NL7908074A - DERIVATIVES OF ESTERS OF PHOSPHORIC ACIDS AND METHODS FOR PREPARING AND USING THESE DERIVATIVES. - Google Patents

Description

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Derivatives of phosphonic acid esters and methods of preparing and using these derivatives.

The invention relates to derivatives of esters of benzylphosphonic acids of formula 1, wherein Yj represents a hydrogen or halogen atom, preferably a chlorine, bromine or fluorine atom, in particular a chlorine atom, Yg represents a hydrogen or halogen atom, at preferably a chlorine, bromine or fluorine atom, in particular a chlorine atom, an alkyl group with at most 10 carbon atoms, an alkoxy group with at most 10 carbon atoms, a cycloalkyl group with 3 to 7 carbon atoms or a cycloalkoxy group with 3 to 7 carbon atoms and Y ^ a hydrogen or halogen atom, preferably a chlorine, bromine or fluorine atom, in particular a chlorine atom, a nitro group, a cyano group, an alkyl group with a maximum of 10 carbon atoms, an alkoxy group with a maximum of 10 carbon atoms C 1-4 alkoxyalkyloxy group, alkenyl group of 2 to 10 carbon atoms, alkenyloxy group of 2 to 10 carbon atoms, or alkylthio group of up to 10 carbon atoms, each alkyl or alkenyl group or portion is unsubstituted or substituted by halogen, preferably chlorine and / or fluorine, a benzyl, phenyl or phenoxy group, each phenyl group or portion being unsubstituted or by up to 2 substituents selected from halogen, preferably chlorine , bromine or fluorine, in particular chlorine, nitro, cyano, alkyl with up to 6 carbon atoms, alkoxy with up to 6 carbon atoms, alkylthio with up to 6 carbon atoms, each alkyl group or part being unsubstituted or by halogen, preferably chlorine and / or fluoro, is substituted, O 9 -COHRxRy; CORp; -COORp; -SRpj -SOgRp; -NRxRy; -CH = U-0Rp group, a group of formula 10 or 11, representing or in which Yg and Y ^ are / §3 80 74 2 "*

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on adjacent carbon atoms and together form a methylene-dioxy or ethylenedioxy group, wherein Rx and Ry independently represent an alkyl group having up to 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms or wherein 5 Rx and Ry together with the nitrogen atom to which they are attached form a pyrrolidine, piperidine, N-methyl-piperazine or morpholine group, Rp is a phenyl group or an unsubstituted or chlorine and / or fluorine-substituted alkyl group having up to 10 carbon atoms and and Zg, independently from each other, 0 or S 10 and either R 4 is an alkyl group of up to 10 carbon atoms which is unsubstituted or is substituted by halogen, preferably chlorine or fluorine, a cyeloalkyl group having 3 to T carbon atoms, which is unsubstituted or halogen, preferably chlorine, is substituted, an alkyl group with at most U 15 carbon atoms which is substituted by an alkoxy group with at most 3 carbon atoms, phenyl or phenoxy group is mono-substituted, wherein the phenyl or phenoxy group is unsubstituted or is substituted by up to 2 substituents selected from halogen, preferably chlorine, alkyl of up to k carbon atoms, alkoxy of up to k carbon atoms, and trifluoromethyl, a alkenyl group having 2 to 6 carbon atoms which is unsubstituted or is substituted by halogen, preferably chlorine, an alkynyl group with 2 to U carbon atoms or a phenyl group which is unsubstituted or by at most 2 substituents selected from halogen, preferably chlorine, alkyl of at most b carbon atoms, alkoxy of at most ^ carbon atoms and / or trifluoromethyl is substituted and Rg represents a hydrogen atom or one of the meanings shown under Rj, or Rl and Rg together with the α-carbon atom is a cycloalkylidene group with 3 to 7 carbon atoms, which is unsubstituted or by halogen, preferably chlorine, and / or alkyl with at most 1 carbon is substituted, X, independently, O, S or IR, R, form an unsubstituted alkyl group of at most 8 carbon atoms, an alkyl group of at most U carbon atoms formed by an alkoxy group of at most 3 carbon atoms, alkylthio group of at most 3 carbon 790 8 0 74 4 3 atoms, alkylthio group with at most 3 carbon atoms and / or halogen, preferably chlorine or fluorine, is substituted, an alkenyl group with 3 to 6 carbon atoms, an alkynyl group with 3 to 6 carbon atoms, a tetrahydrofur-2-ylmethyl group, a tetrahydro-2H-pyran-2-ylmethyl group or a cycloalkyl group with 5 or 6 carbon atoms and and R ^, independently of each other, have a meaning of R ^, or E ^ and R together with the nitrogen atom to which they are attached form a piperidine, pyrrolidine, H-methylpiperazine or morpholine group, as well as to processes for preparing and using these derivatives.

Thus, the invention also relates to a method of preparing a herbicidal composition by introducing one or a number of the above-defined compounds into a dosage form suitable for such application and to controlling ohspice species in a particular region by administering thereto a herbicidally effective amount of Ien or a number of compounds of formula 1, as defined above. Finally, the invention also includes molded preparations having a herbicidal action, which have been obtained by a method described above.

The compounds of the invention of formula 1 of the invention exhibit a wide spectrum of herbicidal activity, both against 25 cotyledonous weeds * such as Apera spica venti, Alonecurus myosuroides, Echinochloa crus-galli, Avena fatua and Agrostis alba, as two cotyledonous weeds such as Amaranthus retro f lexus. Capsella bursa-pastoris, Chenopodium alba, Galium aparine, Senecio vulgaris and Stellaria media, as evidenced by pre- and post-emergence treatments at doses equivalent to 0.1, 1.0 and 5 kg active component per hectare of treated area. The herbicidal activity was determined 28 days after the treatment. During this determination, the greenhouse was kept at a temperature between 20 and 21 ° C and daylight was brought in for 35 hours to 17 hours per day. On the other hand, the 790 80 74

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kk compounds according to the invention under corresponding conditions in the greenhouse have virtually no harmful effect on crops from, such as cereals (for example wheat, barley, rye and corn), carrots, sunflowers and soybeans in dosages corresponding to 5 * 0 kg of active ingredient per acres of the field with crops.

