IL32107A - Carbamoylphosphonates and their use as plant growth regulants - Google Patents

Description

D*nos onn»ax mo'i1? ona Ne carbamoylphoa honates and their use for as plant growth regulants DU PGFT DE NEMOURS AND COMPANY C. 30429 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. In addition, certain of the compounds of this invention are useful for increasing the sugar content of sugar-containing crops.

Related compounds such as the dialkyl carbamoylphosphonates are disclosed in U. S. Patent 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, the method of using the carbamoylphosphonates to increase the sugar content of a sugar-containing crop, and formulations containing said novel carbamoylphosphonates as the active ingredient therein.

More particularly, the carbamoylphosphonates of this invention are represented by the formula: 00 R2 n it R1_0-P-C-N OM X R3 where Ri is alkyl of one through eight carbon atoms, chloroalkyl of one through eight carbon atoms containing up to three chlorine atoms, bromoalkyl of one through eight carbon atoms containing up to three bromine atoms, alkoxy^lkyl of from three through ten carbon atoms, total, alkenyl of two through eight carbon atoms, alkynyl of three through four carbon atoms, phenyl or benzyl; Ra and R3 can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, hydroxy - alkyl of two through four carbon atoms, alkenyl or of three through four carbon atoms, alkynyl of three through four carbon atoms; R2 and R3 can be taken together to form a ring wherein R2 and R3 taken together are -(CH2)2-0-(CH2)2- or -(CH2)n- where n Is 4, 5 or 6 or one of 2 and Ra can be -N'_ where R4 is hydrogen or alkyl of one through four carbon atoms and Rs is hydrogen or alkyl of one through four carbon atoms, and M is hydrogen, sodium, lithium, potassium, calcium, magnesium, zinc, manganese, barium or where Rg, R^ and Rg 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 Rg is hydrogen, alkyl of one through twelve carbon atoms, -M^ where R* is hydrogen or alkyl Rs of one through four carbon atoms and R5 is hydrogen or alkyl of one through four carbon atoms, or benzyl.

Preferred compounds of this invention include those compounds of formula (1) where Ri is alkyl of one through four carbon atoms or alkenyl of three through four carbon atoms R and R3 are each hydrogen; and is ammonium or alkali metal such as sodium, lithium or potassium.

The most preferred compounds of this invention are ammonium allyl carbamoylphosphonate and amnoniiun ethyl carbsr-moylphosphonate for both plant growth retardant and sugar increase utility and ammonium isopropyl earbomoylphosphonate for sugar increase utility.

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.

Yet another aspect of this invention relates to formulations of compounds of formula (1) with suitable agricultural adjuvants and modifiers.

Description of the Invention This invention is founded on the discovery that the compounds of formula (1) are useful for modifying the growth rate of plants. In this regard, it has been noted that the compounds of this invention, as represented by formula (1), 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 retardan s 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. It has further been discovered that when the compounds of formula (1) are applied to sugar-containing plants at the proper time during their growth, a surprising increase in the sugar content of the plant is effected. For sugar cane, sugar beets and sorghum, which are grown for sucrose production, this increase in sugar content is observed directly as an increase in the yield from a given area of cropland. With other plants, the increase is observed by analysis of the plant or by analysis of the harvested parts thereof. Obviously, increased sugar levels improve the palatability of the plant or plant parts and offer improved dietary value. While the physiological mechanism involved in this increase in sugar content is not fully understood, it is apparent that the compounds used in this invention redirect the carbohydrate metabolism of the plant in such a way as to increase the sugar level in the plant juices. In addition, the treatment results in an increase in juice purity and a decrease in the extraneous matter that must be handled at the mill when the sugar cane is harvested, resulting in a more efficient and economical milling of the crop. Similar benefits are observed in treatment of sugar beets and syrup sorghum with the compounds of Formula 1.

Preparation The ammonium carbamoylphosphonate salts of this invention are readily prepared by the interaction of the diesters of carboalkoxyphoaphonic 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 eight carbon atoms, chloroalkyl of one through eight carbon atoms containing up to three chlorine atoms, bromoalkyl of one through eight carbon atoms containing up to three bromine atoms, alkoxy^lkyl of from three through ten carbon atoms, alkenyl of two through eight carbon atoms, alkynyl of three through four carbon atoms, phenyl or benzyl; ^ is alkyl of one through eight carbon atoms, chloroalkyl of one through eight carbon atoms containing up to three chlorine atoms, bromoalkyl of one through eight carbon atoms containing up to three bromine atoms, alkoxy alkyl of from three through ten carbon atoms, alkenyl of two through eight carbon atoms, alkynyl of three through four carbon atoms, phenyl or benzyl; R2 and R-^ can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, hydroxy-alkyl of two through four carbon atoms, alkenyl of three or through four carbon atoms; alkynyl of three through four carbon atoms,' R2 and R^ can be taken together to form a ring system wherein R2 and R3 are collectively -(CH2)2-0-(CH2)-or (CH2)n where n is 4, 5 or 6 or one of R2 and ^ can be R -N where R>, is hydrogen or alkyl of one through four - 5 carbon atoms and R is hydrogen or alkyl of one through four carbon atoms; R^o is alkyl of one through four carbon atoms, preferably methyl or ethyl; and 6 and Hj can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, hydroxy^alkyl of two through four carbon atoms, alkenyl of three through four carbon atoms, alkynyl of three through four carbon atoms, R5 and Hj can be taken together to form a ring system wherein Rg and R7 are collectively -(CH2)2-0-(CHa)- or (CH2)n where n is 4, 5 or 6 or one of R5 and R can be where R is hydrogen or alkyl of one through four carbon atoms and R5 is hydrogen or alkyl of one through four carbon atoms.

