaction was effected with stirring
at ambient temperature and atmospheric pressure. After a
few minutes, the resulting aqueous solution contained 36.0%
by weight of the zwitter ionic polymer purported to have
the structure shown on the following page, was recovered
and dried.
.~
-30-
Y ~1~33~6
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~33~
ANALYSIS
The above products were subjected to infrared
analysis and the results reported in following Table I.
The shift of the carbonyl amide indicates that the present
compounds are complexes.
TABLE I
.
Infrared Carbonyl Wave Length
Product Complex Noncomplexed
of Amide Amide Difference
Example C=O ~ C=O ~ )
1 6.15 5.95 0.20
2 6.12 6.01 0.11
3 6.21 5.95 0.26
4 6.35 6.09 0.26
6.30 6.03 0.27
6 6.07 6.03 0.04
7 6.10 6.03 0.07
6.33 6.12 0.21
6.06 5.89 0.17
11 6.06 6.02 0.04
12 6.25 5.95 0.30
13 6.27 5.97 0.30
14 6.30 5.93 0.37
6.18 5.g3 0.25
-32-
1~339~i
The complex structure of the present compounds was
also determined by the CEPA* concen~ration in the product
by titration in water with NaOH. The CEPA content and
amide content is reported in following Table II.
,
* 2-chloroethylphosphonlc acld
TABLE II
CEPA CONTENT OF PRODUCTS
AS DETERMINED BY TITRATION IN WATER
_ . _
Product Weight % CEPA Mole % CEPA
of
Example Found Theory Found Theory
1 60.74 59.34 51.46 50.00
2 66.66 66.44 50.25 50.00
3 64.53 62.96 51.69 50.00
4 62.04 62.42 49.60 50.00
65.35 66.44 48.79 50.00
6 64.67 71.01 42.83 50.00
7 57.30 56.56 50.53 50.00
8 54.07 56.12 47.g3 50.00
48.22 45.40 52.25 50.00
11 52.9g 52.83 50.16 50.00
12 53.77 53.39 50.38 50.00
13 46.93 46.39 50.59 50.00
14 . 50.85 50.44 50.06 50.00
36.30 36.51 49.77 50.00
.
Alcoholic solutions (methanol) of the complexed
products are also titrated with a standard alcoholic
1~33~j
(isopropanol) KOH solution and compared with similarly
concentrated methanol solutions of CEPA titrated with the
same standard KOH isopropanol solution. The titration
results, reported in following Table III. show that there
is substantially no difference between CEPA and the complex
in the dissociation of the first P-OH bond (Kal), but that
a significant difference between CEPA and the complex
exists in the dissociation of the remaining P-OH (Ka2).
This difference also substantiates the formation of the
present complexes, although the lack of difference in Ka2
value does not indicate the absence of complex formation.
-34-
' ~l33~6
TABLE III
COMPARISON OF CEPA AND
COMPLEX TITRATION WITH KOH IN ISOPROPANOL
-
Product of Kal Ka2
Example (+ 0.1x10 4) (+ 0.07x10
1 1.26x10 4 ~ 1.38x10 10
2 1.41x10 4 1.32x10 10
3 1.07x10 4 2.95x10 10
4 1.00x10 4 0.813x10 10
1.26x10 4 1.05x10 10
6 1.32x10 4 1.51X10-1
7 1.12x10 4 2.95x10 10
8 0.83x10 4 2.45x10 10
1.31x10 4 2.82x10 10
11 0.79x10 4 1.90Xlo-1
12 0.98x10 4 3.16xlo~l
13 1.00x10 4 3.16x10 10
14 0.89x10 4 2.24x10 10
0.76x10 4 1.~6Xlo-lo
CEPA 1.20x10 ~4 0.86x10
-35
~133g~6
BIOLOGICAL ACTIVITY
The compounds of this invention are potent
ethylene release agents and/or stimulate the in vivo
production of ethylene by plants and plant tissue.
Accordinglyr these compounds exhibit standard
physiological effects characteristic of ethylene. Examples
of these effects are well known and include ripening;
stunting; loss of apical dominance; germination; promotion,
inhibition and sex reversal of flowers; leaf senescence,
abscission, floral induction; etc., such as those effects
indicated in Ethylene in Plant Biology by F. B. Abeles.
In both laboratory and field tests, the present
compounds have shown that they strongly stimulate the ln
vivo production of ethylene as well as promote the effect
of ethylene in field application. Some of the present
compounds are more effective stimulators, on a per mole
basis, than 2-chloroethylphosphonic acid.
