CA1058628A - Iminocarbonylphosphonate brush control agents - Google Patents

Abstract

ABSTRACT
Iminocarbonylphosphonates, such as dimethyl 1,1-bis(dimethylamino)methyleneaminocarbonylphosphonate, useeful as plant growth retardants.

Description

BACKGROUND

This invention concerns the discovery that a selected group of iminocarbonylphosphonates are useful for controlling the growth of plants, particularly for preventing bud break and retarding the growth of woody plants.
Bucha and LangsdorfJ in U.S. Patent 3,849,102, issued November 19, 1974, teach the use of certain dialkylcarbamoylphos-phonates as plant growth retardants. And Langsdorf discloses related compounds also useful as plant growth retardant~, such as ammonium ethyl carbamoylphosphcnate, in U.S. Patent No.
3,819,353,issued June 25, 1974.
The present invention results from efforts to develop new compounds that could be applied in areas such as power line rights-of-way where low-growing and slow-growing vegetation i~ especially desirable.

SUMMARY
According to this invention there is provided novel compounds of formula I, processes for making them, formulations containing them, and methods of using them to retard the growth rate of plants.

O O R
~ " ,6 R - O - P - C - N=C - R4 formula I
O-R
where R is alkyl of 1 to 4 carbon atoms or benzyl;
Rl is Na, K, NH4, or R;
R4 is NR2R3 or OR5;

where R2 is hydrogen or alkyl Or 1 to 12 carbon atoms;
R3 is hydroen or alkyl Or 1 to 3 carbon atoms; and R5 ls alkyl Or 1 to 3 carbon atoms; and R6 ls NR2R3, hydrogen, or alkyl Or 1 to 3 carbon atoms.

Appllcation Or a controlled amount Or compound to woody vegetation results ln a decrease in the rate Or plant growth with llttle or hO apparent damage to the treated plant.
These compounds can also be used to prolong the dormancy Or perennial plants. This protects the unsprouted buds rrom rrost damage.

- ~586~8 DETAII ED DESCRIPTION

Preferred Compounds Preferred are compounds in which R is methyl or ethyl.
Likewise preferred are compounds in which R6 is NR2R3 or hydrogen, R2 18 hydrogen or methyl, and R3 is hydrogen or methyl.
More preierred for their outstanding plant growth regulant effect are compounds in which:
R is methyl or ethyl;
R6 is NR2R3 or hydrogen;
R2 i8 hydrogen or methyl, and R3 is hydrogen or methyl.
Specifically preferred for superior activity are these compounds:
(1) dlmethyl l,l-bis(dimethylamino)methyleneamino-carbonylphosphonate;

(2) methyl l,l-bis(dimethylamino)methyleneamino-carbonylphosphonate, sodium salt;

(3) diethyl l-dimethylaminomethyleneaminocarbonyl-phosphonate;

(4) ethyl l-dimethylaminomethyleneaminocarbonyl-phosphonate, sodium salt;

(5) dimethyl l-amino-l-methoxymethyleneaminocarbonyl-phosphonate,

(6) methyl l-amino-l-methoxymethyleneaminocarbonyl-phosphonate, sodium salt.

- ~058628 Synthesis Dialkgl alkoxycarbonylphosphonates are prepared as taught ln the llterature: Nylen, Ber. 57B, 1023 (1924).
The compounds of thls invention can be prepared by refluxing an alkoxycarbonylphosphonate and an alkyl imine in a suitable solvent for one hour and removing the solvent under pressure to yield the iminocarbonylphosphonate.
The sodium salts of these compounds can be pre-pared by refluxing the dialkyl ester of the lminocarbonyl-phosphonate and sodium iodide in a suitable solvent for one-half hour, cooling the mixture, then filtering and drying the precipitate.
Potassium and ammonium salts of these compounds can be prepared from the sodium salts by using the appropriate ion-exchange methods.
me compounds of this invention can al~o be prepared by refluxing a carbamoylphosphonate and an amide acetal in a suitable 801vent, and removing the solvent under reduced pressure to give the iminocabonylphosphonate.
The preparation of these compounds is further illus-trated by the following examples. Parts are by weight unless otherwise specified.
Example 1 A solution of 54 parts of dimethyl methoxycarbonyl-phosphonate and 3~ parts of 1,1,3,3-tetramethyl~uanidine in 1000 parts of anhydrous tetrahydrofuran was refluxed for one hour. The solvent was removed under reduced pressure to yleld 77 parts of dimethyl l,l=bis(dimethylamino)methyleneaminocar-bonylphosphonate, nD7= 1.4855.