The synthesis method, exemplified by equations (2) and (3) involves concurrent or consecutive a inolysis and hydrolysis of the starting dlalkyl car oalkoxyphosphonate 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 carbamoylphosphonate intermediate is proved 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 Ri is alkenyl. This reaction is illustrated by equation (4).

The dialkyl carbamoylphosphona tes prepared as described above or by methods described in the chemical y literature are readily hydrolifzed 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 yi carbamoiyphosphona es 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, 102? (19 ) and Reetz et al., J.A.C.S. 77, ?8l3-l6 (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 DiDuty} carbobutoxyphosphonate Dimethallyl carboethoxyphosphonate The following are illustrative of typical carbamoyl- phosphonate esters: Diethyl carbamoylphosphonate Diallyl carbamoylphosphonate Dipropyl N-methylcarbamoylphosphonate Dimethyl N-allylcarbamoylphosphonate Bi s(2-chloroethy1)carbamoylphosphonate The following are illustrative of the amines which can be used for the amination and/or hydrolysis of the esters Ammonia Methylamine Dimethylamine All lamlne Propylamine Ethylamine Morpholine Piperidine Methylhydrazine Ν,Ν-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 10 is employed. The excess amine insures that amidation of the carboxylic ester rather than hydrolysis is the predominant reaction.

It is also preferred that a concentration of ammonia or amine of from 25$ to 50$ 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 the diester to a stirring aqueous solution of the amine which is cooled and maintained at about 15°C 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 and alkaline earth metals by interchanging the ammonium salt with 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 A solution of 48.5 parts of 29$ aqueous ammonium hydroxide is stirred and cooled with an external ice bath to °C. To the cooled solution 22 parts of diallyl carbomethoxyphosphonate is slowly added over a ten-minute period. The mixture turns cloudy, but clears up after about 15 minutes.

During this time, the mixture is allowed to warm spontaneously to about 30°C. and stirring is continued for two hours.

The clear solution is stripped under reduced pressure (15 mm of Hg.) at a water-bath temperature or 70°C. The residue is a white crystalline solid which is recrystallized from absolute ethyl alcohol, giving 12.3 parts of ammonium allyl carbamoyl-phosphonate, m.p. l60-l62.5°C Nonaqueous titration either as an acid or a base gives a molecular weight of l82†l.

Examples 2-l8 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 carbomethoxyphosphonate ammonium ethyl carbamoylphosphonate 3 bis(2-chloroethyl)carbobutoxy ammonium 2-chloroethyl 32107/2 - 11 dibutyl carboethoxyphosphonate ammonium butyl carbamoylphosphonate m.p. 205.5-206.5 C. diallyl carboethoxyphosphonate ammonium allyl . carbamoylpriosphonate dimethallyl carbomethoxyphosphonate' ammonium methallyl carbamoylphosphonate m.p. 193-197 C '' diisopropyl carboethoxyphosphonate ammonium i'so ropyl carbamoylphosphonate- m.p» 213-216°C (Dec.) dimettfyl carbomethoxyphosphonate ammonium methyl carbamoylphosphonate m.p. 148-151 C dipropyl carbopropoxyphosphonate ammonium propyl carbamoylphosphonate m.p. 190-192°C (Dec.) diisobutyl carbomethoxyphosphonate ammonium isobutyl carbamoylphosphonate m.p. 221-222°C (Dec.) diamyl carbomethoxyphosphonate ammonium amyl carbamoylphosphonate* m.p. 210-213 C dihexyl carbomethoxyphosphonate ammonium hexyl carbamoylphosphonate m.p. 212°C (Dec.) diodyl carbomethoxyphosphonate ammonium octyl carbamoylphosphonate m.p. 20a-211°G. bis(2-methoxye h l) carbomethoxyammonium 2-methoxyethyl phosphonate carbamoylphosphonate bis(2-bromopropyl) carbomethoxyammonium 2-bromopropyl phosphona e carbamoylphosphonate bis(6-chloroheptyl) carbomethoxyammonium 6-chloroheptyl phosphonate carbamo lphosphonate dioct-2-enyl carbomethoxyphosammonium oct-2-enyl phonate carbamoylphosphonate bis(2-ethoxypropyl) carbomethoxyammonium 2-ethoxypropyl phosphonate carbamoylphosphonate bis(2,2,2-trichloroethyl) carboammonium 2.2,2-tri- methoxyphosphonate chloroethylicarbaaoyl- phoephonate - 11a - Example 19 to a stirring ice-chilled solution of 35 fars 40 methylamlne in water is added slowly 8.4 parts of dimethyl car omethoxyphoephonate. The mixture is warned to 25°C and allowed to stir for 3 hours* The clear solution on stripping under reduced pressure yields 9.6 parts methylammonlum methyl methylcarbamoylphosphonate as a colorless oil* The product analyzes or the dihydra e. η?β » 1.4580 .

Examples 20-51 The procedure of Example 19 is repeated substituting an equivalent amount of the indicated "Aqueous Amine" for the methylamine of Example 19 and an equivalent amount of the indicated "Phosphonate Ester" for the dimethyljcarbo-methoxyphosphonate of Example 19 to obtain the indicated "Salt Product." Most of the indicated "Salt Products" are isolated as liquids or low-melting solids.