EXAMPLES 17-29
The ability of the present products to stimulate
ethylene generation was determined by the following ~
procedures: -
In a growth chamber maintained at 30C and 2,000
to 3,000 foot candle light, soybean plants from the same
seed source were grown to the unifoliate state of
development. Each of the fo11Owlng experiments were
carried out in quadruplicate, and the results (found to be
highly reproducible) were averaged and reported in
followin-g Table IV.
-36-
~133~
In each of Examples 17-29, sixteen leaf disc
samples from the unifoliate plant sources were removed by
cutting the leaf with a circular cork borer of 1.78cm
diameter. Each of the sixteen leaf discs were then floated
for 30 minutes in a closed Petri dish on 25 ml of water as a
control or with 25 ml of aqueous solutions containing
either 1,000 ppm (Low Rate) or 3,000 ppm (High Rate) of the
compound to be tested. At the end of 30 minutes, the leaf
discs were removed from the solution, patted dry, and four
each were reinserted in 4 10 ml vials fitted with a septum
through which a syringe could be inserted for extracting a
sample of the supernatant atmosphere. Four replicate gas
samples for each compound were taken after the samples were
allowed to stand in the light for one hour. The samples
were analyzed for ethylene content by gas liquid phase
chromatography. The vials were then placed in the dark for
fifteen hours after which the gas above the leaf discs was
resampled and analyzed in the manner similar to that
described. The results, based on a comparison with the
control, are reported in Table IV in nanoliters of ethylene
,per liter of atmosphere per cm2 of leaf surface per mole of
test compound and are based on the average of four
replicate samples.
-37
1~33~6
TABLE IV
Compound 2
Example of Example R _ nl Ethylene/liter/cm /mmole
1 hr (a.) 15 hr (b)
17 1 Low 6,720 21,904
High 6,690 17,496
18 2 Low 2,923 11,824
High 2,842 12,300
19 3 Low 4,202- 16,919
High 2,859 13,863
4 Low 2,800 13,273
High 3,701 14,923
21 5 Low 2,195 14,586
High 3,631 16,078
22 6 Low 913 8,365
High 2,542 . 11,520
23 7 Low 4,368 15,647
High 4,991 14,681
24 8 Low 4,282 11,850
High 4,603 18,988
25 10 Low 3,379 15,311
High 6,912 15,268
26 11 Low 3,563 16,654
High 4,412 15,295
27 12 Low 3,743 15,090
High :4,805 14,264
28 16 Low 4,679 18,726
High 5,223 16,689
292-Chloro- Low 4,912 15,944
ethylphos- High 4,876 14,035
phonic Acid
Unifoliate Plants
a. in light
b. in dark
c. untreated tissue ~control) gave 125 nl
ethylene/liter/cm after 1 hour and 180 nl
ethylene/liter/cm2 after 16 hours.
Low = 1,000 ppm
High~ 3,000 ppm
-38-
1 ~33~ii
EXAMPLES 29-32
A field test was made as a comparison between
Compound 1 and 2-chloroe~hylphosphonic acid (CEPA) in their
relative ability to cause mature, green, flue-cured tobacco
leaves to turn yellow and ripen. The results of this study
are given in the following Table V.
In the field, 7 separate. plots averaging 50
tobacco plants each, growing under the same conditions,
were reserved for testing. The first two plots were
sprayed with an aqueous solution of CEPA at a rate of
0.00687 lb. mole/acre and the results averaged and reported
in Table V as Plot #I. Another two plots were sprayed with
an aqueous solution of CEPA in the same concentration at a
rate of 0.01374 lb. mole per acre (i.e. the standard
commercial rate employed for CEPA) and the results averaged
and reported in table;V as Plot #2. Another two plots were
sprayed with an aqueous solution of the complex product of
Example I in the same concentration as those above at a
rate of 0.00746 lb. mole/acre and the results averaged and
reported in Table V as Plot #3. The final plot was left
untreated as the control.
, -39-
~33~
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~L~33~6
It is highly significant that the treatment with
the compound of example 1 gave a 7% increase in yield over
2-chloroethyl phosphonic acid, (plot #2), which is the
standard commercial rate for 2-chloroethyl phosphonic acid,
and also provided a ripened harvestable crop within a
quarter of the time required for CEPA, when CEPA and the
compound of Example 1 are applied at substantially the same
rate.
When the present compounds, for example the
compounds of Examples 1 and 8, in a concentration of about
3,000 ppm in aqueous solution are sprayed to run off on
rangy plants during their growing stage (e.g. an
ornamental such as chrysanthenums or a member of the grass
family such as corn), noticeable stunting (10-25%) of the
mature plant results. The compounds of this invention
possess ~any of the other plant growth regulating effects
which are known and are attributed to ethylene. These
effects are realized by the ethylene generating properties
of the present compounds.
