US3846512A

US3846512A - Carbamoylphosphonates

Info

Publication number: US3846512A
Application number: US00283769A
Authority: US
Inventors: W Langsdorf
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1968-05-24
Filing date: 1972-08-25
Publication date: 1974-11-05
Anticipated expiration: 1991-11-05

Abstract

This disclosure teaches a method for employing novel carbamoylphosphonates such as ammonium ethyl carbamoylphosphonate, ammonium isopropyl carbamoylphosphonate and ammonium allyl carbamoylphosphonate to regulate the growth rate of plants.

Description

United States Patent [191 Langsdorf [451 Nov..5, 1974 CARBAMOYLPHOSPHONATES [75] Inventor: William P. Langsdori, Wilmington,

Del.

260/239 B, 260/239 EP, 260/247.7 P,

260/429.9, 2 60/294l7 A, 260/923, 260/924 [51] Int. Cl. C071 9/40, A01n 5/00 [58] Field of Search 260/943 [56] References Cited UNITED STATES PATENTS 3,005,010 10/1961 Grisley ..260/943X Primary ExaminerAnton H. Sutto [57] ABSTRACT This disclosure teaches a method for employing novel carbamoylphosphonates such as ammonium ethyl carbamoylphosphonate, ammonium isopropyl carbamoylphosphonate and ammonium allyl carbamoylphosphonate to regulate the growth rate of plants.

5 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of my copending application Ser. No. 85,221, filed Oct. 29, 1970, which is a continuation-in-partof my application Ser. No. 803,962, filed Mar. 3, 1969, now abandoned, which was in turn a continuation-in-part of my earlier application Ser. No. 731,732, filed May 24, 1968, now US. Pat. No. 3,627,507.

BACKGROUND OF THE INVENTION This invention relates to the discovery that a selected group of novel carbamoylphosphonates can be used to regulate the growth rate of plants. More particularly, the compounds of this invention are useful for controlling the growth of woody vegetation.

Related compounds such as the dialkyl carbamoylphosphonates are disclosed in U.S. Pat. No. 3,005,010 as herbicides.

SUMMARY OF THE INVENTION In summary, this invention relates to a novel group of carbamoylphosphonates, the method of using the carbamoylphosphonates to regulate the growth rate of plants and formulations containing carbamoylphosphonates which are useful to regulate the growth rate of plants.

More particularly, the 'carbamoylphosphonates of this invention are represented by the formula:

wherein:

R is alkyl of one through six carbon atoms,chloroalkyl of one through six carbon atoms containing up to three chlorine atoms, bromoalkyl of one through six carbon atoms containing up to three bromine atoms, alkoxy alkyl of three through seven carbon atoms, alkenyl of two through six carbon atoms, alkynyl of three through four carbon atoms, phenyl or benzyl;

R is hydrogen or methyl;

R is hydrogen, methyl, amino, methylamino, or dimethylamino;

R and R; can be taken together to form a ring selected from (CH O(CH or (CH where n is 2-6;

M is selected from the group consisting of ammonium, hydrogen, sodium, lithium, potassium, calcium, magnesium, zinc, manganese, barium or where R R and R; can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, or hydroxy alkyl of two through four carbon atoms; and R is hydrogen, alkyl of one through 12 carbon atoms, allyl, benzyl, amino, methylamino, or dirnethylamino; R and R, can be taken together to form a riiig that is (CI-I2);

and R and R are H.

Preferred compounds of this invention include those compounds of formula (1) where R is alkyl of one through four carbons or alkenyl of three through four carbons; R and R are each hydrogen; and M is ammonium, hydrogen, or alkali metal such as sodium, lithium or potassium.

The most preferred compounds of this invention are ammonium allyl carbamoylphosphonate, ammonium ethyl carbamoylphosphonate, and ammonium isopropyl carbamoylphosphonate.

Another aspect of this invention relates to the method for modifying the growth rate of plants which comprises applying an effective amount of a compound of formula (1) to a plant to effect modification of the growth rate of said plant. Specifically, the method of this invention results in retarding the growth rate of the treated plants.

Another aspect of this invention relates to fonnula-' tions of compounds of formula (1) with suitable agricultural adjuvants and modifiers or with tree wound dressings.

DESCRIPTION OF THE INVENTION formula l are particularly useful to retard the growth rate of plants without killing them. The compounds of this invention are particularly useful to retard the growth of woody plants. The compounds of this invention can, therefore, be applied in areas such as power line rights-of-way where low-growing and slow growing vegetation is especially desirable.

In addition to their value as plant growth retardants the compounds of this invention can also be used to, control flowering, fruit set and coloration on apples and other fruits. They are useful to control the growth and flowering of ornamental species such as chrysanthemum and azalea.

The compounds of this invention can also be used to prolong the dormancy of perennial plants, and thereby protect the unsprouted buds from frost damage. This can be especially important in the protection of flower buds, which in some years, may sprout early and be killed by cold temperatures.

PREPARATION diesters of carboalkoxyphosphonic acids with aqueous solutions of ammonia, primary amines or secondary amines.

This reaction can be considered to occur in two steps as is illustrated by the following equations.