The compounds of the invention are thus indicated for the selective control of weeds in crops such as cereals (e.g. wheat, barley, rye and corn), carrots, sunflowers and soybeans.

The amount of compound (s) according to the invention that have to be administered to obtain the desired effect will, as will be clear, depend on the plant concerned, the area to be treated and other variables, such as the compound used, method of application, conditions during treatment etc. In general, however, satisfactory results in controlling weeds are obtained if the compound (s) is administered in an amount of about 0.5-6 kg per hectare, for example between 1 and V kg per hectare of treated area. The compounds are preferably administered after emergence.

For a selective herbicidal use, for example in the aforementioned crops, the amount to be used will be chosen such that maximum control of the weed species is obtained with minimal damage to the crops. In general, satisfactory results are obtained for the selective control of weeds if the compound (s) is administered in an amount of 0.5 to U kg per hectare, preferably between 1.0 and 3 kg per hectare.

The compound (s) are preferably used after the emergence of the weeds, in particular after the emergence of both the crops and the weeds.

In general, a relatively rapid onset of activity is observed.

The compound (s) according to the invention can be used and, in fact, are preferably used together with suitable carriers, diluents and / or additives.

As stated above, the preparation of these herbicidal preparations, as well as the shaped preparations thus obtained, is also part of the invention.

The herbicidal compositions according to the invention can be both solid and liquid. The solid preparation forms, for example powder and granular forms, can be obtained by mixing or impregnating solid carriers or diluents suitable for herbicidal application, such as diatomaceous earth, kaolin, lime, talc, limestone or cellulose powder, with the active connection (s).

Examples of additives which can be included in the compositions according to the invention are wetting agents and dispersing agents, for example condensation products of formaldehyde with naphthalene sulphonate and alkyl benzene sulphonates, adhesion improvers, for example dextrin and emulsion stabilizers, for example ammonium caseinate. Such additives are suitable for inclusion in, for example, wettable, powdered preparation forms or for use together with suitable solvents, for example, hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene, alkylated naphthalenes, kerosene, aromatic petroleum hydrocarbon fractions (e.g., commercially available Shellsol AB with a boiling range of 187-213 ° C) ketones, such as isophorone, acetone, cyclohexanone, diisobutyl ketone and methyl ethyl ketone, alcohols such as isopropanol, ethanol and methylcyclohexanol, chlorinated hydrocarbons, such as tetrachlorethylene, ethylene chloride or trichlorethylene, forming trichlorethylene.

In addition to the compound (s) of the invention, the herbicidal compositions may contain other active agrochemicals, such as other herbicides.

Concentrated forms of the compositions of the invention will generally contain as active ingredient between 2 and 80% by weight, preferably between 5 and 70% by weight, of the compound 35 (s) of the invention.

790 80 74

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Administration forms of the compositions according to the invention will generally contain from 0.01 to 10% by weight of the compound (s) of the formula 1 as active ingredient.

Specific examples of herbicidal action formulations are given below.

In the compounds of formula 1, ring A preferably contains at least one substituent.

The translations' et formula 1e, vaeriu, ^, * 3a * ^ 1a * ^ 2a * E3a and ^ a ^ Ua (where <* er Ε, - &) resp. have the meanings of Y ^ »K |, Rg, R ^ and XR ^ (including R ^) given above, where i) if Y ^ a, Yga and Y ^ a represent a hydrogen atom, both OR ^ and XaR ^ a C8 H ^ O or iC ^ H ^ O and R ^ a CHj, C2H5 », nC ^ H ^, iC ^ H ^, represents an allyl or benzyl group, Rga does not represent a hydrogen atom or an alkyl group with 2 to 5 carbon atoms ii) if Υ ^ &, Y3a and R2a represent an atom and OR ^ a and X ^ R ^ both represent an alkoxy group with 2 to 5 carbon atoms, R is not a phenyl group, or

1 £ L

Iii) if Y1 &, Yga and Rga represent a hydrogen atom, Y ^ a represents a methyl group and 0R ^ a and X ^ j ^ both represent the ethoxy group, R ^ a is not a methyl group and iiii) if Y1 &, Y2a and Y ^ a represent a hydrogen atom, R 2a represents a methoxymethyl group, and R 4a and X 2 25 both represent the ethoxy group, R 1 is not a methyl group, are new and constitute another aspect of the invention. If ring A is trisubstituted, it is preferably a trichloro compound. Preferably, however, ring A is mono- or di-substituted.

Examples of substituted alkyl groups in the meaning of Y ^ are -CF ^ and -CHgCHgCl. Examples of substituted alkoxy groups within the meaning of Y ^ are -OCF ^ -OCHF2, -0CF2Cl, O-CHgCHgCl and -OCFgCHFg as an example of a substituted alkenyl group in terms of Y ^ can be mentioned -CH: CC12. An example of a substituted alkylthio-35 group in the meaning of Y ^ is -SCF ^. These are also suitable 790 8 0 74 'r,

a

7 examples of the relevant groups as substituents of an optional phenyl or phenoxy group within the meaning of Y ^.

Of the unsubstituted alkyl groups in the sense of, those having 3 to 6 carbon atoms are recommended. When R1 and Rg are equal and represent an unsubstituted alkyl group, this is preferably the n-propyl, i-propyl or n-butyl group.

If R1 and Rg are different and Rg is a hydrogen atom or a primary alkyl group with at most 4 carbon atoms, then R ^ is preferably branched at the α position and in particular gives the i-propyl, sec.butyl, 3 pentyl, 2-pentyl, 3-hexyl, cyclohexyl or cyclopentyl group.