~0586Z8 Exam~le 2 A solution of 54 parts of dimethyl methoxycarbonyl-phosphonate and 33 parts of 1,1,3-trlmethylguanldlne in 1000 parts of anhydrous tetrahydrofuran was refluxed for one hour.
The solvent was removed under reduced pressure to yield 71 parts of dimethyl l-dimethylamino-l-methylaminomethyleneamino-carbonylphosphonate, nD5= 1.4989.
In a similar manner, starting with the appropriate alkoxycarbonylphosphonate and imino compounds, compounds of the following formula can be prepared:

\ ~ " / 3 P - C - N = C
R10 \ R4 R Rl R2 R3 R4 CH3 CH3 C12H25 H N(CH3)2 1.4631 C2H5 C2H5 CH3 CH3 N(CH3)2 C4Hg C4Hg CH3 CH3 ~(CH3)2 C2H5 C2H5 CH3 CH3 N(C2H5)2 CH3 CH3 CH3 CH3 ( 3~ )2 20 ~ -CH2 ~ CH2 CH CH3 N(CH3)2 Example 3 A solutlon of 25 parts of dimethyl l,l-bls(dimethyl-amino)methyleneaminocarbonylphosphonate and 15 part~ of sodium iodlde in 300 parts of anhydrous tetrahydro~uran was refluxed for one-half hour. me mixture was then cooled and the pre-cipitate filtered and dried to give 34 parts of methyl 1,1-bis(dimethylamino)methyleneaminocarbonylpho~phonate, sodium salt, m.p. 173.

Example 4 10 A solution of 24 parts o~ dimethyl l-dimethylamino-l-methylaminomethyleneaminocarbonylphosphonate and 15 parts of sodlum lodlde in 300 part~ of anhydrous tetrahydrofuran wa~ refluxed for one-half hour. m e mixture wa~ then cooled and the precipltate filtered and drled to give 16 parts oi methyl l-dimethylamino-l-methylaminomethyleneaminocarbonyl-phosphonate, sodlum salt, m.p. 181.
In a slmilar manner, starting with the approprlate carbonylphosphonate, compounas of the following formula can be prepared:

\ ~ ~ NR2R3 / P - C - N = C
R10 ~ R4 R Rl R2 ~ R4 ~ 4_ CH3 Na C12H25 H N(CH3)2 1.5055 C2H5 Na+ CH3 CH3 N(CH3)2 C4Hg Na+ CH3 CH3 N(CH3)2 C2H5 Na+ H H NH2 C2H5 Na+ CH3 CH3 N(C2H5)2 ~' ` lOS86ZI~

R Rl R2 R3 R4 CH3 Na+ CH3 CH3 ( 3 7)2 CH2 Na+ CH3 CH3 N(CH3)2 C2H5 Na+ C3H7 C3H7 NH2 By using the appropriate ion exchange methods, the following salts can be prepared from the sodium salts of the correspondlng imlnocarbonylphosphonate.

R0 \ ~ / NR2R3 P - C - N = C
Rl ~ \ R4 R Rl R2 R3 R4 10 CH3 K+ H H NH2 -CH2 K+ CH3 CH3 N(CH3)2 n-C4Hg NH4+ H H NH2 CH3 K+ n~C3H7 n-C3H7 N(CH3)2 C2H5 NH4+ CH3 CH3 N(n~C3H7)2 CH3 K+ C12H25 H N(CH3)2 Example 5 A mixture of 23 parts of 0-methylisourea and 54 parts of dimethyl methoxycarbonylpho~phonate in 1000 parts of anhydrous tetrahydrofuran was refluxed for one hour. me solvent was re-moved to glve dlmethyl l-amino-l-methoxy-methyleneaminocarbonyl-phosphonate, nD7 = 1.4774.