In equations (2) and (3) R is alkyl of one through six carbon atoms, chloroalk-yl of one through six carbon atoms containing up to three chlorine atoms, bromoalkyl of one through six carbon atoms containing up to three bromine atoms, alkoxy alkyl of from three through seven carbon atoms, alkenyl of two through six carbon atoms, alkynyl of three through four carbon atoms, phenyl or benzyl; R is alkyl of one through four carbon atoms, preferably methyl or ethyl; R is alkyl of one through six carbon atoms, chloroalkyl of one through six carbon atoms containing up to three chlorine atoms, bromoalkyl of one through six carbon atoms containing up to three bromine atoms, alkoxy alkyl of three through seven carbon atoms, alkenyl of two through six carbon atoms, alkynyl of three through four carbon atoms,'phenyl or benzyl; R is hydrogen or. methyl; R is hydrogen, methyl, amino, methylamino, or dimethylamino; R and R can be taken together to form a ring selected from (CH O(CH or (CH2)1| where 'n is 2-6; M is selected from the group consisting ofammonium, hydrogen, sodium, lithium,.potassium, calcium, magnesium, zinc, manganese, barium or where R R and R can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, or hydroxy alkyl of two through four carbon atoms; and R is hydrogen, alkyl of one through 12 carbon atoms, allyl, benzyl, amino, methylamino, or dimethylamino; R and R can be taken together to form a ring that is -(CH O-(CH or -(CH where n is 2-6 and R and R are H.

The synthesis method, exemplified by equations (2) and (3) involves concurrent or consecutive aminolysis and hydrolysis of the starting dialkyl carboalkoxyphosphonate by interaction with water and the amine reactant.

While equations 2) and (3) represent the route predominantly taken by the reaction when combined in one operation, some hydrolysis may occur during or before aminolysis. However, the postulated reaction sequence as represented by equations (2) and (3) favoring formation of the carbamoyl-phosphonate intermediate isproved experimentally, as it is possible in some instances to isolate the carbamoylphosphonate intermediate shown as the product of equation (2). It has, of course, also been experimentally demonstrated that the product of equation (3) is in fact obtained.

An alternate method for synthesis of those compounds of this invention where R is substituted by chlorine or bromine consists of the addition of halogen or hydrogen halide to'the double bond of the compounds of this invention where R is alkenyl. This reaction is illustrated by equation (4).

The dialkyl carbamoylphosphonates prepared as described above or by methods described in the chemical literature are readily hydrolized to the monoester salt compounds of this invention by addition to aqueous ammonia or amine solutions. This procedure may be used therefore to obtain a mixed product, comprising a salt of one amine and an amide of another. This will be discussed and exemplified below.

The dialkyl carboalkoxyphosphonates and dialkyl carbamolyphosphonates used for the synthesis of the compounds of this invention can be prepared by methods available in the literature, such as Nylen, Chem. Ber. 57, 1023 (1924) and Reetz et al., J.A.C.S. 77, 3813-16 1955) using appropriate ester intermediates.

Generally, the alkoxy group of the carboalkoxyphosphonate is limited for practical purposes to methyl and ethyl, since there appears to be no advantage to increasing the size of the alcohol moiety. However, higher alcohol derivatives are useful in some instances.

The following are illustrative of typical diesters of the carboalkoxyphosphonates:

Diethyl carbomethoxyphosphonate Diallyl carbomethoxyphosphonate Diisopropyl carboethoxyphosphonate Dibutyl carbobutoxyphosphonate Dimethallyl carboethoxyphosphonate The following are illustrative of typical carbamoylphosphonate esters;

Diethyl carbamoylphosphonate Diallyl N,N-dimethylcarbamoylphosphonate Diallyl carbamoylphosphonate Dipropyl N-methylcarbamoylphosphonat Dimethyl piperidinocarbonylphosphonate Bis( 2-chloroethyl )carbamoylphosphonate The following are illustrative of the amines which can be used for the amination and/or hydrolysis of the esters:

Ammonia Methylamine Dimethylamine Allylamine Propylamine Ethylamine Morpholine Piperidine Methylhydrazine N,N-Dimethylhydrazine Ethanolamine More particularly, in the preferred procedure for preparing the ammonium alkyl carbamoylphosphonates of this invention, a dialkyl carboalkoxyphosphonate or dialkyl carbamoylphosphonate is added to a stirred'aqueous solution of ammonia or other amine.

Stirring is'continued until a clear solution is obtained. The resultant salt can then be isolated by removal of the water through evaporation or by stripping under reduced pressure. In general, these salts are stable white crystalline solids or viscous liquids. Those which are solid can be recrystallized from one or a mixture of several lower alcohols. However, most of the products are suitable for use without purification.

It is preferred that an excess of ammonia or amine be employed in this reaction to insure good yields and rapid reaction. A ratio of diester to amine of 1 to 2 or greater is employed. Preferably the ratio of diester to amine of between 1 to 2'and 1 to is employed. The excess amine insures that amidation of the carboxylic ester rather than hydrolysis is the predominant reactron.

It is also preferred that a concentration of ammonia or amine of from to 50 percent be employed, although the reaction can be operated at higher or lower concentrations.

When the amine reactant is not highly soluble in water, another solvent, such as methanol or ethanol can be added to the aqueous system to solubilize the amine reactant and thereby increase its reactivity.

This process can conveniently be carried out at about room temperature, although higher temperatures can also be employed if it is desired to speed up the rate of reaction. This process is moderately exothermic, and therefore must .be controlled by regulation of the diester addition rate and/or by external cooling to maintain the desired temperature.

- A highly satisfactory procedure is to slowly add thediester to a stirring aqueous solution of the amine and alkaline earth metals by interchanging the ammonium salt with appropriate bases or salts.

Another method is to convert the ammonium salt to the free acid, and then neutralize the free acid with the appropriate base or salt.

The following illustrative examples are presented to further illustrate this invention. In the following examples, parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 C. and stirring is continued for 2 hours. The clear solution is stripped under reduced pressure (15 mm of Hg) at a water-bath temperature or 70C. The residue is a white crystalline solid which is recrystallized from absolute ethyl alcohol, giving 12.3 parts of ammonium allyl carbamoylphosphonate, m.p. l60-162.5C. Nonaqueous titration either as an acid or a base gives a molecular weight of 182121.