Recommended meanings of X in the compounds of formula 1 are 0 and IRR. An optional unsubstituted alkyl-15 group, in the meaning of R 1 and R 1, preferably contains 2 to 6 carbon atoms.

A particularly recommended group of compounds of the formula 1 are the compounds of the formula 1b, wherein Yg 'is a hydrogen or a chlorine atom, Y ^' is a chlorine or bromine atom, an alkoxy group with at most 5 carbon atoms, an alkenyl oxy group with 3 t / m 5 carbon atoms or an alkyl group with at most 5 carbon atoms, R 1 'an unsubstituted alkyl group with 3 to 6 carbon atoms or a cyeloalkyl group with 3 to 6 carbon atoms, Rg' a hydrogen atom or an unsubstituted alkyl group with at most b carbon atoms, X 'an oxygen atom or a -HR ^' group and R ^ ', R ^' and R ^ f, independently, represent an unsubstituted alkyl group with 2 to U carbon atoms.

If Yg and Y both represent a chlorine atom, then these chlorine atoms are preferably in the 2- and b-30 position.

The compounds of the formula 1 according to the invention can be obtained by a) preparing compounds of the formula 1c, wherein Y 1, Yg, Y 1, R 1, R 1, R 1, R and X have the aforementioned meanings and Rg A previously indicated meaning of Rg has 790 80 74 * 8 where Rg "represents a hydrogen atom if X = 0 or HR ^.

(wherein R 1 has a meaning as defined above), by reaction of a compound of formula 2, which represents a chlorine atom or an -ORg group and Yg, Y ^, R ^, Hg "and R ^ represent the above meanings with a compound of formula 3, wherein X and R ^ have the meanings indicated above and either M is a hydrogen atom if X * is 0 or HR ^, or M is an alkali metal cation (preferably sodium) when X is a sulfur atom, or 10 fa) preparation of compounds of formula 1d, wherein Y ^, Y ^, Yg, Rg and XR ^ have the meanings indicated above

and R 1 has an unsubstituted alkyl group with at most 1 III

10 carbon atoms and R 1 represent a hydrogen atom, or both III ^ III

substituents R ^ and Rg represent a phenyl group or a substituted phenyl group, by reacting a compound of formula U, wherein Y ^, Yg, Yg, R ^ ^ and Rg "^ have the meanings indicated above and Qg represents a halogen atom (eg chlorine or bromine, in particular a bromine atom), with a compound of formula 5, wherein X, Rg and R ^ have the meanings indicated above, or c) preparation of compounds of formula 1e, wherein R and R * V have the previously indicated meanings R1 has meanings '^ τγ jy' and R?, where not both substituents R1 and R. have a d. 1 ά ii

phenyl group or a substituted phenyl group, X

25 0 or NR ,. and Y ^, Yg, Yg, Rg, and Rj. have the meanings indicated above, by a compound of formula 6, wherein

R /; a hydrogen atom, a phenyl group or a substituted O II

phenyl group and X, Y ^, Yg, Yg, Rg and R ^ have the meanings indicated above, to be mono- or disubstituted with one or two compounds of formula 7, wherein R ^ has the aforementioned meaning of R ^, wherein this substituent is not a phenyl or substituted phenyl group and Qg represents a cleavable group such as bromine, iodine, mesyloxy or tosyloxy or with a compound of formula 7a wherein Rg is unsubstituted or by halogen (preferably chlorine) and / or alkyl of alkylene group having 2 to 6 carbon atoms which is at most 790 80 74 9 substituted U carbon atoms and has a meaning as indicated above, or d) preparation of compounds of formula 1f, 5 in which X ^, Y ^, Y ^, and R ^ have the meanings indicated above and Rv represents a methyl, phenyl or substituted phenyl group, by a compound of formula 8, wherein a halogen atom (for example chlorine, iodine or bromine) represents and Y Y, Yg, Y ^ and R ^ de above have meanings, to react with a compound of formula 9, wherein Rg, Rl and Xxx have the meanings indicated above.

The above-described reactions can be carried out in a conventional manner.

If in process a) a chlorine atom represents -15, this process is preferably carried out such that 2 moles of a compound of formula 3 react with 1 mole of a compound of formula 2.

In process a) a compound of formula 2 is reacted with an amine or an alcohol, the mixing process is suitably conducted in the presence of a tertiary amine, such as pyridine or triethylamine and, optionally, in the presence of catalytic amounts of an acylation accelerator, such as p- dimethylamine pyridine, from. Suitably a compound of the formula II is added, optionally dissolved in a solvent, such as 1,2-dichloroethane, benzene, toluene, xylene, glyme (1,2-dimethoxyethane), diglyme. CH ^ OCHgCHgJgOCH ^ 7 or an excess of R ^ XH, at a temperature between 0 and 30 ° C, to a mixture of the amine or alcohol reagent with the tertiary amine and optionally an acylation accelerator and allow the reaction to proceed to the end by stirring the reaction mixture for 1 to 18 hours at a temperature between 20 and 100 ° C, preferably at room temperature. If an amine is used as the reagent, the recommended reaction media are formed by ethers and hydrocarbons.

In process a) if a compound of formula II is reacted with an alkali metal thiolate, the reaction is carried out suitably at a temperature between 0 and 30 ° C in an ether or hydrocarbon solvent, such as glyme, diglyme, henzene, toluene, xylene or in CHgClg, optionally in the presence of a phase transfer catalyst such as benzyl trimethyl ammonium 5 bromide or in a dipolar solvent such as dimethylformamide. Process a) is especially useful for preparing compounds of formula 1 wherein either X = S or XR ^ is part of a primary alcohol R ^ OH or of an amine HNR ^ R ^, wherein the α-carbon atoms of both substituents R ^ and R ^ are unbranched.