Aqueous Amine Phosphonate Ester Salt Product methylamine (40#) diethyl carboethoxy- meth lammonium phosphonate ethyl -meth l^ carbamoylphos- phonate 21 methylamine (40#) diisopropyl carbo- methy.lammonium methoxyphosphonate isopropyl N- methylcarbamoy 1 phosphonate 22 methylamine (40#) diallyl carboethoxy- methylammonium phosphonate allyl N-metayl- carDamoylphos- phonate 23 dimethylamine (25%) diethyl carbomethoxy- dimethylammoniu phosphonate ethyl N,N- dimethylcarbamo phosphonate 2 all lamine (30$) diallyl carbomethoxy- allylammonium phosphonate allyl N-allyl- carbamoylphos- phonate methylhydrazine (50 ) diethyl carboethoxy- methyl carbazoy phosphonate phosphonic acid »©-¾©ethyl ester salt with methy hydrazine n2¾ 1.4920 26 diethanolamine diethyl carbomethox - diethanolammoni phosphonate ethyl N,N-bis- ( 2-hydroxyethyl carbamoylphos- phonate 27 butylamlne (5 ) dibutyl carbomethox - butylammonium phosphonate butyl N-butyl- carbamoylphos- phonate 32107/2 13 - Ex. Aqueoun Am1n» Phosphonate Ester Salt Product 29 diethylamide (25#) dimethylallyl carbo- dieth lammonium propoxyphosphonate methallyl.N,N- diethylcarbamoyl- phosphonate " , piperidine (5056) dibenzyl carbomethoxy- piperidiniura phosphonate benzylpiper- idinocarbony1- phosphonate 31 1,1-dimethylhydrazine dipropyl carbomethoxy- 1,1-dimethyl • (35 ) phosphonate hydrazinium propyl 3,3-dimethylcar- . bazoylphosphonate Example 32 Eight parts of diethyl N-methylcarbamoylphosphonate is added slowly to l8 parts of a 29$ aqueous solution of ammonia, while holding the temperature at 25°C. by external cooling. The unreacted ammonium hydroxide is allowed to evaporate, giving a white, crystalline, solid residue.

Recrystallization from absolute ethanol g^ives 5 parts of ammonium ethyl N-methylcarbamoylphosphonate, ra.p. l89°C.

Examples 33-4- The procedure of Example 32 is repeated substituting an equivalent amount of the indicated "Aqueous Amine" for the ammonia of Example 32 and an equivalent amount of the indicated "Phosphonate Ester" for the diethyl methyl-carbamoylphosphonate of Example 32 to obtain the indicated "Salt Product." Phosphonate Ester Salt Product 33 ammonia (20$) diethyl N-butyl- ammonium ethyl carbamoylphosphonate N-butyl carbamoylphosphonate 33a ammonia (20 ) diethyl N-methylammonium ethyl carbamoylphosphonate N-methyl carbamoylphosphonate m.p. 189°C 34 ammonia (29$) diallyl N-allylcarbamoyl- ammonium allyl 32107/2 Bz. Aqueous Amine Phosphonate Ester Salt Product .methylamine (25%) dimethyl N,N-diallyl methylammoniurr: carbamoylphosphonate methyl N,N-di- allylcarbamoyl- . phosphonate 37 dimethylamine 2596) diethyl carbamoyldimethylammonium phosphonate ethyl car-r bamoylphosphonate 38 propylamine (20#) dimethyl N-propylear- propylammonium bamoylphosphonate ; methyl N-propyl carbamoylphos¬ - - : ■■. phonate 39 allylamine (25%) diallyl carbamoylallylammonium ' phosphonate allyl carbamoylphosphonate 40 isobutylamine (20%) diisopropyl N-methyl- isobutylammonium carbamoylphosphonate isopropyl limethylcarbamoyl- phosphonate 41 methylamine (20#) diisopropyl morpholino-methylammonium carbonylphosphonate isopropyl morpholinocar- bonylphosphonate 42 morpholine (50 ) dioctyl Ν-butyl-car· morpholinium bamoylphosphonate octyl N-butyl- carbamoylphosphonate 43- butylhydrazlne diethylearbamoyl- butylhydraziniur.. phosphonate ethyl carbamoylphosphonate 44 triethanolamine diallyl carbamoyltriethanolammonium phosphonate allyl carbamoyl¬ ,:-.J_. phosphonate ammonia (29 ) diethyl N-( 2-hydroxy- ammonium ethyl N- ethyl) carbamoylphos( 2-hydrox ethyl)— phonate carbamoylphosphtnabe 44b diethyl N,N-dimethyl- ammonium ethyl N,N- carbamoylphosphonate dimethylcarbamoyl- phosphonate m.p. 140-142.5°G. 44c diethyl pyrrolidino- ammonium ethyl carbonyll hosphonate pyrrolidiriocarbonyl- phosphonate m.p. 189-192°C (D?c.) 44d diethyl morpholino- ammonium ethyl carbonylphpsphonate morpholinocarbonyl- - 14a - To a mixture of 12,1 parts of ammonium allyl carbamoylphosphonate and 100 parts of ethanol is added dropwise 8 parts of bromine. The reaction mixture is filtered giving 8.5 parts of ammonium 2,3-dibromopropyl carbamoylphosphonate, m.p. 165-168°C.