EXAMPLES 2-9 The procedure of Example 1 is repeated by substituting an equivalent amount of the indicated Phosphonate Ester for the diallyl carbomethoxyphosphonate of Example 1 to produce the indicated Salt Product.

Ex. Phosphonate Ester Salt Product 2 diethyl carboxymethoxy hosphonate ammonium eth l carbamoylphosphonate m.p. 173-176 3 bis(2-chloroethyl)carbo utoxyphosammonium 2-c 1oroethylcarbamoylphosphonate, mp. 117-120 phonate 4 dibutyl carboethoxyphosphonate ammonium butyl carbamoylphosphonate m.p. 205.5-2065 5 diallyl carboethoxyphosphonate ammonium allyl carbamoylphosphonate 6 dimethallyl carbomethoxyphosphonate ammonium methallyl carbamoylphosphonate, mp. 193-197 7 diisopropyl carboethoxyphosphonate ammonium isopropyl carbamoylphosphonate, mp. 213-216 (dec.)

8 diemethyl carbomethoxyphosphonate ammonium methyl carbamoylphosphonate, mp. 148-151 9 dipropyl carbopropoxyphosphonate ammonium propyl carbamoylphosphonate, mp. 190-192 (dec.) 10 diisobutyl carbomethoxyphosphonate ammonium isobutyl carbamoylphosphonate, mp. 221-222 (dec.) 1 1 dihexyl carbomethoxyphosphonate ammonium hexyl carbamoylphosphonate,m.p. 212 (dec.)

12 bis( lethyl-2-butenyl)carbomethoxyammonium (1-ethyl-2-butenyl)carbamoylphosphonate phosphonate '13 bis(2-methoxyethyl)carbomethoxyammonium Z-methoxyethyl carbamoylphosphonate phosphonate 14 bis(2-bromopropyl)carbomethoxyphosammonium 2'bromopropyl carbamoylphosphonate honate 15 is(6-chlorohexyl)carbomethoxyphosammonium 6-chlorohexyl carbamoylphosphonate phonate 16 bis(6-brom0hexyl)carbomethoxyphosammonium fi-bromoliexyl carbamoylphosphonate phonate l7 bis(2-butoxyethyl)carbomethoxyphosammonium 2-butoxyethyl carbamoylphosphonate, hydgroscopic solid phonate l8 bis(2,2,2-trichloroethyl)carbomethoxyammonium 2,2,2-tnchloroethylcarbamoylphosphonate hosphonate 19 is(2,2,2-tribromethyl)carbomethoxyammonium 2,2,2-tribromoethylcarbamoylphosphonate phosphonate which is cooled and maintained at about 15C. When addition of the diester is complete, the temperature of the mixture is allowed to come to room temperature or slightly above. Generally, the reaction is complete in a few minutes to several hours depending on the reactants and conditions used.

The ammonium salts prepared as described above can be converted to salts of other bases or of alkaline EXAMPLE 20 To a stirring ice-chilled solution of parts percent methylamine in water is added slowly 8.4 parts of dimethyl carbomethoxyphosphonate. Thev mixture is warmed to 25C. and allowed to stir for 3 hours. The clear solution on stripping under reduced pressure yields 9.6 parts methylammonium methyl N-methylcarbamoylphosphonate as a colorless ,oil. The product analyzes for the dihydrate.

EXAMPLES 21-27 of the indicated SaltProducts are isolated as liquids or low melting solids.

Ex. Aqueous Amine Phosphonate Ester Salt Product 21 methylamine I diethyl methylam- (40%) carboethoxyphosphonmonium ethyl ate N-methylcarbamoylphosphonate 22 methylamine diisoporpyl methylam- (40%) carbomethoxyphosmonium phonate isopropyl N-methylcarbamoylphosphonate 23 methylamine diallyl methylam- (40%) carbethyxyph0sphon monium allyl ate N-methylcarbamoylphosphonate 24 dimethyalmine diethylcarbomethoxydimethylam- (25%) phosphonate monium ethyl N,N-dimethylcarbamoylphosphonate 25 methylhydrazine diethyl methyl 0%) carboe thoxyphosphoncarbazoylphosate phonic acid,

monoethyl ester, salt with methyl hydrazine 26 pipcridine (50%) dibenzyl piperidinium carbomethoxyphosbenzyl phonate piperidinocarbonylphosphon ate Y 27 l,l-dimethylhydradipropyl l,l-dimethylhyzine (35%) carbomethoxyphosdrazinium propyl phonate 3,3-dimethylcarbazoylphosphonate EXAMPLE 28 Eight parts'of diethyl N-methylcarbamoylphosphonate is added slowly to 18 parts of a 29 percent aqueous solution of ammonia, while holding the temperature at 25C. by external cooling. The unreacted ammonium hydroxide is allowed to evaporate, giving a white, crystalline, solid residue. Recrystallization from absolute ethanol gives 5 parts of ammonium ethyl N-methylcarbamoylphosphonate, mp. 189C.

EXAMPLES 29-41 the diethyl methylcarbamoylphosphonate of Example 28 to obtain the indicated Salt Product.