TO Process b) is suitably carried out in a solvent such as glyme or toluene, suitably by reacting at the reflux temperature or in dimethylformamide or hexamethylphosphoric triamide, or in a mixture of solvents, for example a mixture of toluene and hexamethylphosphoric triamide (HMPT), at 15 room temperature. It is also possible to run the reaction in the absence of a solvent at a temperature between 20 and 120 ° C. A suitable reaction time, with or without solvent, will be between 0.5 and 18 hours. Process b) is preferably used for the preparation of compounds of formula 1 in which both substituents R 1 and R 5 are a phenyl or substituted phenyl group or in which R 1 is an unsubstituted alkyl group with at most 10 carbon atoms and R 9 represents a hydrogen atom. Q2 preferably represents a bromine atom.

If in method c) there is a connection

IV

In order to obtain a formula of formula wherein R_ is a hydrogen atom IV IV ^ or in which R ^ and Rg are joined together, the reaction is preferably carried out such that the compounds of formulas 6 and 7 or 7a in a molar ratio of 1: 1 comment. Is the

IV

desired to obtain a compound of formula 1e wherein R_

IV

30 does not represent hydrogen and is not equal to R 1, the reaction is suitably carried out in two steps, in the first step reacting a compound of formula 6 with a compound of formula 7 (in a molar ratio of 1: 1) and, in the second step, the product thus obtained reacts with another compound of the formula 7 790 8 0 74 J 11

In process c), if one wishes to react a compound of formula 6 with 1 mole of a compound of formula 7 or 7a, the reaction is suitably conducted in the presence of a base such as sodium hydride and in a solvent such as glyme, dimethylformamide, dimethyl sulfoxide (DMSO), IMPT or toluene or in a mixture of solvents, for example, of toluene and HMPT. A suitable reaction temperature is between 0 and 80 ° C and a suitable reaction time between 15 min and 18 hours. Separation of the resulting reaction product from an optionally remaining unreacted compound of formula 6 is suitably chromatographically or by selective hydrolysis of the latter compound, for example, by treatment with 5 Pf potassium hydroxide in a mixture of ethanol and water (9: 1) for 2-18 hours and carried out at a temperature between 20 and 80 ° C. If desired, instead of sodium hydride, a stronger base, such as sodium amide, can be run while decreasing the reaction temperature and / or shortening the reaction time.

If in process c) it is desired to dialkylate a compound of formula 6 (as described above) * then the reaction is suitably conducted in the presence of at least 2 equivalents of a strong base, such as sodium methylsulfinyl carbaanion in dimethyl sulfoxide or a mixture of dimethyl sulfoxide and toluene or sodium amide in an organic solvent as described above or in liquid ammonia. If the reaction is allowed to proceed in an organic solvent, the reaction is allowed to proceed for 5-60 min at a temperature between -10 and 1 + 5 ° C, if desired by stirring for 30 min to 2 h at a temperature between 25 and 70 ° C. An optionally formed mixture of the disubstituted product and the monosubstituted product can be chromatographically separated.

If sodium methylsulfinylcarbanion is used as base, this ion can be freshly prepared by reacting sodium hydride with stirring in a nitrogen atmosphere for 1 + 5 to 60 min with an excess of dry dimethyl sulfoxide at a bath temperature of 70 ° C. If sodium amide is used as the base, the reaction is suitably carried out in the presence of an equivalent amount of hexamethyldisilazane. The latter method is suitably applied if steric interference occurs.

process d) is suitably carried out by heating a mixture of the reagents, generally preferably in the presence of potassium iodide, or a temperature between 60 and 200 ° C. The reaction is then suitably completed by heating the reaction mixture at a temperature between 60 and 210 ° C for 5 minutes to 8 hours, preferably 30 minutes at a temperature of about 160 ° C. However, if the compound of formula 8 is a diphenylchloromethane or a para-nitrobenzyl halide, the reaction is preferably conducted in the absence of the potassium iodide, but using a compound of formula 8 in which a chlorine or bromine atom is carried out. 15 represents a methyl group, preferably an iodine atom.

R.J represents a phenyl group or a substituted phenyl group, preferably is a chlorine atom.

The resulting compounds of the formula I according to the invention can be separated and purified in a usual manner.

The processes a), b), c) and d), insofar as they relate to the preparation of compounds of formula 1a, are also part of the invention.

In order to indicate in the process claims that the process a), b), c) and d) relate to the preparation of new compounds of formula 1a, the substituents in the respective formula are labeled "V", for example R,, X 'etc.

1a a

The starting materials used in the above-described processes are known or can be prepared from available starting materials in a conventional manner.

Thus, the compounds of formula 6 are conveniently obtained according to method b) or d).

As will be appreciated, converting one compound of formula 1 into another can be a conventional 790 80 74. j 13 operation.

It will also be appreciated that the compounds of the formula I of the invention have asymmetric centers if R1 and Rg are different and / or if XR1 and OR1 are different, which may then allow them to exist in optically active, diastereomeric or racemic forms. The invention is of course not limited to some special Torm.

In the following examples, all parts and percentages are resp. parts by weight and percentage percentages.

10 Example I:

Preparation of the di-n-hexyl ester of α-isopropyl-4-chlorobenzylphosphonic acid (process a) _

4.04 g (0.015 ml) of α-isopropyl-4-chlorobenzylphosphonic acid were dropped. dichloride in 12 ml of chloroform for 15 min., with stirring and at a temperature between 10 and 25 ° C, to a mixture of 3.06 g (0.03 mol) of 1-hexanol, 3.5 g of pyridine and 0, 77 g (0.0063 mol) of 4-dimethylaminopyridine and the reaction mixture thus obtained was stirred at room temperature for 18 hours. This reaction mixture was then poured onto ice, extracted with diethyl ether and the extract obtained was washed successively with water, twice with 1N sodium hydroxide, water, 6L sulfuric acid, water and a saturated aqueous sodium chloride solution, then dried over magnesium sulfate and evaporated. Chromatographing the obtained residue gave the title compound, n ^ = 1.4898. Example II:

The ethyl ester of N, N-diethyl-a- (2-butyl) -4-chlorobenzylphosphonic acid amide (method a).