In a slmilar manner, starting with the appropriate carbonylphosphonate and imino compounds, compound~ of the following formula can be prepared:

RO O ~ NR2R3 P - C - N = C
R10V~ \ R4 R Rl R2 R3 R4 CH2 ~ CH2 CH3 CH3 OCH3 CH3 CH3 n~C3H7 n~C3H7 OCH3 Example 6 A solution of 21 part~ dimethyl l-Pmlno-l-methoxy-methyleneaminocarbonylphosphonate and 15 part~ of sodium lodide was stirred for 18 hours in 300 parts of anhydrous tetrahydrofuran. m e solution i8 cooled and then riltered to give the methyl l-amino-l-methoxymethyleneaminocarbonylphos-phonate, ~odium salt, m.p. 83d.
In a similar manner compound~ of the following formula can be prepared:

, ~,,, - lOS86Z8 RO \ ~ " / NR2R3 / P - C - N = C ~

R Rl R2 R3 R4 ~ CH2 Na+ CH3 CH3 OC3H7 CH3 Na~ n~C3H7 n~C3H7 OCH3 n-C4Hg Na+ ~ CH3 CH3 OCH3 CH3 Na+ CH3 C2H5 OCH3 CH3 Na+ C12H25 CH3 OCH3 Compounds o~ the following formula can be made by conventional ion exchange method~, ~tarting with the 80dium ~alt~ of the corre~ponding iminocarbonylphosphonate~, RO O ~ NR2R3 P - C - N = C
Rl ~ ~ R4 R Rl R2 R3 R4 _ CH3 K+ H H OCH3 CH3 NH4+ CH3 CH3 OCH3 2 NH4+ CH3 CH3 OC3H7 CH3 K+ n~C3H7 n~C3H7 OCH3 n-C4Hg K+ CH3 CH3 OCH3 CH3 NH4+ CH3 CH3 OC3H7 CH3 K+ C12H25 CH3 OCH3 .,.~,"
, .

Example 7 A solution of 54 parts of diethyl carbamoylphosphon-ate and 36 parts of dimethyl formamide dimethyl acetal was refluxed in 1000 parts of anhydrous tetrahydrofuran for eight hours. m e solvent was removed under reduced pressure to give 70 parts of diethyl l-dimethylaminomethyleneaminocarbonyl-phosphonate, n24 = 1.4970.

Example 8 A solution of 24 parts of diethyl l-dimethylamino-methyleneaminocarbonylpho~phonate plus 17 partæ of sodium iodidein 300 parts of anhydrous tetrahydrofuran was refluxed for two hours, cooled, and filtered to give 15 parts of ethyl l-dimethylaminomethyleneaminocarbonylphosphonate, sodium salt, m.p. 174d.

Example 9 A ~olution of 98 parts of diethyl methoxycarbonyl-phosphonate plus 47 parts of acetamidine hydrochloride in 1000 parts of anhydrous tetrahydrofuran can be refluxed for 8 hours and the solvent then removed under reduced pressure to give diethyl l-amino-methylmethyleneaminocar-bonylphosphonate. In a similar manner, starting with the appropriate alkoxycarbonylphosphonate and imino compounds, the following compounds can be prepared:
O O

P - C - N = C
Rl ~ \ R4 R Rl R4 R6 -CH2 ~ CH2 NH2 CH3 C4Hg C4Hg NH2 CH3 CH3 CH3 N(CH3)2 CH3 CH3 CH3 N(CH3)2 H
C2H5 C2H5 ( 3 7)2 H
lO CH3 CH3 OCH3 Exam~le lO

A ~olution o~ 22 part~ of dlethyl l-amlno-l-methyl-methyleneaminocarbonylphosphonate and 15 parts of sodium lodide can be re~luxed in 300 parts of anhydrous tetrahydro-furan for one hour, cooled, and then flltered to give ethyl l-amino-l-methylmethyleneaminocarbonylpho~phonate, sodium salt.
In a slmilar manner, starting with the appropriate aminocarbonylphsophonate, the following compounds can be prepared:

RO \ ~ ,, ~ R6 P - C - N = C
RlO ~ R4 `~

R Rl R4 R6 C2H5 Na+ OCH3 CH3 ~ CH2 Na+ NH2 CH3 C4Hg Na+ NH2 CH3 CH3 Na+ MH2 C3H7 C2H5 Na+ OC3H7 CH3 CH3 Na+ N(CH3)2 CH3 C2H5 Na+ ( 3 7)2 H
CH3 Na+ OCH3 H

Compounds oi the following formula can be made by conventional ion exchange methods startlng w~th the sodium ~alts of the corresponding methyleneamlnocarbonylpho~phona~es:

RO ~ ~ n ~ R6 ~ P - C - N = C ~

R Rl R4 R6 C2H5 K+ OCH3 CH3 -CH2 NH4+ NH2 CH3 C4Hg K~ NH2 CH3 -:1058628 R Rl R4 R6 3 4+ N(CH3)2 CH3 C2 5 4 ( 3 7)2 H
CH~ K+ OCH3 H