Ex. Aqueous Amine Phosphonate Ester Salt Products ammonium phenyl N-methyl carbamoylphosphon ate 29 ammonia diphenyl N-methyl carbamoylphosphonate -Continued Ex. Aqueous Amine Phosphonate Ester Salt Products 30 methylamine dimethyl N,N-dimethyl methylam- (25%) carbamoylphosphonate monium methyl N,N-dimethylcarbamoylphosphonatate 31 diemtylamine diethylcarbamoylphosdimethylam- (25%) phonate monium ethyl carbamoylphosphonate 32 allylamine (25%) diallyl allylammonium carbamoylphosphonate allyl carbam'oylphosphonate 33 isobutylamine diisopropyl N-methyl' isobutylam- (20%) carbamoylphosphonate monium isopropyl N-methylcar- I bamoylphosphonate 34 methylamine diisopropyl methylam- (20%) morpholino'carbonylmonium phosphonate isopropyl morpholinocarbonylphosphonate 35 triethanolamine diallyl triethanolamcarbamoylphosphonate monium allyl carbarn0ylphosphonate 36 ammonia (29%) diethyl ammonium ethyl pyrrolidinocarbonylpyrrolidinocarphosphonate bamoylphosphonate, mp. 189-192 (dec.)

37 ammonia (29%) diethyl ammonium ethyl morpholinocarbonylmorpholinocarphosphonate bonylphosphonate, mp. 183-185 i (dec.)

38 ammonia (29%) diethyl ammonium ethyl N,N-dimethylcar- N,N-diemthylcarbamoylphosphonate bamoylphosphonate, m.p.

39 ammonia (29%) bis(3-butynyl)N,N-. ammonium dimethylcarbamoyl- 3'butynyl phosphonate N,N dimethylcarbamoylphosphonate 40 ammonia (29%) diethyl ammonium ethyl N-methylcarbamoyl- N-methylcarphosphonate bamoylphosphonate 4l ammonia diethyl ammonium ethyl aziridiniumcarbamoylaziridiniumcarphosphonate bamoylphosphonate EXAMPLE 42 EXAMPLES 43-44 The procedure of Example 42 is repeated substituting an equivalent amount of the indicated Alkenyl Reagent for the ammonium allylcarbamoylphosphonate of Example 42 and an equivalent amount of the indicated Halogen for the bromine of Example 42 to obtain the indicated Product.

ammonium methallyl 43 chlorine ammonium carbamoylphosphonate 2,3-dichloro-2- methylpropyl carbamoylphosphonate 44 ammonium but-Z-enyl bromine ammonium carbamoylphosphonate 2,3-dibromutyl carbamoylphosphonate EXAMPLE 45 An aqueous solution of 45 parts ammonium hydroxide is stirred and chilled with an ice bath, while 24.4 parts benzyl methyl carbomethoxyphosphonate is added slowly. Stirring is continued until a clear solution is obtained. Unreacted ammonium hydroxide and water are removed from the mixture under reduced pressure, leaving as a solid residue ammonium monobenzyl carbamoylphosphonate, mp. 186, after recrystallization from ethanol.

EXAMPLES 46-5 1 The procedure of Example 45 is repeated substituting an equivalent amount of the indicated Aqueous Amine for the ammonium hydroxide of Example 45 and an equivalent amount of the indicated Phosphonate Ester for the benzyl methyl carbomethoxyphosphonate of Example 45 to obtain the indicated Salt Product as a principal product of this procedure.

To a stirring suspension of 21.2 parts ammonium butyl N-methylcarbamoylphosphonate and 100 parts methanol is added 42 parts of a 40 percent solution of N-benzyltrimethylammonium hydroxide in methanol. Ammonia and methanol are stripped from the mixture at 40C. under reduced .pressure, leaving benzyltrimethylammonium butyl -N-methylcarbomoylphosphonate as a residue.

EXAMPLES 53-56 The procedure of Example 52 is repeated substituting an equivalent amount of the indicated Base for the N-benzyltrimethylammonium hydroxide of Example 52 and an equivalent amount of the indicated Ammonium Phosphonate for the ammonium butyl N-methylcarbamoylphosphonate of Example 52 to obtain the indicated Salt Product.

Ammonium Ex. Base Phosphonate Salt Product 53 tetraethylammonium allyl tetraethylammonium ammonium carbamoylphosmonoallyl hydroxide phonate carbamoylphosphonate 54 trimethylamammonium ethyl trimethylammonium ine (large N methylcarmonoethyl excess) bamoylphosphon- N-methylcarbamoylphosate phonate 55 ethanolamine ammonium ethanolammonium methallyl methallyl hexahydroazepinohexahydroazepinocarcarbonylphos bonylphosphonate phonate 56 benzylamine ethylammonium benzylammonium isopropyl isopropyl carbamolyphoscarbamoylphosphonate phonate EXAMPLE 57 A 5 percent aqueous solution of ammonium ethyl carbamoylphosphonate is passed through a packed column of sulfonated polystyrene copolymer hydrogentype resin to convert the salt to the free acid. Evaporation of the water gives a residue of the acid ester, ethyl carbamoylphosphonic acid, mp. C.

EXAMPLES 58-60 The procedure of Example 57 is repeated, first obtaining the indicated Acid Ester in aqueous solution and then removing the water to obtain the water-free product, usually a solid.

Ex. Ammonium Phosphonate Acid Ester 58 ammonium methyl methyl N-methylcarbonylphosphonate N-methylcarbamoylphosphonic acid 59 ammonium isopropyl isopropyl carbamoylphosphonate carbamoylphosphonic acid 60 ammonium alkyl alkyl carbamoylphosphonate carbamoylphosphonic acid EXAMPLE 61 A 5 percent aqueous solution of ammonium propyl N-methylcarbamoylphosphonate is passed through a packed column of sulfonated polystyrene copolymer hydrogen type resin to convert the salt to the free acid.