EXAMPLES 46-48 The procedure of Example 45 is repeated substituting an equivalent amount of the indicated "Alkenyl Reagent" for the ammonium allyl carbamoylphosphonate of Example 45 and an equivalent amount of the indicated "Halogen" for th bromine of Example 45 to obtain the indicated "Product".

Alkenyl Reagent Halogen Product ammonium oct-2-enyl bromine ammonium 2,3-dibromooctyl carbamoylphoephonate carbamoylphosphonate ammonium methallyl chlorine ammonium 2,3-dichloro- carbamoylphoephonate 2-methylpropyl carbam- oylphosphonate ammonium but-2-enyl bromine ammonium 2, 3-dibromobutyl carbamoylphosphonate carbamo lphosphonate Example 9 An aqueous solution of 5 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 «e»e— benzyl carbamoylphosphonate/ m.p. 184-186°C.

Examples 50-56 The procedure of Example 9 is repeated subsitut-ing an equivalent amount of the indicated "Aqueous Amine" for the ammonium hydroxide of Example 49 and an equivalent amount of the indicated "Phosphonate Ester" for the benzyl methyl carbomethoxyphosphonate of Example 49 to obtain the indicated "Salt Product" as the principal product of this procedure.

Ex. Aqueous Amine Phosphonate Ester Salt Product 50 methylamine (40#) benzyl methyl methylammonium carbomethoxyphosphonate benzyl N- methylcarbamoyl phosphonate 51 ammonia (29$) methyl phenyl carboammonium methoxyphosphonate phenyl carbamoy phosphonate _ , m.p. 197-199°C(D 52 dimethylamine {5%) butyl ethyl carbo- dimethylammoniu methoxyphosphonate butyl N,N-di- methylcarbamoyl Aqueous Amine Phosphonate Ester Salt Product eth lamlne ( °#) methyl propargyl ethylammonium- carbomethoxyphos- propargyl N- phonate ethylcarbamoyl- phosphonate all lamine (2 %) methyl allyl carbo- allylammonium ethoxyphosphon te allyl N-allyl- carbamoyl- phosphonate pyrrolidine ( 30 ) methyl propyl carbo- pyrrolidinium methoxyphosphonate propyl pyrro- lidinocarbonyl- phosphonate ammonia ( 99^) methyl octyl carbo- ammonium octyl methoxyphosphonate ca rbamoylphos- phonate Example 57 To a stirring suspension of 25.4 parts ammonium butyl N-butylcarbamoylphosphonate and 100 parts methanol is added 42 parts of a o# solution of JT-benzyltrimethylammonium hydroxide in methanol. Ammonia and methanol are stripped from the mixture at 40°C. under reduced pressure, leaving benzyltrimethylammonium butyl N-butylcarbamoylphosphonate as a residue.

Examples 58-63 The procedure of Example 57 ie repeated substituting an equivalent amount of the indicated "Base" for the Jit-benzyltrimethylammonium hydroxide of Example 57 and an equivalent amount of the indicated "Ammonium Phosphonate" for the ammonium butyl N-butylcarbamoylphosphonate of Example 57 to obtain the indicated "Salt Product." Ammonium Base Phosphonate Salt Product tetraeth lammonium ammonium allyl tetraethylammonium hydroxide carbamoylphosphonate men allyl carbamoy phosphonate trimethylamine ammonium ethyl trimethylammonium (large excess) N-methylcarbamoylmeaeethyl N-methyl phosphonate carbamoylphosphona tetramethylammonium ammonium isobutyl tetramethylammoniu hydroxide N,N-dibutylcarbam- mone-isobutyl oylphosphonate N,N-dibutylcarba- moylphosphonate dodecyltriethyl methyl ammonium dodecyItriethyAmm ammonium hydroxide butyl N-butyl- ium meaebutyl N- carbamoylphosphonate butyl^arbamoy1- phosphonate 62 ethanolamine ammonium methallyl ethanolammonium hexahydroazepino- methallyl hexahydr carbonylphosphonate azepinocarbonylpho phonate 65 benzylamine ethylammonlum iso- benzylammonium iso- prop l carbamoyl- propyl carbamoyl phos honate phosphonate Example 64 A 5 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 sodium bicarbonate to give a solution of essentially pure sodium propyl N-methylcarbamoylphosphonate.

Evaporation of this solution gives the solid salt product.

Examples 65 - J2 The procedure of Example 64 is repeated, first obtaining the free acids of the indicated "Ammonium Phosphonate" as was done in Example 64 and then neutralizing the acid with the indicated "Base" according to the procedure of Example 64 to obtain the indicated "Salt Product." Ammonium Phosphonate Base Salt Product < ammonium phenyl sodium bicarbonate sodium phenyl carbamo lphos- carbamoylphosphonate phonate ' ammonium benzyl calcium hydroxide hemicalcium benzyl carbamoylphos- carbamoylphosphonate. phonate < ammonium ethyl barium hydroxide hemibarlum ethyl carbamoylphoscarbamoylphosphonate phonate 67a lithium carbonate lithium ethyl carbamoylphosphonate m.p. >30Q°C 67b sodium bicarbonate sodium ethyl carbamoylphosphonate m.p. 256°C (D$c.) 67c clacium hydroxide hemicalcium ethyl I carbamoylphosphonate m.p. > 300 C 67d zinc carbonate1. hemizinc ethyl carbamoylphosphonate m.p. 244 C (Dec.) 67e manganese (II) hemimanganese (II) carbonate ethyl carbamoylphosphonate m.p. >'300 C. 68 ammonium methyI'hydroxyethyltri- hydroxyethyltri- ll,N-dimethy1- methylammonium methylammonium ca bamoy1 phoshydroxide methyl N,N-dimethyl- » phonate carbamoylphosphonate 69 ammonium benzyl benzyltrimeth l- benzyltrimethyl- carbamoylphosammonium hydroxide ammonium benzyl phonate carbamoylphosphonate 70 ammonium allyl magnesium hydroxide hemimagneeium allyl carbamoylphoscarbamoylphosphonate phonate 71 ammonium butyl morpholine morpholinium N-methylucarbam- butyl N-methyl- oylphoephonate carbamoylphosphonate 72 ammonium mene- trimeth lamine trimethylammonium isopropyl morpho- isopropyl morphollno- linocarbonyl- carbonylphosphonate phosphonate - 18a - EXAMPLE 75 To a stirred solution cf 10 parts of potassium bicarbonate and 50 parts of water is added 13· parts ammonium isobutyl earbamoylphosphonate. Stirring is continued until solution is complete. The solutio is evaporated to dryness, giving the solid product, potassium isobutylcarbamoylphosphonate.