Formulatlon Useful formulations of the compounds of Formula I
can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wet-table powders, emulslflable concentrates and the like.
Nany of these may be applied dlrectly. Sprayable ~ormula-tlons can be extended in suitable media and used at spray volumes of irom a few liters to several hundred liters per hectare. High strength composltions are primarily used as intermediates for ~urther formulation. The formulation~, broadly, contaln about 1% to 99~ by weight of activc ingre-dlent(s~ and at least one of a) about 0.1~ to 20% surfactant(s) and b) about 5~ to 99~ solid or liquid diluent(s). More specifically, they will contaln these lngredients in the following approximate proportion~:
Percent by Weight Active Ingredlent Diluent(s) Surfactant(s) Wettable Powders 20-90 0-74 1-10 Oil Suspensions, Emulsions, Solutions (including Emulsifi-able Concentrates) 5-50 40-95 0-15 ; - 14 -~0586Z8 Percent by Weight Active Ingredient Diluent(s) Surfactant( 8 ) Aqueous Suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 1-95 5-99 0-15 High Strength Composltions 90-99 0-10 0-2 Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physi-cal properties of the compound. Higher ratios of surfactant to actlve ingredient are sometimes desirable, and are achleved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd. Edn., Dorland Books, Caldwell, N.J. m e more absorptive diluents are preferred for wettable powders and the denser ones ~or dusts. Typical liquid diluents and solventsare described in Marsden, "Solvents Guide", 2nd Edn., Interscience, New York, 1950. Solubility under 0.1~ is pre~erred for suspension concentrates, solution concentrates are preferably stable against phase separation at 0C. "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingre-dients should be approved by the U.S. Environmental Protec-tlon Agency for the use intended.

-~oss6zs The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredi-ents. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Sus-pensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,o60,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th. Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.
For further information regarding the art of formu-lation, see for example:
J. B. Buchanan, U.S. Patent 3,576,834, April 27, 1971, Col. 5 Line 36 through Col. 7 Line 70 and Ex. 1-4, 17, 106, 123-~40 ~. R. Shaffer, U.S. Patent 3,560,616, Feb. 2, 1971, Col. 3 Line 48 through Col. 7 Line 26 and Examples 3-9, 11-18.
E. Somers, "Formulation", Chapter 6 in Torgenson, "Fungicides", Vol. 1, Academic Press, New York, 1967.
H. M. Loux, U.S. Patent 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through Col. 7, Line 19 and ExamPles 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192, March 1~, 1967, Col. 5 Line 43 through Col. 7 Line 62 and Ex. 8, 12, 15, 39 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, 169-182.
H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3 Line 66 through Col.
Line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961 pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Handbook', 5th Edn. Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

ExamPle 11 Percent Dimethyl l,l-bis(dimethylamino)methyleneamino-carbonylphosphonate 20 Blend of oil soluble sulfonates with polyoxy-ethylene ethers 6 Isophonone plus inerts in technical 74 m e above ingredients are mixed to give a homo-geneous solution.

Example 12 Percent Methyl l,l-bis(dimethylamino)methyleneamino-carbonylphosphonate, sodium salt 90 Synthetic fine silica 2 Magnesium sulfate heptahydrate plus inerts in technical 8 After blending, the above ingredients are hammer milled so that all particles will pass a U.S.S. 50 mesh (297 mm) screen.

ExamPle 13 Percent Methyl l,l-bis(dimethylamino)methyleneamino-carbonylphosphonate, sodium salt 25 Water plus inerts in technical 75 me above ingredients are mixed to yield ~ h~mo-geneous solution.
Example 14 Percent Diethyl l-dimethylaminomethyleneamino-carbonylphosphonate 25 Blend of oil soluble sulfonates and poly-oxyethylene ethers 15 Paraffinic spray oil, such as Sunspray 7N~ 10 Cyclohexanone plus inerts in technical 50 All of the lngredients, except the paraffinic oil, are stirred to~ether and warmed gently to effect solution.
After solution is complete, the oil is added and stirring is continued to give a homogeneous liquid.
ExamPle 15 Percent Ethyl l-dimethylPm~nomethyleneaminocarbonyl-phosphonate, sodium salt 90 Sodium dialkylsulfosuccinate 0.5 Solid condensate of ethylene oxide with base formed by condensing propylene oxide with propylene glycol 3 Synthetic fine silica plus inerts in technical 6.5 me above ingredients are blended, hammer milled, and then passed through a USS 50 mesh screen.
Example 16 Percent Dimethyl l-amino-l-methoxymethyleneamino-carbonylphosphonate 33 Blend of oil Qoluble sulfonates and polyoxyethylene ethers 10 Xylene plus inerts in technical 57 m e ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in the packaginæ operation to remove any extraneous undis-solved material in the product.
Example 17 Percent Methyl l-amino-l-methoxymethyleneamino-carbonylphosphonate, sodium salt 20 Blend of polyethoxyalcohols 4 Methanol 36 Water plus inerts in technical 40 m e ingredient 8 are stirred together and warmed gently to effect solution. Extraneous insolubles are re-moved by passing the solution through a fine screen or cloth ~llter.