This is neutralized with the equivalent amount of so-.

dium bicarbonate to give a solution of essentially pure sodium propyl N-methylcarbamoylphosphonate. Evaporation of this solution gives the solid salt product.

EXAMPLES 62-75 The procedure of Example 61 is repeated, first obtaining the free acids of the indicated gAmmonium Phosphonate as was done in Example 1" and then neutralizing the acid with the indicated Base according to the procedure of Example 61 to obtain the indicated Salt Product.

Ammonium Ex. Phosphonate Base Salt Product 62 ammonium sodium bicarbonate sodium phenyl phenyl carbamoylphosphoncarbamoylphosate phonate Bicarbonate Salt Salt Product sodium bicarbonate potassium bicarbonate tetramethylammonium bicarbonate benzyltrimethylammonium sodium ethyl N methylcarbamoylphosphon ate potassium benzyl carbamoylphosphonate tetramethylammonium allyl piperidinocarbonylphosphonate benzyltrimethylammonium butyl bicarbonate phonate carbamoylphosphonate Continued Ammonium Ex. Phosphonate Base Salt Product 63 ammonium calcium hydroxide hemicalcium benzyl benzyl carbamoylphosphon carbamoylphosate phonate 64 ammonium ethyl barium hydroxide hemibarium ethyl carbamoylphoscarbamoylphosphonphonate ate 65 ammonium hydroxyethhydroxyethmethyl-N,N- yltrimethylamyltrimethylammonium dimethylcarmonium hydroxide methyl bamoylphos- N,N-dimethylcarphonate bamoylphosphonate 66 ammonium benzyltrimethylambenzyltrimethylambenzyl monium hydroxide monium benzyl carbamoylphoscarbamoylphosphom phonate ate 67 ammonium allyl magnesium hemimagensium allyl carbamoylphoshydroxide carbamoylphosphonphonate ate 68 ammonium butyl morpholine morpholinium butyl N-mcthyl Nmethylcarbamoylcarbamoylphosphosphonate phonate 69 ammonium trimethylamine trimethylammonium monoisopropyl isopropyl morpholine morpholino-carcarbonylphosphonate bonylphosphonate 70 ammonium ethyl tetrabutylammonium tetrabutylammonium carbamoylphoshydroxide ethyl phonate carbamoylphosphonate, hygroscopic solid 71 ammonium ethyl lithium carbonate lithium ethyl carbamoylphoscarbamoylphosphonphonate ate, m.p. above 300C. 72 ammonium ethyl zinc carbonate hemizinc ethyl carbamoylphoscarbamoylphosphonphonate ate, m.p. 244 (dec.) 73 ammonium dodecylamine dodecylammonium isopropyl isopropyl carbamoylphoscarbamoylphosphonphonate ate 74 ammonium allyl manganous hemimanganous allyl carbamoylphoscarbonate carbamoylphosphonphonate ate 75 ammonium butyl dodecyltrimethyl dodecyltrimethylammorpholinumcaammonium monium butyl rbonylphoshydroxide morpholiniumcarphonatc bonylphosphonate EXAMPLE 76 To a stirred solution of parts of potassium bicarbonate and 50 parts of water is added 18.4 parts ammonium isobutyl carbamoylphosphonate. Stirring is continued until solution is complete. The solution is evaported to dryness, giving the solid product, potassium isobutylcarbamoylphosphonate.

EXAMPLES 77-80 The procedure of Example 76 is repeated substituting the indicated Bicarbonate Salt for the potassium bicarbonate of Example 76 and an equivalent amount of the indicated Carbamoylphosphonate for the ammonium monoisobutyl carbamoylphosphonate of Example 76 to obtain the indicated Salt Product.

Formulation Plant growth modifying compositions of the present invention can be prepared by admixing at least one of the compounds of this invention with pest control adjuvants or modifiers to provide compositions in the form of dusts, water-soluble powders, solutions, granules or pellets. In addition, the plant growth modifying agents such as maleic hydrazide and Alar (N-dime thylaminosuccinamic acid) can be included in the compositions of this invention in combination with the compounds of this invention.

Compositions of the invention, may contain as a conditioning agent one of more surface-active agents, sometimes called surfactants, in amounts sufficient to render a given composition containing the compounds of this invention readily soluble in water or capable of wetting foliage efficiently.

The surface-active agent used in this invention can be a wetting, dispersing or an emulsifying agent which will assist dispersion and solution of the active compound. The surface-active agent or surfactant can include such anionic, cationic and non-ionic agents as have heretofore been generally employed in plant control compositions of similar type. Suitable surface-active agents are set forth, for example in Detergents and Emulsifiers 1967 Annual by John W. McCutcheon, lnc.

In general, less than 10 percent by weight of the surface-active agent will be used in compositions of this invention and ordinarily the amount of surface-active agents will range from 1-5 percent but may even be less than 1 percent by weight.

Additional surface-active agents can be added to the formulations to increase the ratio of surfactantzactive ingredient up to as high as 5:1 by weight. Such compositions may have a greater effectiveness than can be expected from a consideration of the activity of the components used separately. When used at higher rates, it is preferred that the surfactant be present in the range of one-fifth to five parts surfactant for each one part of active agent.

The classes of extenders suitable for the watersoluble powder formulations of this invention are the natural clays, diatomaceous earth, synthetic mineral fillers derived from silica and silicate, starch, sugar, and inorganic salts. Most preferred fillers for this invention are kaolinites, attapulgite clay, montmorillonite clays, synthetic silicas, synthetic magnesium silicate, calcium sulfate dihydrate, and disodiuin hydrogen phosphate.