EXAMPLE 33
Apple Reddening
Four replicate groups of Cornell McIntosh fruit
bearing apple trees were sprayed to run-off with the
aqueous solutions noted in Table VI below. Another
replicate group of trees was left untreated as a control.
After one week, the apples were harvested and physical
measurements taken. The replicate results were averaged
and reported as follows:
-41-
TABLE VI
Rate
Treatment mmoles/l % Red Color
None -- 36
Ethephon 0.248 53
Ethephon 0.497 67
NMP/CEPA Complex ~.270 69
NMP/CEPA Complex 0.540 74
-
NMP is N-methyl-2-pyrrolldone and CEPA iS 2-chloroethyl-
phosphonic acid.
It has been found that 1.03 mmoles/liter of
Ethephon is required to produce 72~ reddening of Cornell
McIntosh apples in a similar treatment (see Table II of the
paper published in The Journal of American Society for
Horticultural Science, Volume 99, #3, Page 239, May 1974).
EXAMPLE 34
Apple Reddening
Three groups of 4 year old Millersturdeespur apple
trees (5 in each group) were sprayed to run-off with the
aqueous solutions noted in Table VII below. Another group
of 5 four year old trees was left untreated as a control.
After two weeks, the apples were harvested and physical
measurements taken. The replicate results were averaged
and reported as follows:
-42-
~339~g6
TABLE VII
Rate
Treatment mmoles/l ~ Red Color
None -- 33.3
Ethephon 0.248 38.1
Ethephon 0.497 58.4
NMP/CEPA Complex 0.270 64.2
NMP and CEPA are as defined above.
EXAMPLE 35
Walnut Loosening
Two groups of Ashley nut bearing walnut trees (5
trees in each group) were sprayed to run-off with the
aqueous solutions noted in Table VIII. Another group of 5
trees was left untreated as a control. After 10 days, the
replicate results were averaged and reported as follows:
TABLE VIII
Rate Harvestability
Treatment mmoles/Gal. Leaf FaIl% Removable
None ~~
Ethephon 0.0145 3.0 99.5
NMP/CEPA Complex 0.0078 1.2 86.0
NMP and CEPA are as defined above.
Of the Abscission ratings, 3 is considered
excessive, 1 is considered slight and not harmful to the
tree. The harvestability data in the above table was taken
during normal harvest.
-43-
1~L339~6
EXAMPLE 36
Sour Cherry Loosening
Two groups of Montmorency fruit bearing sour
cherry trees (3 trees in each group) had their branches
sprayed to run-off with the aqueous solutions noted in
Table IX. Another group of 3 trees was left untreated as a
control. After one week, replicate results were averaged
and reported as follows. The fruit removal force
measurements were made after seven days on a 100 fruit
sample per replicate.
TABLE IX
Rate Fruit Removal
Treatment mmoles/1 Force, Grams
None ~~ 445
Ethephon 1.375 281
NMP/CEPA Complex 0.716 278
-
NMP and CEPA are as defined above.
The above field test establishesthat it requires
about twice as much Ethephon to obtain a result approaching
the present complex.
-44-
... . , " ..... , . ,, . , . " , ..
~339~6
EXAMPLE 37
.... ... . . _
Filbert Loosening
-
Four groups of Barcellona nut bearing hazel trees
(5 trees in each group) had their branches sprayed to run-
off with the aqueous solutions noted in Table X. Another
group of 5 trees was left untreated as a control. After two
weeks, the replicate results were averaged and reported as
follows:
TABLE X
Rate
Treatment Moles/100 Gal.~ Drop
None -- 13.8
Ethephon 1.31 30.7
Ethephon 2.61 42.9
NMP/CEPA Complex 1.87 50.8
NMP/CEPA Complex 2.82 55.0
NMP and CEPA are as defined above.
EXAMPLE 38
Grape Color Enhancement
Four groups of Zlnfandel fruit bearing grape vines
(5 vines in each group) were sprayed to run-off with the
aqueous solutions noted in Table XI. Another group of 5
vines was left untre~ated as a control. The grapes were
harvested when the control brix was 22~ after which the
grapes were ]uiced to give solutions from which optical
density measurements could be made. The replicate results
were averaged and reported as follows:
-45-
L339~6
TABLE XI
Rate
Treatment mmoles/l % Color
None -~ 50
Ethephon 3.93 91
NMP/CEPA Complex 2.45 100
NMP/CEPA Complex 0.67 71
NMP/CEPA Complex 0.09 39
.
NMP and CEPA are as defined above.