Use mis invention is based on the discovery that the compounds of formula I are effective in modifying the growth rate of plants. More particularly they are useful as plant growth retardants. The term "plant growth retardant" as used in this disclosure means an agent which will slow the growth of a plant and prevent bud break in the spring when applied to the plant or its locus.
The compounds of this invention are especially useful for preventing bud break and retarding the growth of woody plants. They, therefore, can be applied in areas such as power line rights-of-waywhere controlled vegetation is required. Treatment with these compounds greatly reduces the growth of the trees and shrubs which effectively increases the time until the next trimming is required to keep the trees from growing into the power lines. This can result in a sub-stantlal savings in expenditures for powerline maintenance.
These compounds are also effective for retarding the growth rate of viney plants, such as bindweed and morningglory.
m ese compounds can also be used to prolong the dormancy of perennial plants. mis protects the unsprouted buds from frost damage. m is delaying action can be especi-ally important in the protection of flower buds, which in some years may sprout early and be ~illed by cold temperatures.
Application to plants during the stage when the following year's buds are forming or developlng produces marked re-tardation of bud break the following spring and greatly reduce 8 growth.
m ese compounds can be employed as foliar sprays or soil applicatlons. Preferably they are applied as foliar or dormant wood sprays to the polnt of run-off although lower-volume application can also be ef~ective. mey are very versatile and can be applied during different time periods to suit the convenience cf the person applying them. For example, they may be applied in spring a short time before the perlod when maximum plant growth is expected or later in the growing season just after trimming to cause growth retardation. mey can also be applied when the year's growth has ceased (late summer, fall, or winter) with the result that treated plants will remain dormant the following sprlngJ while untreated plants will sprout and grow.
me application rate is dependent on the species to be treated and the results desired. In general, rates of 0.25 to 20 kilograms per hectare are used although higher or lower rates can sometimes achieve the desired effect.
To illustrate the growth retardant activity of the compounds and salts of this invention, the following data are presented.
m e compounds used in these tests are represented in the tables by the following letter designations.
A = dimethyl l,l-bis(dimethylamino)methyleneaminocarbonyl-phosphonate, B = methyl l,l-bis(dimethylamino)meth~leneaminocarbonyl-phosphonate, sodium salt;
0 C = dimethyl l-dimethylamino-l-methylaminomethyleneamino-carbonylphosphonate;
D = methyl l-dimethylamino-l-methylaminomethyleneamino-carbonylphosphonate, sodium salt;

- 20 _ E = diethyl l-dimethylaminomethyleneaminocarbonylphosphonate;
F = ethyl l-dimethylaminomethyleneaminocarbonylphosphonate, sodium salt, m.p. 174 (dec), G = dlmethyl l-amino-l-methoxymethyleneaminocarbonylphosphonate;
H = methyl l-amino-l-methoxymethyleneaminocarbonylphosphonate, sodium salt, m.p. 83 (dec);
I = dimethyl l-dimethylamino-l-dodecylamnnomethyleneamino-carbonylphosphonate;
J = methyl l-dimethylamino-l-dodecylaminomethyleneamino-carbonylphosphonate, sodium salt.

Brush Control Testm e test compounds were applied in a non-pnytotoxic solvent with a wetting agent and a humectant to pots o~ privet (Llgustrum sp.), willow (Salix sp.), Forsythia (Forsythia sp.) and apple (Molus sp.). m e plants were maintained in a green-house. Plant response ratings were taken one week and eight weeks after application.