Suitable surfactants for use in such compositions are those listed by J. W. McCutcheon in Detergents and Emulsifiers 1967 Annual. Among the more preferred surfactants are the non-ionic and anionic type, and

those most suitable for the preparation of the dry, soluble products of this invention are solid forms of com- Wetting and dispersing agents in these preferred water-soluble compositions of this invention are usually present at concentrations of from about 0.5 weight percent to 5 weight percent. The inert extender then completes the formulation. Where needed, 0.1 weight percent to 1.0 weight percent of the extender may be replaced by a corrosion inhibitor or an anti-foaming agent or both.

Thus, water-soluble formulations of the invention will contain from about to 95 weight percent active material, from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 5.0 weight percent dispersant, and from 4.25 to 74.25 weight percent inert extender, as these terms are described above.

When the water-soluble powder contains a corrosion inhibitor or an anti-foaming agent or both, the corrosion inhibitor will not exceed about l-percent of the composition, and the anti-foaming agent will not exceed about 0.5 percent by weight of the composition, both replacing equivalent amounts of the inert extender.

Solution Concentrates The aqueous solution concentrates are prepared by mixing a water-soluble active compound of this invention with water. A portion of the water may be replaced with methanol, ethanol, isopropanol, ethylene glycol, cellosolve or methyl cellosolve. Surfactants and buffering agents can optionally be present.

These aqueous solution concentrates will contain from 15 to 60 percent of active ingredient, and from 40 to 85 percent water or mixture of water and hydroxylated organic solvent. Surfactants, corrosion inhibitors, buffering and anti-foam agents may also be included in which case they may replace up to 10 percent of the solvent system.

Dusts Dusts are dense powder compositions which are intended for application in dry form, inaccordance with the preferred compositions and methods of the invention. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid extender.

Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, adsorptive grinding aid. For the dust compositions of this invention, the inert extender may be either of vegetable or mineral origin, the wetting agent is preferably anionic or non-ionic and suitable adsorptive grinding aids are of mineral origin.

Suitable classes of inert solid extenders for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very freeflowing. They are also characterized by possessing relatively low surface areas and are poor in liquid adsorption. Suitable classes of grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and non-ionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease in incorporation some liquid non-ionic agents are also suitable in the dust formulations.

Preferred inert solid extenders for the dusts of this invention are micaceous tales, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock such as that known as Phosphodust," a trademark of the American Agricultural Chemical Company.

Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates. Preferred wetting agents are those previously described under water-soluble powder formulations. The inert solid extenders in the dusts of this invention are usually present in concentrations of from about 30 to weight percent of the total composition. The grinding aid will usually constituteS to 50 weight percent of the composition, and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent.

The water-soluble powders described above can also be used in the preparation of dusts. While such watersoluble powders could be used directly in dust form, it is more advantageous to dilute them by blending with the dense dust diluent. In. this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Thus,- the dust compositions of this invention will comprise about 5 to 20 weight percent active material, 5 to 50 weight percent adsorptive tiller, 0 to 1.0 weight percent wetting agent, and about 30 to 90 weight percent dense, free-flowing dust diluent, as these terms are used herein. Such dust formulations can contain, in addition, minor amounts of dispersants, corrosion inhibitors, and anti-foam agents, derived from the watersoluble powders used to make the dusts.

Granulesand Pellets Under some circumstances it may-be advantageous One method of preparation suitable for both granules and pellets involves blending the active ingredient with clays, water-soluble salts, surfactants and a small amount of water. After pelleting and/or granulating,

the formulation is dried prior to use. A second method suitable for the preparation of granules formulation involves spraying a solution of the active material on porous, adsorptive, preformed clay or vermiculite granules. Surfactants listed by McCutcheon can also be included in the spray solution. After drying, the granules are ready for application.

The preferred granules or pellets will contain about 5 to 30 weight percent of active material, about to weight percent wetting agent and about 65 to 95 weight percent inert mineral carrier.

paints. At the low levels employed (1 5 percent),

there is generally little effect on the physical properties of the systems, and commercial materials need not be reformulated. At relatively high levels, the active ingreclient, being a salt can cause conventional emulsions to thicken or break. In the former case mere dilution with water is effective to restore physical properties; in the latter case. a salt-tolerant emulsifier must be selected.

As the compounds of formula (1) have rather low solubility in organic solvents, they must be finely ground and well dispersed to be effective in systems such as solvent-based varnishes and paints. In such systems, the active ingredient must be treated as a pigment would be. Additionally, water must be rigorously excluded, otheriwse the active material will not remain well-dispersed.

When packaged as an aerosol, similar considerations apply. The preferred type of formulation is an emulsion with the compound of formula (1) in the aqueous phase and the film former, solvent and propellant system in the organic phase. Dispersions in organic systems are possible but not preferred becausev of difficulty in assuring adequate-mixing before use, the need to-rigorously exclude moisture, and the expense of assuring an adequately tine particle size.

Application As stated earlier, this invention is founded on the discovery that the compounds of formula (1) are useful for modifying the growth rate of plants. More particularly the compounds of this invention are useful as plant growth retardants. They also affect the flowering and fruit set of numerous plants.

The term plant growth retardant as used in this disclosure is to be understood to mean an agent which when applied to a plant or its environs will slow the growth of the plant without killing or causing extensive injury to said plant. This also includes a delaying response on bud sprouting or prolonging of the dormancy period.

The compounds of this invention can be used to retard bud break and the growth of woody vegetation.

The compounds of this invention can also be used to control the growth of turf and other herbaceous vegetations.

The compounds of this invention can be applied as foliar sprays or as soil applications to retard the growth rate of such plants or to affect flowering and fruit'set.