Examples 7*..- 79 The procedure of Example 73 is repeated substituting the indicated "Bicarbonate Salt" for the potassium bicarbonate of Example 73 and an equivalent amount of the indicated "Carbamoylphosphonate " for the ammonium mono-isobutyl carbamoylphosphonate of Example 73 to obtain the indicated "Salt Product." Carbamoyl- Bicarbonate Salt phosphonate Salt Product sodium bicarbonate ammonium ethyl lisodium ethyl limethylcarbamoyl- methylcarbamoyl- phosphonate phosphonate potassium bicarammonium benzyl potassium benzyl bonate carbamoylphosphonate carbamoylphosphonate lithium bicarbonate ammonium methyl N- lithium methyl N- butylcarbamoy1- butylcarbamoyl- phosphonate phosphonate 77 tetramethylammonium ammonium mono- tetramethylammonium bicarbonate allyl piperidino - allyl piperidino- carbonylphosphonate carbonylphosphonate benz Itriammonium butyl benzyl rimethylammonium carbamoylphosmethylammonium butyl bicarbonate phonate carbamoylphosphonate pentamethylhydra- ammonium butyl pentamethylhydra- zinium bicarbonate carbamoylphoszinium butyl phonate carbamoylphosphonate Formulation Compositions of the present invention can be prepared by admixing at least one of the compounds of formula (1) -with" pest control adjuvants or modif ers to provide compositions in the form of dusts, wettable or water- soluble powders, solutions, granules or pellets. In addition, the plant growth modifying agents such as maleic hydrazide and "Alar" (N-dimethylaminosuccinamic 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 or 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" 167 Annual by John W.

McCutcheon, Inc.

In general, less than 10$ 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$ but may even be less than 1 by weight.

Additional surface-active agents can be added to the formulations to increase the ratio of surfactant:active ingredient up to as high as 5:1 by weight. Such compositions may have a greater effectiveness than can be expected f om 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.

Water-Soluble Powders Water-soluble powders are compositions containing the water-soluble active material, an inert solid extender which may or may not be water-soluble, and optionally one or more surfactants to provide rapid wetting and solution. A buffer, which may also function as an extender, can be present to improve formulation stability and to control the pH of the final spray solution.

The classes of extenders suitable for the water-soluble 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 disodium 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 compounds known to the art as wetters and dispersants. Occasionally a liquid, non-ionic compound classified primarily as an emulsifier may serve as both wetter and dispersant.

Most preferred wetting agents are alkylbenzene- and alkylnaphthalene-sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are meth leellulose, polyvinyl alcohol, lignin sulfonates, polymeric alk lnaphthalenesulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium N-methyl-N- (long-chain acid) taurates.

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 25 to 98 weight percent active material, up to 2 .0 weight percent wetting agent, up to 5.0 weight percent dispersant, and from 2 to 75 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 1 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 5 of active ingredient, and from 50 to 85$ 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$ of the solvent system. ettable powders Certain compounds of this invention have sufficiently low water-solubility so that most of the active ingredient will not go into solution at the concentration at which it will be applied in the spray slurry. In this case the wettable powder formulations are preferred. Wettable powders contain from about 25 to 95 weight percent active material, from about 0.5 to 2.0# wetting agent, from about 0.25 to 5.0# dispersant, and from .25$ to inert extender; these terms referring to the same limits of formulation additives described for the water-soluble powders. As described above, small amounts of corrosion inhibitor and antl-foaming agents may replace some of the inert extender.

Dusts Dusts are dense powder compositions which are intended for application in dry form, in accordance 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 in n 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 free-flowing. They are also characterized by possessing relatively low surface areas and are poor in liquid adsorption.

Suitable classes of grinding aids are natural clays , diatoma-ceous 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 talcs, 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 90 weight percent of the total composition.

The grinding aid will usually constitute 5 to 50 weight percent of the composition, and the wetting agent will constitute from about 0 to 1.0 weight percent of the surfactants such as dispersing agents in concentrations of up to about 0.5 xveight percent.

The water-soluble powders described above can also be used in the preparation of dusts. While such water-soluble 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, to 50 weight percent adsorptive filler, 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 water-soluble powders used to make the dusts.