Application Privet Willow Forsythia Apple Rate, ~ ~8 Compowld Kg/Ha wk wks wk wks wk wk ~ wk wks 4 0 9G O 9G O - O lOG

4 0 lOB O O O O O lG

4 0 8G 4C - lC O 0 2X

4 0 6G 5C 3G O O O lG

4 09G O lG O O 0 5X
F 1 06G O lG O O O O
4 0lOG 5P 9G O 8G lC ~G
lD 5D 4X
G 1 0lOG O O O O O O

*"wk. " = week(s) The plant response ratings are composed of a number and a letter. m e number describes the extent of the response and ranges from zero to ten with zero representing no response, and ten repre-senting 100~ response. The letter describes the type of the response, as explained below:
B - burn C - chlorosis/necrosis D - defoliatlon G - growth retarded H - formative ef~ect (malformation or hormone type) P - terminal bud injury X - axillary ætimulatlon Brush Overwintering Test In early October, 1974, the test compounds were applied ln non-phytotoxic solvent with a wetting agent and a humectant to pot~ of whlte birch (Betula alba), Sassafras (Sassafras albldum var.
Molle)J willow (Salix sp.), loblolly plne (Pinus Toeda), California prlvet ~Ligustrum ovalifolium), apple (Pyrus mal~s ev. Rome), forsythia (Forsythia sPectabilis)~ and redbud (Cercis canadensis).
The plants were maintained in a greenhouse for five days and then were moved out of doors to a slathouse where they overwintered and remained until July, 1975, when the plant response ratings in the table below were taken.

~1 o o o o ~o o ~ ~ ~o o ,, Q~
~i ~ o~ o o ¢

~s h a~ C~
o ~ O ~ o ~u~

t, O t-,~ O O

~1 c~
o u~ o ~n ~ C~ X ~
u~o o , o~ ~1 d S~
~ ~ ~0 0 ~0 :~ m ~1 ,1 ~ 5~ N 0 C~l 0 o C cl m The plant response ratlngs are composed of a number and a letter. The number describes the extent of the re~ponse and range~ from zero to ten with zero representing no response, and ten representing 100%
response. m e letter describes the type of the response as explained belo~:
C - chlorosis/necrosis G - growth retarded P - terminal bud ln~ury X - axillary stlmulation ~1~, Seeds of crabgrass (Digitaria sp.), barnyard-grass (Echinochloa crus~alli), wlld oats (Avena fatua), Cassia tora, morningglory (I~omoea spp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rlce, wheat and nutsedge tubers were planted ln a growth medium and treated preemergence with the chemicals dissolved in a non-phytotoxic ~olvent. At the same time, cotton having flve leaves (including cotyledonary ones), bush beans wlth the second trifoliate leaf expanding, crab-grass with two leaves, barnyardgrass with two leaves, wild oats with one leaf, cassia with three leaves (including the cotyledonary ones), cocklebur with four leaves (including the cotyledonary ones), sorghu~
with three leaves, corn with three leaves, soybean with two cotyledonary leaves, rice with two leaves, wheat with two leaves, and nutsedge with three-five leaves were sprayed. Treated plants and controls were maintained in a greenhouse for sixteen days, then all species were compared to controls and visually rated ~058628 for response to treatment.
Ratlngs for compounds tested by this procedure are recorded in the following table.

~0~628 os o o -- o ~ o 3~ I o o o o __ _ _ 11~0~ o o o o N~O.~ o o o o _ ~
~~HM O O O O
Sl~;~O a~IIM o o o o ss~ a~ O O O O
~ _ PSS~ O O O O
~a~s~n~ O O O o _ _~. _~ .
~ISS~) o o o o E~ .
o~ o o o o _ __ ~ ~dO10 ~MIN~aO~ o o o o o _. , E~ ~UlH~IOS ~I v u~~ c~ ~ ~D ~
~: _ o o o ,I m N~OS ~ c~ ~ c~
_ _ __ N~OD t~ ,~ o N~ O
~HM o o o o ~q . . . , S~O alIM o o o o ~ ss~ a~ o ~ O ~ al ~i . ,r SS~ O O O_ O
E~'~ ~a~s~QN O O O O
0~ . ~..................... . ... ~_ ~ ~ss~ ~, ~c~ o o ~.1 ~1~ 0~ ~c~ ~ c~ ~ t~ ~ ~ ~ m ~01~ ~3NIN~0~[ 0 ~ o~ ~ ~ ,~ ~ ~ ~ ,I m NO~O~ oo t~ U~ H 0 t~ H ~--~ CS~ l m u~a~ Usna ~O ~ ~ ~ ~ t~ ~i ~ ~ tl: ~ ~
_ . ~ . .
dq~ c~ cu N c,l . ~ l ._ .