6.18 g (0.02 mol) of the mono-chloride of the monoethyl ester of α- (2-butyl) -4-chlorobenzylphosphonic acid in 5 ml of 1,2-dimethoxyethane were added with cooling to a mixture of 4.7 g (0.064 mol) diethylamine, 2.45 g (0.02 mol) 4-dimethylaminopyridine and 5 ml 1,2-dimethoxyethane and the reaction mixture was stirred at room temperature for an additional 24 hours.

The reaction mixture was then taken up in diethyl ether, washed 790 80 74-4 with water and saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. Chromatographing the obtained residue gave the title compound in the form of a colorless oil, n = 1.5065. This compound is a mixture of diastereoisomers.

Example III;

The diethyl ester of a- (3-pentyl) -4-phenoxybenzylphosphonic acid (method b).

To 0.38 g (7.81 mMol) of a 50% dispersion of sodium hydride in 1.01 g (7.81 mMol) of diethylphosphite was slowly added in a nitrogen atmosphere. Under slight cooling, under development of hydrogen, a gray, thick paste was obtained, which was reacted with 2.0 g (6.0 mmol) of a- (3-pentyl) -4-phenoxybenzyl bromide. The reaction mixture was then stirred for a further 16 hours at 80 ° C. After cooling, a little water was added and the reaction mixture was extracted with diethyl ether. The extract was then washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. Chromatographing the obtained residue (50 g of silica gel with a mixture of equal parts of hexane and ethyl acetate) gave the title compound 20 '. as a colorless oil, n ^ 1.5293.

Example IV;

Preparation of the diethyl ester of α-1-sopropyl-4-25 chlorobenzylphosphonic acid (method c, monoalkylation) / the compound of formula 127 It was added dropwise to 4.32 g of 80% sodium hydride (0.144 mol) in 270 ml of dimethylformamide for 45 min and in a nitrogen atmosphere add a mixture of 34.5 g (0.131 mol) of the diethyl ether of 4-chlorobenzylphosphonic acid and 33.4 g (0.196 mol) of 2-iodopropane and the resulting suspension is stirred for another 20 hours at room temperature The mixture was then cooled slightly, 20 ml of water was added and extracted with diethyl ether, the ether extract was then washed in the back, then with water, twice with 1N sodium hydroxide, again with water and finally 790 8 0 74 15 with a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. The residue obtained "contained a mixture of the title compound and the diethyl ester starting material in a ratio of 60: U0, which mixture was stirred for 2 hours in 200 ml of a 5% solution of potassium hydroxide in a mixture of ethanol and water (9: 1) and the title compound, extracted with diethyl ether, as described above, to separate n * 1.5010 as an chromatographically pure, colorless oil.

10 Example Y:

Preparation of the diethyl ester of a-n-hexyl-2, U-dichlorobenzyl-phosphonic acid (method c, monoalkylation). / “Compound of formula 137 ·

31.5 ml of a 50 {S's (0.355 mol) of sodium amide suspension in toluene was added to 350 ml of toluene and this mixture was added, under gentle cooling, in a nitrogen atmosphere for 20 minutes, with stirring, to 105 g (0.355 mol) ) of the diethyl ester of 2, H-dichlorobenzylphosphonic acid. The resulting orange-colored suspension was then stirred for an additional 20 minutes.

He cooled to 5 ° C at 35 ° C, after which 58.6 g (0.355 mol) of 1-bromo-hexane was added for 25 min at a temperature between 5 and 15 ° C. After removing the cooling bath, the mixture was stirred for an additional 1 hour and 15 minutes, water was added and extracted with diethyl ether. The resulting extract was then washed with water and then a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. The resulting yellow oil was purified by chromatography (1 kg of silica gel with a mixture of hexane and ethyl acetate (7: 3)) to give the title compound in pure form ,30. = 1.50Uo.

Example VI:

Preparation of the di-n-butyl ester of α-isopropyl-1-chlorobenzylphosphonic acid and the di-n-butyl ester of α, α-diisopropyl-chlorobenzylphosphonic acid 35 (method e, mono and di-alkylation).

790 80 74 16 4

6.1+ g (0.02 mol) of the di-n-butyl ester of 1 + chlorobenzylphosphonic acid were added dropwise to 1.8 ml of a 50% (0.2 mol) sodium amide suspension in a nitrogen atmosphere and room temperature. in 2b ml of a mixture of equal parts of benzene and HMPT and then cooled the slightly warm mixture to 10 ° C. A solution of 5.1 g (0.03 mol) of 2-iodopropane in 5 ml of benzene was then added for 25 minutes at a temperature between 10 and 15 ° C, and after removing the cooling bath, the resulting reaction mixture was stirred for an additional 30 minutes.

The mixture was then cooled again, 20 ml of water was added and the resulting product was extracted with diethyl ether, after which the ether extract obtained was successively washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. After chromatographic separation 15 (200 g silica gel with a mixture of hexane and ethyl acetate 7: 3), the title compounds were obtained in pure form, the first with n ^ 1.1 + 91 + 2, the second with * 1.5075. Example VII:

The diethyl ester of a- (3-pentyl) - + - (3-pentyloxy) -20 benzylphosphonic acid (method c). monoalkylation).