Granules and Pellets Under some circumstances it may be advantageous to apply the compounds of this invention in the form of granules or pellets. Suitable carriers are natural clays, some pyrophyllites and vermiculites . Wetting agents of the type listed by J. W. McCutcheon in "Detergents and E ulsifiers" 1967 Annual can also be present to aid leaching of the active componen .

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 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 0 to 5 weight percent wetting agent and about 65 to 5 weight percent inert mineral carrier.

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. One aspect of this invention relates to the use of the compounds of this invention 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 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 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.

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 .

Another aspect of this invention relates to a method for increasing the sugar content of sugar-containing crops by applying an effective amount of a compound of formula (1) to such crop from two to eight weeks prior to normally scheduled harvest.

It has been discovered that the compounds of formula (1) when so applied to plants will enhance the yield of sugar when compared to untreated plots grown under the same growing conditions . The practice of this invention also increases the Juice purity with a significant decrease in extraneous matter at the time of harvest which results in a more efficient and economical milling of the crop.

Generally, the compound of formula (1) is applied to the plant during the last quarter of the period of plant growth and is timed to coincide with the development of sugar in the useful portion of the plant. In most situations this means that a physiologically effective amount of the compound of formula (1) will be applied during the period of two to eight weeks prior to the normal time of harvest.

It vfill be appreciated that the amount of a compound content of sugar-containing crops will vary, for example with the particular crop involved, plant density, the type of formulation and application method utilised, maturity of the crop, soil type, season of the year, prevailing weather conditions, the particular active ingredient utilized and the frequency of the application. Since many factors are involved, it is not possible to indicate generally one rate of application which is preferred or even suitable for all situations. However, effective resolution of these factors in determining the effective amount in any given situation is well within the ability of persons of ordinary skill in the art.

Usually only one application ranging from 0.25 to 20 kilograms of active per hectare is needed. Preferably the composition will be applied at a rate of from 1 to 4 kilograms of active per hectare.

It will also be appreciated that there are a number of methods that can be used for applying the active compound to the plant. Spray application being the most convenient, is therefore the most commonly used method. The compositions can be sprayed from air or ground carriers. In the application of the active compound particular attention should be given to thorough and uniform coverage of the crop treated to obtain the desired results.

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 80 A dust having the following formula is prepared.

Ammonium ally^carbamoylphosphonate 5.0$ Talc 6 .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 he understood that the other compounds of this invention can also be formulated in a like manner.

The dust formulation of Example 80 is applied., using a helicopter, at a rate of 100 kilograms per hectare to an area under an electric power line in which the brush and trees have been freshly trimmed in spring 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 nigra), hawthorn (Crataegus spp . ) } sweet gum (Liquidamber styraciflua) and yellox poplar (Liriodendron tulipifera) .

The dust formulation of Example 80 can also be applied, using a helicopter, at the rate of 100 kilograms per hectare, to a three-hectare field of sugar cane six weeks prior to harvest. At harvest the treated field will yield significantly more raw sugar per hectare than a similar untreated plot in the §ame field. This treatment will also result in juice of increased purity with a sig nificant decrease in extraneous matter at the time of crushing, re m n Example 81 A water-soluble powder of the following formula is prepared.

Ammonium allyl carbamoylphosphonate 95·0$ Synthetic silica 3« 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 Pour kilograms of the water-soluble powder formulation of Example 81 is dissolved in 200 liters of water and 0.5 of a non-phytotoxic wetting agent is added. This solution is sprayed on one hectare of freshly trimmed Norway maple (Acer plantanoldes ) 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 80 can be dissolved in water at the rate of 2000 p.p.m. of active ingredient and applied to one 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.

Pour kilograms of the water-soluble powder formulation of Example 8l is dissolved in 200 liters of water and 0.5$ of a non-phytotoxic wetting agent is added. This solution is sprayed on one hectare of syrup sorghum four weeks prior to harvest. The treatment results in an increase in the sucrose content of the plant sap over a similar but untreated hectare in the same field. As a result, the yield of syrup is increased when the sap is extracted and refined.

Example 82 A wettable powder of the following formula is prepared.

Hemibarium benzyl dibutylcarbamoyl 50.0$ phosphonate ontmorrilonite 43.0$ Synthetic silica 4.0$ Disodium hydrogen phosphate 1.0$ Sodium alkylnaphthalenesulfonate 1.0$ Sodium lignin sulfonate 1.0$ The above ingredients are mixed and then ground to pass a Ο.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 82 hectare of newly trimmed hedgerov/ in the spring after the leaves have expanded. This treatment greatly reduces the growth of plants growing in the hedgerow such as osage orange (Madura pomifera)3 but does not seriously injure them. The hedgerow is thus kept neat with a minimum of labor expended for trimming it.

Ten kilograms of the formulation of Example 82 are added to OO liters of water and agitated until the active ingredient dissolves. This solution is then sprayed on one hectare of sugar cane five weeks prior to harvest. At harvest, the treated field yields more raw sugar per hectare than a similar but untreated plot in the same field.

Example 83 A solution of the following formula is prepared.

Ammonium ethyl carbamoylphosphonate 2 .0% Disodium hydrogen phosphate 1.0% Sodium laurylsulfate 0.5 Water The above components are blended to form a homogeneous solution.

The following compounds can be formulated in like manner.