o ~: m ~ H
t~

-- 10586~8 _ ~nH~OS o o u~ ~ o o o o o o o . _ __ M~UOS o o cu c~ o o l _ ~ N~IO~ o o c~l ~ o ~ ~
Z;
~:aHM O o o o o S~O aqIM o o o o o _ .___ __ _ ss~ a~ o o ~ o o ~ ___ _ _ I
SS~ o cu ~ cu~, o o . _ ~ . _ ~a~s~nN O O O O O
_ ~SS~ O ~C~ ~ ~ O O
____ ._ o~ O c~l ~ O O O
~IOl~ ~NIM~O~ o C~J ~ N ~ O O
_ ~ OS ~ ~ o o . _ ~ ,1 :q o o o o ._ __ M~3:~OS ~ m ~ N~, O O
~_ _ __ M~O~ ~c~,I m o ~c~ ~ o ~ . .__ _ L~HM o o o o o S~O alIM o o o o o ~; , , a~M~ o o o o o ~ss~ o o o o o - ~
E~~a~s~nN o O O O O
~0 l _ .
bTISS~ cu ~ o ,1 ~: o o o~ ~ ,I m ,1 :~ cu ~ ~ o ~01~ ~MI~O~ t--c~ N m .1~ ~c~ ,I v ~D ~ ,I v ~0~;0~ ~c~ ,I m u~ ~: co ~ cu :~ ~ x u~a 3 ~sn~[ m ~ ~ m ,~ ~ ~ v ~ o , a~aa ~ ql C~J C\l C~ ~U
l .

P~
o v ~ ~ ~ :~:
v _ 28 -me plant response ratings are composed of a number and a letter. me number describes the extent of the response and ranges from zero to ten with zero representlng no response, and ten representing 100~
response. The letter describes the type of the response, as explained below (Note: "6y~' is an exception to this descrlption, and is identified below):
B - burn C - chlorosis/necrosis D - defoliation E - emergence inhibited G - growth retarded H - formative effect (malformation or hormone type) I - increased chlorophyll U - unusual pigmentation 6Y - abscised buds or flowers Bean Growth Modifier Test me test compounds were applied in a non-phytotoxic solvent with a wetting agent and a humectant to pots of 10-day old Black Valentine (pole) snap beans with the primary leaves fully expanded and 3 1/2-week old Tenderette (or Tender Crop) (bush) snap bean plants with the earl~ flower buds barely visible. The plants were maintained in a greenhouse, and plant response ratings were taken 1 and 3 weeks after application. me bush beans were retained and harvest measurements were made about one week later.

o u~ ~ o 1~

31 ~

~1~ o ~ o ~ . ~

l b ¦ ~ O O 1~ 0 0 1~ 0 O
I ~
. I
~a I ~ ~1 ' ~U
I O

~ o o O O o O O
P~ ~ ~1 ~

m e plant response ratings are composed of a number and a letter. me number describes the extent of the respon~e and ranges from zero to ten with zero representing no response and ten representlng 100% response. The letter describes the type of the response, as explained below (Note: ll6F" and "7Q"
are exceptions to this description, and are identified below):
C - chlorosis/necrosis G - growth retarded H - iormatlve effect (malformation or hormone type) 6F - delayed flowering 7Q - decreased number of fruit Soybean Growth Modifier Test The test compounds were applled in a non-phytotoxic solvent with a wetting agent and a humectant to pots of 30 cm tall Kent soybean plants at the early flowering stage and with 5-6 trifoliate leaves. m e plants were maintained in a greenhouse, and plant response ratings were taken 2, 5 and 10 week~
after application. Following the 10-week ratings, the plants were allowed to mature and dry, after which measurements were taken of the number of pods, number of seeds, and seed weight.

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CU ~i ~i N

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cr~ ~ ~ ~ ~ ~
U~

0 ~D O C~l O O
IS~ ~D ~ 00 E~ a~
~ ~Q

:~ N
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C~
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V o o o o o ~I C~J CU
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:I
~1 c, m ~0s8628 The plant response ratings are composed of a number and a letter. The number describes the extent o~ the response and range~ from zero to ten with zero representlng no response, and ten representing 100 response. me letter describes the type o~ the response, as explained below:
C - chlorosis/necro~is ~ - growth retarded X - axillary stlmulation

Claims (25)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;
R1 is Na, K, NH4, or R;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 i5 alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms.

2. me compound of claim 1 in which R ig methyl or ethyl.