105.8 g (0.337 mol) of the diethyl ester of 1 + - (3-pentyloxy) -benzylphosphonic acid at 3 ° C and in a nitrogen atmosphere were added within 20 min to 18.1+ g of solid sodium amide (50 # precipitate sodium amide suspension in toluene) 23 in 250 ml of dry toluene. 56 g (0.33 mol) of 3-pentylmethanesulfonate were then added. After removing the cooling bath, the temperature of the reaction mixture rose to 1 + 5 ° C (once 1 + 0 ° C was reached, the mixture was cooled a little more with an ice bath), dripping slowly and stirring until the reaction mixture had reached room temperature. After a reaction time of 1+ hours, the mixture was cooled, 50 ml of water was added and extracted with diethyl ether. The extract was then washed with water and then a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. Fractional distillation of the residue gave the 790 8 0 74 17 pure title compound, boiling point: 170 ° C / 0.08 mm

Hg.

Example VIII:

The diethyl ester of α, α-di-n-propyl-1 + - (2-butyl-5 oxv) benzylphosphonic acid (method c, di-alkylation).

3.00 g (0.01 mol) of the diethyl ester of U- (2-butyloxy) benzylphosphonic acid were added dropwise at 15 ° C to a solution of sodium methylsulfinylcarbanion in dimethylsulfoxide (freshly prepared by reaction of 1.50 g (0.031) mol) of a 50% T0 sodium hydride dispersion in oil with 15 ml of dry dimethyl sulfoxide at a bath temperature of 70 ° C, in a nitrogen atmosphere and stirring for 15 minutes). 5 min. Of ar, after cooling to 5 ° C, 3.80 g (0.031 mol) of 1-bromopropane were added dropwise, resulting in a vit precipitate. The cooling bath was then removed and the mixture was stirred for an additional 15 min., Water was added and extracted with diethyl ether. The extract obtained was washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. Chromatography of the obtained residue (50 g of silica gel with a mixture of hexane and ethyl acetate: 75-125) gave the title compound o® as an oil, n ^ * 1, ^ 9 ^ 9 ·

Example IX:

The diethyl ester of α, α-di-n-butyl-1 + -chloro-benzyl-phosphonic acid (process c, dialkylation).

25 Hg 3 ° C 8.1 hg (0.031 mol) of the diethyl ester of U-chlorobenzylphosphonic acid was added dropwise in a nitrogen atmosphere to 3.0 g solid sodium amide (precipitated portion of a 50% sodium amide suspension in toluene) in 2k ml of a mixture of equal parts of benzene and HMPT. After 35 min, 11.1+ g (0.062 mol) of n-butyl iodide were added at 30 ° C. After removing the cooling bath, the reaction mixture was stirred at room temperature overnight. Water was then added, the reaction mixture was extracted with diethyl ether, the extract was washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. By purifying the obtained yellow oil by chromatography 790 8 0 74 τ - 18 (100 g silica gel with a mixture of hexane and ethyl acetate 8: 2) and distilling »the title compound» boiling point: 138 ° C / 0.06 mm Hg.

Example X: 5 The diethyl ester of α- (1 + -chlorophenyl) -1-chlorobenzylphosphonic acid (method d).

13.6 g (0.05 mol) of di- (U-chlorophenyl) -chloromethane with 12.5 g (0.075 mol) of triethyl phosphite were first stirred in a nitrogen atmosphere at 160 ° C for 3 hours (oil bath temperature:

200 ° C) and then for 6 hours at a temperature between 160 and 172 ° C

(temperature of the oil bath 200-210 ° C). By chromatographic purification of the reaction mixture obtained (250 g of silica gel with a mixture of hexane and ethyl acetate: 7; 3), the 2 rf title compound was obtained, * 1.5508.15 According to the procedure of the suitable example I X, given above, using suitable starting materials, the following compounds of formula 1 have been prepared: 790 8 0 74 19 0) • o -d

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Example CLXXXIX:

The diethyl ester of U-chlorobenzylphosphonic acid (compound of formula 6).

U, 37 g (0.032 mol) diethyl phosphite was added to 0.95 g (0.032 nol) of an 80% sodium hydride dispersion in 25 ml in a nitrogen atmosphere, at the reflux temperature and for 25 min. 1,2-dimethoxyethane, after which the resulting mixture was stirred for an additional 1.5 hours. Thereafter, k.6k g (0.029 nol) 4-chloro-10 benzyl chloride in toluene was added dropwise to the mixture cooled to room temperature and the resulting mixture was then stirred at reflux for an additional 3 hours. After adding 0.30 g of the sodium hydride dispersion (at 45 ° C) and 2.0 g of diethylphosphite (at the reflux temperature), the reaction was completed by stirring the reaction mixture at 80 ° C for 18 hours. After cooling the reaction mixture, a little water was added and extracted with diethyl ether, the extract was then washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated. By chromatography of the residue thus obtained (100 g of silica gel with a mixture of equal parts of hexane and ethyl acetate), the title compound is obtained as a colorless oil with a boiling point between 100 DEG and 1 9 ° C / 0.1 mm. Hg.

Examples aimed at preparing preparations having a herbicidal action.

25 Example A:

A wettable powder.

25 parts by weight of a compound of formula 1.5 parts of a condensation product of formaldehyde and naphthalene sulfonate, 2 parts of an alkylbenzene sulfonate, 5 parts of dextrin, 1 part of ammonium caseinate and 62 parts of diatomaceous earth are mixed and this is ground. mixture then to an average particle size smaller than microns. Example Bi

Emulsion concentrate.

25 wt. parts of a compound of formula 790 80 74 β 30, 65 parts of xylene and 10 parts of the mixed reaction product of an alkyl phenol and ethylene oxide and calcium dodecyl benzene sulfonate until a homogeneous mixture was obtained.

The emulsion concentrate thus obtained is diluted before use.

Example C;

Granular preparation.

5 kg of a compound of the formula 1 were dissolved in 25 ml of methylene chloride. The solution thus obtained was then added to 95 kg of granular attapulgite (particle size 2 ± 28 / inch). The solvent was finally evaporated under reduced pressure.