Benzyltrimeth lammonium benzyl N-butylcarbamoyl- phosphonate Trime n lammonium ethyl N-methylcarbamoylphosphonate Meth lammonium isopropyl morpholinocarbonyl- phosphonate Trieth lammonium ethyl carbamoylphosphonate Ten kilograms of the solution prepared in Example 83 are added to 200 liters of water and applied with a fixed boom sprayer to one hectare of Kentucky bluegrass (Poa This treatment greatly reduces the rate of growth of the bluegrass for a period of four to eight weeks and the mowing required to maintain the area in an attractive condition is reduced.

Ten kilograms of the solution prepared in Example 83 are added to 200 liters of water and applied with a fixed-boom sprayer to one hectare of sugar cane eight weeks prior to harvest. As a result of this treatment the cane ripens with a significant increase in sugar yields. This treatment also reduces lodging before harvest.

Example 84 A solution of the following formula is prepared .

All lammonium allyl N,N-diallylcarbamoyl- 24.0$ phosphonate Trimethylnonylpolyethyleneglycol ether 1.0$ Water 20.0$ Ethylene Glycol 55.0$ The above components are blended to form a homogeneous solution.

The following components can be formulated in like manner.

Ethanolammonium methallyl hexahydroazepino- carbonylphosphonate Dodecyltrimethylammonium butyl butylcarbamoyl- phosphonate Ammonium octyl carbamoylphosphonate Six kilograms of the formulation of Example 84 are added to 400 liters of water containing 0.5$ Tween 20 (polyoxyethylenesorbitan monolaurate) . This solution is sprayed to runoff on a freshly trimmed privet (Ligustrum ovalifolium) in May. The treatment greatly reduces the growth of the hedge. Little labor is required to keep it attractive all season.

A solution containing 227 gms. of active ingredient formulated as above is sprayed on an area of red delicious apple trees about two 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 shoots known as "water sprouts" and ameliorates the tendency to biannual bearing which is strong in this variety.

Six kilograms of the formulation of Example 84 are added to 400 liters of water containing 0.5$ Tween 20 (poly-oxyethylenesorbitan monolaurate) . This solution is sprayed to runoff on one hectare of sugar beets. As a result of this treatment the crop matures with a significant increase in sugar yield.

Example 85 The following formulation is prepared.

Ammonium methyl carbamoylphosphonate 25.0$ Sodium lauryl sulfate 50.0$ Magnesium silicate 10.0$ Kaolinite 15. % The above components are blended, micropulverized to pass a O.jJO mm. screen and reblended.

The following compounds can be formulated in lii:e manner.

Morpholinium ethyl carbamoylphosphonate Sodium phenyl carbamoylphosphonate Hemicalcium benzyl carbamoylphosphonate Five kilograms of the formulation of Example 85 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.

Five kilograms of the formulation of Example Cn are suspended in 100 liters of water and then sprayed on one hectare of sugarjeane four weeks prior to harvest. At harvest the treated area yields more raw sugar than a similar untreated hectare in the same field.

Example 86 An aqueous concentrate solution is prepared which contains the following ingredients : ammonium ethyl carbamoylphosphonate 2 .0% N-dimethylaminosuccinamic acid 12.0$ water 32.0$ methanol 22.0$ The above ingredients are stirred together with slight warming until a homogeneous solution results.

A water solution of the formulation of Example 86 is prepared to contain 600 p.p.m. total active ingredient.

This solution is sprayed on Mcintosh apples to run-off in early September. " The treatment prevents coloration in the Example 87 The following wettable powder is prepared: ammonium ethyl carbamoylphosphonate J>0.0$ maleic hydrazide 20.0$ synthetic silica .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 reblended.

The wettable powder of Example 87 is suspended in water at the rate of , 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 87 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 spring warm period the trees in these orchards begin to break dormancy and buds sprout. The treated trees, on the other hand, remain dormant and do not sprout nor flower while there is danger of frost. In this manner, a more reliable yield is assured.

Example 88 A wettable powder of the following formula is prepared : Ammonium isopropyl carbamoylphosphonate 50$ Montmorillonite 43$ Synthetic silica K%> Disodium hydrogen phosphate 1$ Sodium alkylnaphthalenesulfonate Sodium alkylnaphthalenesulfonate Sodium lignin sulfonate 1 The above ingredients are mixed and then ground to pass a 0.25 screen. The active ingredient in the above formulation dissolves when the composition is added to water.

Ten kilograms of the formulation of Example 88 are added to 400 liters of water and agitated until the active ingredient dissolves. This solution is then sprayed on one hectare of sugar cane 6 weeks prior to harvest. The treatment results in an increase in the yield of sugar. The treatment also increases the juice purity with a significant decrease in extraneous matter at the time of crushing resulting in a more efficient and economical milling.

Claims (39)

1. A compound of the formula:

where R^ is alkyl of one through eight carbon atoms, chloroalkyl of one through eight carbon atoms containing up to three chlorine atoms, bromoalkyl of one through eight carbon atoms containing up to three bromine atoms, alkoxy^alkyl of from three through ten carbon atoms, total, alkenyl of two through eight carbon atoms, alkynyl of three

through four carbons, phenyl or benzyl; Rs and

Rs can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms, hydroxyalkyl of two through four carbon atoms,

or

alkenyl of three through four carbon atoms, alkynyl of three through four carbon atoms; Ra and R3 can be taken together to form a ring wherein R2 and

R3 taken together are -(CH2)a-0-(CH2)2- or

or 6 or one of R2 and R3

hydrogen or alkyl of one

through four carbon atoms and Rs is hydrogen or alkyl of one through four carbon atoms; and

M is hydrogen, sodium, lithium, potassium, calcium, magnesium, zinc, manganese, barium or where

g, R^ and Rg can be the same or different and each can be hydrogen, alkyl of one through four carbon atoms or hydroxyalkyl of two through four

RQ is hydrogen, alkyl of one through twelve

carbon atoms, benzyl or -IT where R is

Rs

hydrogen or alkyl of one through four carbon

atoms and Rs is hydrogen or alkyl of one

through four carbon atoms.