3. The compound of claim 1 in which R6 is NR2R3 or hydrogen, R2 is hydrogen or methyl, and R3 is hydrogen or methyl.

4. The compound of claim 1 in which:
R is methyl or ethyl;
R6 is NR2R3 or hydrogen;
R2 is hydrogen or methyl; and R3 is hydrogen or methyl.

5. The compound of claim 4: dimethyl 1,1-bis-(dimethylamino)methyleneaminocarbonylphosphonate.

6. The compound of claim 4: methyl 1,1-bis(di-methylamino)methyleneaminocarbonylphosphonate, sodium salt.

7. The compound of claim 4: diethyl 1-dimethyl-aminomethyleneaminocarbonylphosphonate.
.

8. The compound of claim 4: ethyl 1-dimethyl-aminomethyleneaminocarbonylphosphonate, sodium salt.

9. The compound of claim 4: dimethyl 1-amino-1-methoxymethyleneaminocarbonylphosphonate.

10. The compound of claim 4: methyl 1-amino-1-methoxymethyleneaminocarbonylphosphonate, sodium salt.

11. A method for preventing bud break and re-tarding the growth rate of plants which comprises applying to the plants an effective amount of a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;
R1 is Na, K, NH4, or R;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 is alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms.

12. The method of claim 11 in which R is methyl or ethyl.

13. The method of claim 11 in which R6 is NR2R3 or hydrogen, R2 is hydrogen or methyl, and R3 is hydrogen or methyl.

14. The method of claim 11 in which R is methyl or ethyl; R6 is NR2R3 or hydrogen, R2 is hydrogen or methyl;
and R3 is hydrogen or methyl.

15. The method of claim 14 in which the compound is dimethyl 1,1-bis(dimethylamino)methyleneaminocarbonyl-phosphonate.

16. The method of claim 14 in which the compound is methyl 1,1-bis(dimethylamino)methyleneaminocarbonylphos-phonate, sodium salt.

17. The method of claim 14 in which the compound is diethyl 1-dimethylaminomethyleneaminocarbonylphosphonate.

18. The method of claim 14 in which the compound is ethyl 1-dimethylaminomethyleneaminocarbonglphosphonate, sodium salt.

19. The method of claim 14 in which the compound is dimethyl 1-amino-1-methoxymethyleneaminocarbonylphosphonate.

20. The method of claim 14 in which the compound is methyl 1-amino-1-methoxymethyleneaminocarbonylphosphonate, sodium salt.

21. A method for retarding the growth rate of viney plants which comprises applying to the plants an effective amount of a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;
R1 is Na, K, NH4, or R;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms, and R5 is alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms.

22. A process for preparing a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;
R? is R;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 is alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms;
which comprises: refluxing in a suitable solvent a compound of the formula where Y is oxygen or sulfur; and R7 is C1-C4 alkyl;
with a compound of the formula:

23. A process for preparing a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;

R? is R;
R? = NR2R3;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R? = hydrogen or alkyl of 1 to 3 carbon atoms;
which comprises:
refluxing in a suitable solvent a compound of the formula with a compound of the formula:

where Q = CH3 or C2H5.

24. A process for preparing a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl;
R? is Na, K or NH4;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 is alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms;
which comprises: refluxing in a suitable solvent a compound of the formula where R1 is R;
with NaI; and optionally then using conventional ion exchange with K+ or NH4.

25. A process for preparing a compound of the formula:

where R is alkyl of 1 to 4 carbon atoms or benzyl, said process being selected from the group consisting of process (A), when R1 is R;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 is alkyl of 1 to 3 carbon atoms; and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms;
which comprises: refluxing in a suitable solvent a compound of the formula where Y is oxygen or sulfur, and R7 is C1-C4 alkyl;
with a compound of the formula:

(B), when R1 is R;
R4 = NR2R3;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R6 = hydrogen or alkyl of 1 to 3 carbon atoms;
which comprises:
refluxing in a suitable solvent a compound of the formula with a compound of the formula:

where Q = CH3 or C2H5, and (C), when R1 is Na, K or NH4;
R4 is NR2R3 or OR5;
where R2 is hydrogen or alkyl of 1 to 12 carbon atoms;
R3 is hydrogen or alkyl of 1 to 3 carbon atoms; and R5 is alkyl of 1 to 3 carbon atoms, and R6 is NR2R3, hydrogen, or alkyl of 1 to 3 carbon atoms;
which comprises: refluxing in a suitable solvent a compound of the formula where R1 is R;
with NaI; and optionally then using conventional ion exchange with K+ or NH4+.