9 790 8 0 74

Claims (19)

1¾ 1. Process for preparing a preparation of a herbicidal activity, characterized in that one or a number of compounds of the formula I, in which a hydrogen or halogen atom is represented, Yg is a hydrogen or halogen atom, an alkyl group with at at most 10 carbon atoms, alkoxy group with at most 10 carbon atoms, cycloalkyl group with 3 to 7 carbon atoms or cycloalkoxy group with 3 to 7 carbon atoms and Y ^ represents a hydrogen or halogen atom, a nitro group, a cyano group, an alkyl group with at most 10 carbon atoms, alkoxy group of up to 10 carbon atoms, C 8-6 alkoxyalkyloxy group, alkenyl group of 2 to 10 carbon atoms, alkenyloxy group of 2 to 10 carbon atoms, or alkylthio group of up to 10 carbon atoms, wherein any alkyl or alkenyl group or portion unsubstituted, * 15 or halogen-substituted -is, a benzyl, phenyl or phenoxy group, wherein each phenyl group or portion is unsubstituted or by at most 2 sub stituents selected from the group of halogen, nitro, cyano, alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, and / or alkylthio of up to 20 carbon atoms, each alkyl group or alkyl moiety being unsubstituted or halogen substituted, 0 represents a -COHRxRy, -CQRp, -COORp, -SRp, -SO ^ Rp, NRxRy, or -CH = N-ORp group or a group of formula 10 or 11, or wherein Yg ^ and Y3 are adjacent carbon atoms, and together form a methylenedioxy or ethylenedioxy group, each Rx and Ry substituent independently representing an alkyl group having at most 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms, or wherein Rx and Ry together with the nitrogen atom to which they are attached form a pyrrolidine, piperidine, N-methyl-piperazine or morpholme group, Rp a phenyl group or an unsubstituted alkyl group having up to 10 carbon atoms or a chlorine and / or fluorine-substituted alkyl group network is at most 10 carbon atoms and and Zg, independently, represent 0 or S, R ^ is a 35 790 80 74 * - unsubstituted alkyl group with at most 10 carbon atoms or a halogen-substituted alkyl group with at most 10 carbon atoms a cycloalkyl group of 3 to 7 carbon atoms which is unsubstituted or substituted by halogen, a 5 by alkoxy having 1 to 3 carbon atoms, phenyl or phenoxy, wherein phenyl or phenoxy is unsubstituted or by at most 2 halogen, alkyl of at most h carbon atoms, alkoxy of at most k carbon atoms and / or trifluoromethylsubstituents is substituted, monosubstituted alkyl group of at most carbon atoms, an unsubstituted alkenyl group of 2 to 6 carbon atoms or a halogen-substituted alkynyl group of 2 to 6 carbon atoms, alkynyl group with-2 to h-carbon atoms or phenyl group, which is unsubstituted or by at most 2 halo n, represents alkyl of at most H carbon atoms, alkoxy of at most 1 * carbon atoms and / or trifluoromethyl substituents, and Rg is a hydrogen atom or one of the meanings of R ^, or wherein R ^ and Rg together with the a carbon atom, a cycloalkylidene group of 3 to 7 carbon atoms, which is unsubstituted or is substituted by halogen and / or alkyl 20 with up to 4 carbon atoms, X independently represents 0, S or HR ,, R ^ a unsubstituted alkyl group with at most 8 carbon atoms, an alkyl group with at most 3 carbon atoms, alkylthio with at most 3 carbon atoms and / or halogen-substituted alkyl group with at most k carbon atoms, an alkenyl group with 3 to 6 carbon atoms, an alkynyl group with 3 through 6 carbon atoms, represents a tetrahydrofur-2-ylmethyl, tetrahydro-2H-pyran-2-ylmethyl, or cycloalkyl group, and R 1 and R 2, independently, have a meaning of R 1, or wherein R ^ and R ^, etc amen with the nitrogen atom to which they are attached form a piperidine, pyrrolidine, H-methylpiperazine or morpholine group, in a dosage form suitable for such use. 2. Process according to claim 1, characterized in that one or a number of compounds of formula 1b is used, wherein Yg 'represents a hydrogen or chlorine atom, Yg' represents a chlorine 790 8 0 74 or bromine atom, an alkoxy group of at most 5 carbon atoms, an alkenyloxy group of 3 to 5 carbon atoms or an alkyl group of at most 5 carbon atoms, "an unsubstituted alkyl group of 3 to 6 carbon atoms or a cyclo-5 alkyl group of 3 to 6 carbon atoms Rg 'represents a hydrogen atom or an unsubstituted alkyl group with at most ^ carbon atoms, X' is 0 or HR, - * and R ^ ', R ^' and R '', independently, are an unsubstituted alkyl group with 2 t / m U represent carbon atoms. Method for controlling weed species, characterized in that it is controlled with a preparation according to claim 1 or 2. Method according to claim 3, characterized in. that weeds are controlled in a field with cereals. Compounds of formula 1a, wherein V T2a · V BU> V ®3a "XAa (used in BjJ, the meanings indicated in claim 1 for, Yg, Y ^, R ^, Rg, and (including R ^) respectively, where, i) if Υ ^ &, Tga and Y ^ a represent a hydrogen atom, both OR ^ and XaR ^ a substituents represent the C18 ^ O or iC ^ H ^ O group and R ^ a the -CH ^, -CgH ^, -nC ^ H ^, -nC ^ H ^, -iC ^ H ^, allyl or benzyl group, Rga is not a hydrogen atom or an alkyl group having 2 to 5 carbon atoms, ii) if Y1 &, Yga » Y ^ a and Rga represent a hydrogen-25 atom and 0R ^ & and xaR ^ a both represent an alkoxy group with 2 to 5 carbon atoms, R1a is not a phenyl group, or iii) if Y1 &, Yg & and Rg & represent a hydrogen atom, Y ^ a a methyl