EXAMPLE 39
Sex Éxpression of Cucumbers
Two groups of Galaxy cucumbers (2 plants in each
group) were sprayed to run-off after the first true leaf
stage with the aqueous solutions noted in Table XII.
Another group of 2 plants was left untreated as a control.
The replicate results were averaged and reported as follows:
TABLE XII
RateMale/Female Internode Distance*,
Treatment_mmoles/lFlower RatioCentimeters
None -- 38.6 144
E.hephon 0.0412 8.8 131
Ethephon 0.1237 . 4.1 123
NMP/CEPA Complex 0.0445 3.4 117
NMP/CEPA Complex 0.1336 1.3 105
-
NMP and CEPA are as def1ned above.
*Total distance of l-lS interno~es.
-46-
~339g~;
In the above examples, it is to be understood that any
of the other haloalkyl phosphonic acids such as ~o~ example the
fluorinated, chlorinated, brominated or iodinated methyl, ethyl,
propyl or butyl phosphonic acids, can be substituted in
Examples 1 through 16 above to produce the corresponding complex
product and that the product thus obtained can be substituted in
any of the foregoing examples showing biological effects to
provide compounds having similar utility. Moreover, any of the
monoamides or polymers thereof, such as N,N-diethyl butyramide,
N-propyl butyramide, propamide, N-methyl propamide, N-methyl
acetamide, N,N-dimethyl acetamide, acetamide, N,N-dimethyl
formamide, N-ethyl acetamide, N-butyl acetamide, N-ethyl
pyrrolidone, N-methyl-2-pyrrolidone, N-butyl-2-pyrrolidone,
N-ethyl pyridone, N-methyl pyridone, N-propyl pyridone, 2
pyrrolone, N-methyl pyrrolone, N,N'-dimethylantipyrine, N-methyl ~
piperidone, N-ethyl piperidone, N-naphthyl-2-piperidone, 2- ~.
piperidone, N-butyl plperidone, N-hydroxyethyl pyrrolidone, N- -
isooctyl pyrrolidone, N-isopropyl pyrrolidone, N-¦o-tolyl)
pyrrolidone, N-(2-trichloroethyl) pyrrolidone, polyvinyl
pyrrolidone of between about 20,000 and about 550,000 number
average molecular weight, vinyl-2-pyrrolidone dimer, trimer or
tetramer, N-dodecyl pyrrolidone, N-cyclohexyl pyrrolidone,
N-phenyl pyrrolidone, N-(2-chlorophenyl) pyrrolidone, N-naphthyl ~;:
pyrrolidone, etc. can be substituted in Examples 1 through 16 : .
above, which may also have substituted therein another haloalkyl
phosphonic acid, to produce the corresponding compound, and the
resulting product can be substituted in any of the foregoing
examples showing biological effects to provide compounds having ~ ~:
similar utility. :
. -47-
.. ,, .; .
~1~39~
The monoamide and the ~ -haloethylphosphonic acid, and in particular
~-chloroethylphosphonic acid form a complex under conditions which approach
being anhydrous. As the amount of water present increases the complex tends
to dissociate. At a water content of about 30% there is no more than a
trace of the complex and the components are present individually. As the
amount of water decreases the percentage of complex increases as follows:
Wt. %
Complex Wt. % H20
trace to 2% 32%
6 - 9% 20%
10 -15% 15%
22 -30% 10%
50 -70% 5%
80 -90% 2%
As a result of this behaviour in the~,presence of water composition
of the monoamide and the ~-haloethylphosphonic acid, in the presence of
water, may, depending on the amount of water comprise a tertiary mixture of
the monoamide, the ~-haloethylphosphonic acid and a complex thereof. In the
situation when the carrier is substantially anhydrous the composition will
tend to be in the form of a complex when the preformed complex is added there-
~0 to.
It is to be understood, however, that the present cornplex, alone
or in combination with a minor amount of its dissociation components, can al-
so be applied to the plant in the form of a paste, powder or granulate solid
by use of extenders such as talc, bentonite, clays, diatomaceous earth,
Koalins and other inert and conventional solid extenders in the same concen-
tration ranges set forth for the liquid carriers.
Alternatively the present complex can be first formed on the
plant by separately applying the cyclic monoamide and/or polyvinylpyrrolidone
and the ~.-haloethylphosphonic acid components to the plant. This may also
occur when applying the monoamide in an aqueous carrier and the ~-haloethyl-
i - 47a -
~, ,.'
~L~33~
phosphonic acid in a separate aqueous carrier to the plant and permitting
the ~ater to evaporate. Similarly when fine aqueous sprays are utilized
the carrier may evaporate prior to contacting the plant situs so that the
complex ~çr s~ is applied to the plant.
~ 47b -