Preferably, the compounds of this invention are applied as a foliar spray to the point of runoff although lower-volume application may also be effective.

It is preferred that the application be made a short time prior to the period when maximum plant growth is anticipated, but application can also be made during the dormant stage or just after the plants have been trimmed. Or if flowering and fruit set are to be modified, the treatment is applied before, during, or shortly after flowering.

To prevent bud break it is preferred that the application be made at the time the buds for the next year are being developed. For most plants this is from July to a few weeks before leaf-fall.

It will be recognized that the rate of application is dependent upon the species to be treated and the results desired. In general, rates of from 0.25 to 20 kilograms per hectare are used although higher or lower rates can achieve the desired effect in some instances.

The following examples are presented to further illustrate the formulation and application of the compounds of this invention. Parts and percentages in the following examples are by weight unless otherwise indicated.

EXAMPLE 8 l A dust having the following formula is prepared.

Ammonium allyl carbamoylphosphonate 5.0% Talc 64.0% Attapulgite 30.0% Sodium benzenesulfonate 1.0%

The active component is ground with the minor diluent and the surfactant to pass a 0.149 mm. screen. This material is then blended with the major diluent to form a dust composition.

It will be understood that the other compounds of this invention can also be formulated in a like manner.

The dust formulation of Example 81 is applied, using a helicopter, at a rate of kilograms per hectare to an area under an electric power line in which the brush and trees have been freshly trimmed inspring at the time when the leaves on most of the plants are just fully expanded. The application is made in the early morning when the foliage is wet with dew or just after a rain; This treatment retards the growth of a large number of species along the right-of-way including the following species: red maple (Acer rubrum), black willow (Salix EXAMPLE 82 A water-soluble powder of the following formula is prepared.

Ammonium allyl carbamoylphosphonate 95.0% Synthetic silica 3.5% Disodium hydrogen phosphate 1.0% Dioctylsodium sulfosuccinate 0.5%

The above ingredients are mixed and then ground to pass a 0.42 mm. screen. The resulting formulation is water-soluble powder, with the exception of the synthetic silica conditioning agent.

The following compounds of this invention can also be formulated in like manner.

Ammonium 2-chloroethyl carbamoylphosphonate Ammonium methyl carbamoylphosphonate Sodium phenyl carbamoylphosphonate Hemicalcium benzyl carbamoylphosphonate Hemibarium ethyl carbamoylphosphonate Ammonium 2,3-dibromopropyl carbamoylphosphonate Diethylammonium ethyl carbamoylphosphonate Ammonium hexyl carbamoylphosphonate Four kilograms of the water-soluble powder formulation of Example 82 is dissolved in 200 liters of water and 0.5 percent of a non-phytotoxic wetting agent is added. This solution is sprayed on one hectare of freshly trimmed Norway maple (Acer plantanoides) growing along struts under a power line. This treatment greatly reduces the rate of growth of the trees and extends the time interval between trimmings. The trees are not significantly injured by the treatment.

The water-soluble powder of Example 82 can be dissolved in water at the rate of 2,000 p,p.m. of active ingredient and applied to 1 acre of Virginia bunch peanuts at the time they are beginning to flower. The treatment prevents excessive vegetative growth and promotes flowering and fruit set of the treated plants. As a result of the treatment the plants are easier to harvest and'dry and more high quality nuts are harvested.

Example 83 Ammonium ethyl carbamoylphosphonate 90% Silica aerogel 4% Sugar 6% The ingredients are combined, blended, crushed through a U.S.S. No. 20 sieve (0.84 mm. openings) and reblended.

In mid-September, active ingredient formulated as described above was dissolved in water containing 0.2 percent sorbitan monolaurate and applied to the foliage of red maple (Acer rubrum), sweet gum (Liquidambar styraciflua) and green briar (Smilax spp.) at the rate of 3 kg/ha in 800 l. of water. The treatment had no apparent effect on the plants for the remainder of the season. However, the next July the treated plants had developed almost no leaves.- What buds that had broken had produced only minute red-tinged leaves. Except for some tips, the bare branches were still alive. The floor beneath-the treated brush was green with herbaceous vegetation.

Water EXAMPLE 84 A wettable powder of the following formula is prepared.

Hemibarium benzyl carbamoylphosphonate Montmorrilonite Synthetic silica Disodium hydrogen phosphate Sodium alkylnaphthalenesulfonate Sodium lignin sulfonate The above ingredients are mixed and then ground to pass a 0.25 mm. screen. The active ingredient in the above formulation dissolves when the composition is added to water.

Twenty kilograms of the formulation of Example 84 t is added to 400 liters of water and agitated until the active ingredient dissolves. This solution is then sprayed on 1 hectare of newly trimmed hedgerow in the spring after the leaves have expanded. This treatment greatly reduces the growth of plants growing in the hedgerow such as osage orange (Maclura pomifera), but does not seriously injure them. The hedgerow is thus kept neat with a minimum of labor expended for trimming it.

EXAMPLE 85 A solution of the following formula is prepared.

Ammonium ethyl carbamoylphosphonate Disodium hydrogen phosphate Sodium laurylsulfate Water The above components are blended to form a homogeneous solution.

The following compounds can be formulated in like manner. I 4

Benzyltrimethylammonium benzyl N,N-dimethylcarbamoylphosphonate I Trimethylammonium ethyl N-methylcarbamoylphosgrowth of the bluegrass for a period of 4 to 8 weeks and the mowing required to maintain the area in an tive condition is reduced.