or -0R ^ a group and X & R ^ a both represent a CgH ^ O group, Rla is not a methyl group and iiiiii) if Υ ^ &, Yga and Y ^ a represent a hydrogen atom, Rg represents the methoxymethyl group ® 0R ^ a and x £ Rjfa • both are the CgH ^ O group, R 1a is not a methyl group. Compounds according to claim 5, wherein ring A is substituted and wherein R 1, when this substituent is an unsubstituted alkyl group, represents an alkyl group having 3 to 6 790 80 74> 3U f 'carbon atoms. Compounds of formula 1b defined in claim 2. Compounds according to claim 7, wherein Y ^ '5 Η-Cl, R1' de 2-butyl, R ^ 'de ethyl, X'R ^' de N (CgH, _) g and Y2 'and Rg' represent hydrogen atoms. A compound according to claim 7, wherein the 1- (3-pentyloxy) group, R ^ T the 3-pentyl group, R ^ 'the ethyl group, -X'R ^' the ethoxy group and Y2 'and Rg' represent a hydrogen atom 10. A compound according to claim 7, wherein Yg 'is the (2-butyloxy) group, R ^' and Rg 'is the nC ^ H ^ group, -OR ^ * and -X'R ^' is the ethoxy group and Yg 'is a hydrogen atom introduce. A compound according to claim 7, wherein R 1 '15 lt-Cl, R 1' and Rg 'represent the n-C 1 -group, -OR 1' and -X'R 1 * the ethoxy group and Yg 'represent a hydrogen atom. 12. A compound according to claim 7, wherein Y ^ 'the U- (2-butyloxy) group, R ^ the 2-butyl group, -OR ^' and -X'R ^ 'the ethoxy group and Yg' and Rg ' represent a hydrogen atom. A compound according to claim 7, wherein Y2 'represents the U- (2-butyloxy) group, R ^' the cyclopentyl group, -OR ^ 'and -X'R ^' the ethoxy group and Yg 'and Rg' represent a hydrogen atom. 14. Method according to claim 1 or 2, characterized in that one or a number of compounds according to claims 5-13 are used. Method according to claim 1, 2 and 1, characterized in that a herbicidal carrier and / or diluent is also included in the preparation. 16. Process according to claim 3 or U, characterized in that a compound according to claims 5-13 or a preparation according to claim 1¼ or 15 is used. 17. Process for preparing an aromatic compound, characterized in that a compound according to claim 5 is prepared by preparing a) a compound of formula 1ea, 790 8 0 74 wherein Υ1 &, Yga, Υ ^ &, Rga » R ^ a and xa have the meaning, ie 5 have indicated meanings and R_ "has a meaning of R_ in claim 5 2a 2a, wherein R0" represents a hydrogen atom when X = 0 or L L HR ^ a, by a compound of formula 2a wherein Q1 represents a chloro-5 atom or OR3a and Y, a, Υ &, 1 ^, R, a> R2a ”and R? a have the meanings indicated above, with a compound of formula 3a, wherein X & and R ^ a have the meanings indicated in claim 5 and M is a hydrogen atom if X - 0 or NR ^, wherein R_ has a meaning as defined in claim 5, or 10 represents an alkali metal cation if X is a sulfur atom, a or b) Preparation of a compound of formula 1da, wherein Y ^ a, Y2a, Y ^, Rga and the meanings set forth in claim 5 have either R1 represents an unsubstituted alkyl-1a TTT 15 group having up to 10 carbon atoms and R_ represents a hydrogen III III atom, either both substituents R1a and Rga represent a phenyl group or a substituted phenyl group, by a compound of formula Ua, wherein Y, Y_, Y_, R1 and R_ x have the meanings indicated above and Q_ is a 2a 2 20 halogen, to react with a compound of formula 5a, wherein X &, R ^ a and R ^ a have the meanings indicated above, or c) preparation of a compound of formula 1ea, IY XY wherein R, and R0 have the meanings of ia 2a jy jy indicated above R1a and Rga have wherein both substituents R1a and Rga represent a phenyl group or a substituted phenyl group, X ^ 1 * 0 or ®5a and Y1a, Y2a, Y3a, R3a, Ela and? 5a have the meanings indicated above, by mono- or di-substitute a compound of formula 6a, in which R 1 represents a hydrogen atom, a phenyl group or a substituted α a 30 phenyl group and X & xYia * Y2a> Y3a &quot; R3a and R i * a have the meanings indicated above. one or two compounds of formula 7ab, wherein R ^ a has a previously indicated meaning of R ^ a, which is not a phenyl or substituted phenyl group and represents a cleavable group 35, or with a compound of formula 7aa, wherein Rga is a 790 80 74 t represents unsubstituted alkylene group of 2 to 6 carbon atoms or an alkylene group of 2 to 6 carbon atoms substituted by halogen and / or alkyl of at most U carbon atoms and has the meaning indicated above, or d) preparation of ve compounds of the formula 1fa, 7. ii wherein »Yia * Y2a» ^ 3 ^ »R3a and Rija have the meanings indicated above and B, v is a methyl, phenyl or substituted ia phenyl group, by a compound of formula 8a, wherein Q . a . v ** is halogen and Y1ft, Y2a, Y ^ ft and R1a have the meanings indicated above, to react with a compound with 1U. II. formula 9a, in which R ^, RJ | a and X have the meanings indicated above. 18, Methods as described in the description and / or examples. ^ T9. Herbicidal molded compositions obtained by a method according to claims 1, 2, 1U, 15 and 16. 790 8 0 74. * κ Improvement of errata in the description associated with patent application No. 79-08074 Ned. proposed by Applicant dd. November 9, 1979 Page 1, line 23: after "carbon atoms" add: "is substituted", page 6, line 10: insert between "of" and "Y ^": ΙΙττ V 11 Γ 2 'Page 20, Example XXXIV: below Rj "-CH ^" should be "-0 ^ 1" and page 30 ,. line 9: "ml" must be "1". .f S ^ hut / RR 790 80 74