2. A compound of the formula:

where i is alkyl of one through four carbon atoms, alkenyl of three through four carbon atoms,

2 and R3 are each hydrogen; and

M is hydrogen, sodium, lithium or potassium.

3. Ammonium allyl carbamoylphosphonate .

h . Ammonium ethyl carbamoylphosphon te.

5. Ammonium isopropyl carbamoylphosphonate.

6. A method for retarding the growth rate of plants which comprises applying an effective amount of a compound of Claim 1 to said plant to effect growth retardation.

7. A method for retarding the growth rate of plants which comprises applying an effective amount of a compound of Claim 2 to said plant to effect growth retardation.

ψ

8. A method for retarding the growth rate of plants which comprises applying an effective amount of

ammonium allyl carbamoylphosphonate to said plant to effect growth retardation.

9. A method for retarding the growth rate of plants which comprises applying an effective amount of a compound of Claim 1 to the locus of said plants.

10. A method for retarding the growth rate of plants which comprises applying an effective amount of a compound of Claim 2 to the locus of said plants.

11. A method for retarding the growth rate of plants which comprises applying an effective amount of

ammonium allyl carbamoylphosphonate to the locus of

said plants.

12- A method for retarding the growth rate of woody vegetation which comprises applying an effective

amount of a compound of Claim 1 to said vegetation.

13. A method for retarding the growth rate of woody vegetation which comprises applying an effective

amount of a compound of Claim 2 to said vegetation.

14. The method of Claim 12 which comprises applying an effective amount of ammonium allyl carbamoylphosphonate

15 · The method of Claim 13 which comprises applying an effective amount of ammonium ethyl carbamoylphosphonate

- 40 -

16. The method of Claim 13 which comprises applying an effective amount of ammonium allyl carbamoylphosphonate.

17. A method for retarding the growth rate of

woody vegetation which comprises applying an effective

amount of a compound of Claim 1 to the locus of said vegetation.

18. A method for retarding the growth rate of

woody vegetation which comprises applying an effective

amount of a compound of Claim 2 to the locus of said vegetation.

19 · The method of Claim l8 which comprises applying an effective amount of ammonium allyl carbamoylphosphonate .

20. A method of increasing the sugar content of a sugar-containing crop comprising applying to said crop from two to eight weeks prior to normally scheduled harvest an effective amount of a compound of Claim 1.

21. The method of Claim 20 wherein the compound applied is represented by the formula:

where is alkyl of one through four carbon atoms, or

alkenyl of three through four carbon atomsj R2.and are each hydrogen; and M is hydrogen, sodium, lithium or potassium.

22. The method of Claim 20 wherein said compound is ammonium allyl carbamoylphosphonate.

23. The method of Claim 20 wherein said compound is ammonium ethyl carbamoylphosphonate.

- 41 -

24. The method of Claim 20 wherein said compound is ammonium isopropyl carbamoylphosphonate .

25. The method of Claim 20 wherein the crop is sugar cane.

26. The method of Claim 20 wherein the crop is sorghum.

27. The method of Claim 20 wherein the crop is sugar beets.

28. The method of Claim 21 wherein the crop is sugar cane.

29. The method of Claim 21 wherein the crop is sorghum.

30. The method of Claim 21 wherein the crop is sugar beets.

31. The method of Claims 22 through 2 wherein the crop is sugar cane.

32. The method of Claims 22 through 2 wherein the crop is sorghum.

33. The method of Claims 22 through 24 wherein the crop is sugar beets.

34 . A plant growth regulant composition comprising an effective amount of a compound of Claim 1 in combination with suitable agricultural adjuvants and modifiers.

35. A plant growth regulant composition comprising from 5 to 95 weight percent of a compound of Claim 1 in combination with to 75 weight percent suitable agricultural adjuvants and modifiers .

- 42 -

36. A plant growth regulant composition comprising from 5 to 95 weight percent of a compound of Claim 1 , from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 5.0 weight percent dispersant and from 4.25 to 94.25 weight percent inert extender.

37. A plant growth regulant composition comprising an effective amount of a compound of Claim 2 in combination with suitable agricultural adjuvants and modifiers.

3¾ A plant growth regulant composition comprising from 5 to 95 weight percent of a compound of Claim 2 in combination with 5 to 95 weight percent suitable agricultural adjuvants and modifiers.

39. A plant growth regulant composition comprising from 5 to 95 weight percent of a compound of Claim 2 ,

from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 5 · 0 weight percent dispersant and from 4.25 to 9^ .25 weight percent inert extender.

40» A plant growth regulant composition comprising an effective amount of a compound of Claim 3 in combination with suitable agricultural adjuvants and modifiers.

4l. A plant growth regulant composition comprising from 5 to 95 weight percent of a compound of Claim 3 in combination with 5 to 95 weight percent suitable agricultural adjuvants and modifiers.

42„ A plant growth regulant composition comprising from 5 to 9 'weight percent of a compound of Claim 4 , from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 5 - 0 weight percent dispersant and from 4.25 to 9 .25 weight