EXAMPLE 86 A solution of the following formula is prepared.

attrac- Allylammonium allyl N,N-dimethylcarbamoyl- 24.0% phosphonate Trimethylpolyethyleneglycol ether 1.0% 20.0%

Ethylene Glycol 55.0%

A solution containing 227 gms. of active ingredient formulated as above is sprayed on an area of red delicious apple trees about 2 weeks after petal fall. This treatment prevents the June drop and gives a higher yield of apples per acre than that from a similar untreated acre of trees. It also reduces the growth of spurious sheets known as water sprouts and ameliorates the tendency to biannual hearing which is strong in this variety.

EXAMPLE 87 The following formulation is prepared.

Ammonium methyl carbamoyphosphonate 25.0% Sodium lauryl sulfate 50.0% Magnesium silicate 10.0% Kaolinite 15.0%

The above components are blended, micropulverized to pass a 0.30 mm. screen and reblended.

The following compounds can be formulated in like manner.

Morpholinium ethyl carbamoylphosphonate Sodium phenyl carbamoylphosphonate Hemicalcium benzyl carbamoylphosphonate Five kilograms of the formulation of Example 87 are suspended in 100 liters of water and then sprayed to runoff on freshly trimmed trees and brush along the edge of a power line right-of-way. This treatment greatly reduces the growth of the trees and shrubs without permanent injury to them and they are prevented from growing over into the power line. The vegetation on the right-of-way is controlled by applying herbicides. This treatment reduces the labor required to maintain the line.

EXAMPLE 88 An aqueous concentrate solution is prepared which contains the following ingredients:

ammonium ethyl carbamoylphosphonate 24.0%

Ndimethylaminosuccinamic acid l2.0% water 32.0% methanol 32.0%

The above ingredients are stirred together with slight in early September. The treatment prevents coloration in the apples and prevents premature fall before the apples are harvested.

Example 89 Water The ingredients are combined and stirred to produce a solution containing approximately 4 pounds active ingredient per gallon (480 g. per liter). After filtration through a bed of diatomaceous earth, the product is packed in glass or plastic containers until use.

IriSe pte mb er, oaks (Qu ercus sppfl), hickory (Carvd 1 spp.) and Loblolly pine (Pinus taeda) were treated with a foliar spray of the above formulation at the rate of 6 kg/ha in 800 liters of water. The treated plants showed no response that fall but next spring the deciduous spe cies failed to develop new leaves and the pine did not develop new shoots. The treatment had prevented the new buds from breaking in the spring although plant stems and limbs were observed to be alive when examined closely.

EXAMPLE 90 The following wettable powder is prepared:

ammonium ethyl carbamoylphosphonate 30.0% maleic hydrazide 20.0% synthetic silica 2.5% montmorillonite 45.0% sodium alkylnaphthalene sulfonate 2.0% partially desulfonated sodium lignin sulfonate 0.5%

The above ingredients are blended, micropulverized to a particle size essentially below 50 microns and re blended.

The wettable powder of Example 90 is suspended in water at the rate of'4,000 p.p.m. of active ingredient and sprayed on an area of mixed brush under a power line. The application is made in mid-May just after the brush has been trimmed back to keep it away from under the power line. The solution is sprayed to run-off on the lower two-thirds of the trees which were not cut. This treatment effectively retards the growth of the trimmed vegetation for the next growing season as well as the one in which the vegetation is treated.

The formulation of Example 90 is suspended in water at the rate of 1,000 p.p.m. of active ingredient and sprayed to the point of run-off on single trees located at random throughout orchards of apple, peach and cherry varieties. The treatments are applied while the trees are still in the dormant stage. During an early EXAMPLE 91 The following aerosol preparation is prepared:

(ammonium ethyl carbamoylphosphonate 1.0%

( water 29.0%

' (asphalt 20.0%

B lxylene 25.0%

-Continued polyglycerol stearate dic 20.0%

C i hloro difluoromethane The predissolved aqueous phase (A), comprising active ingredient in water, is combined with the organic phase (B), comprising a solution of asphalt, emulsifier, and xylene, with agitation. To this is added, under pressure in an aerosol dispenser, the propellant C.

Trees under a power line are trimmed back in early May to prevent them growing into the lines. The cut ends are treated with the wound dressing described above. The treatment reduces the break of lateral buds and retards the rate of growth of those that do break. In addition, the treatment causes overall retardation in the rate of growth of the treated plants. This lengthens the time between trimmings, reducing the cost of maintaining the power line. Trees treated include sweetgum (Liquidambar styraciflua L.), black willow (Salix nigra Marsh.), apple (Malus sp. Mill.), and red maple (Acer rubrum L.).

EXAMPLE 92 The following asphalt emulsion is prepared:

ammonium ethyl carbamoylphosphonate 4.0% sodium oleate 2.0% water I 47.0% asphalt 47.0%

The active compound, sodium oleate and water are combined and heated to 90C. In a high' shear mixer,

maple (Acer saccharum Marsh.), growing under a power line. The treatment retards the breaking of lateral buds and the rate of growth of laterals. This remolten asphalt is added. The suspension is cooled and duces the future trimming necessary to maintain the area.

I claim: 1

l. A compound of the formula:

IULN

where R is alkyl of one through four carbon atoms, or alkenyl of three through four carbon atoms, R and R are each hydrogen; and

M is ammonium, hydrogen, sodium, lithium 'or potassium.

3. Ammonium allyl carbamoylphosphonate.

4. Ammonium ethyl carbamoylphosphonate.

5. Ammonium isopropyl carbamoylphosphonate.

Claims

1. A COMPOUND OF THE FORMULA:

2. A compound of the formula:

3. Ammonium allyl carbamoylphosphonate.

4. Ammonium ethyl carbamoylphosphonate.

5. Ammonium isopropyl carbamoylphosphonate.