DE2944598A1 - PHOSPHONIC ACID ESTER DERIVATIVES - Google Patents

Description

as; ierbicid,

wherein Y. hydrogen or halogen (advantageously chlorine, bromine or

Fluorine, preferably chlorine),
Y hydrogen, halogen, (advantageously chlorine, bromine or fluorine,

preferably chlorine), (l-lOC) -alkyl, (l-lOC) -alkoxy, (3-7C) -

Cycloalkyl or (3-7C) -cycloalkoxy and Y_ hydrogen, halogen (advantageously chlorine, bromine or Fluorine, preferably chlorine), nitro, cyano, (l-lOC) -alkyl, (l-lOC) -alkoxy, (2-10C) -alkoxy-alkyloxy, (2-10C) -alkenyl, (2-10C) -alkenyloxy or (l-10C) -thioalkyl, where each alkyl or alkenyl radical or a part of these alkyl or alkenyl radicals are unsubstituted or substituted by halogen (advantageously chlorine and / or fluorine) are; also Y benzyl, phenyl or phenoxy and each of these phenyl radicals or some of these phenyl radicals are unsubstituted are or are substituted by one or two substituents and the substituents of the above Phenyl radicals halogen (advantageously chlorine, bromine or fluorine, preferably chlorine), nitro, cyano, (1-6C) -alkyl, (1-6C) -alkoxy, (1-6C) -thioalkyl, and each of these alkyl radicals or parts of these alkyl radicals are unsubstituted are or by halogen (advantageously chlorine and / or

030021/0736

2SU598

Case 130-3S66

Fluorine) are substituted; Ί V- R _p , -SO ₂ -Rp, -NR _x R _y ,

o also -CONR R, -COR, -COOR,

^{J x} ypp

-CH = N-OR, P.

or

-CH

means,

or the two radicals Y ~ and Y-, if they are attached to adjacent C-

Atoms in ring A are bound, together can form a methylcndioxy or ethylenedioxy group,

wherein R and R independently of one another in each case (l-iOC) -alkyl or χ y

(3-10C) -alkenyl, or R and R together form with the N atom attached to it a pyrrolidine, piperidine, morpholine or N-methylpiperazine ring,

in which R is in each case phenyl, an unsubstituted (l-lOC) -alkyl radical or a (l-10C) -alkyl radical substituted by chlorine and / or fluorine

and Z and Z "each independently represent 0 or S, wherein R. is an unsubstituted (l-lOC) -alkyl radical or a

(i-10C) -alkyl radical substituted by halogen (advantageously chlorine or fluorine); an unsubstituted (3-7C) -cycloalkyl radical or one by halogen (advantageous Chlorine) substituted (3-7C) cycloalkyl radical; a (1-4C) -alkyl radical which is replaced by a (1-3C) -alkoxy group is substituted by a phenyl or a phenoxy radical, and the phenyl or phenoxy radicals are unsubstituted or substituted by

"Or 2 substituents are substituted and. these. jJubstituenten

Halogen (advantageously chlorine), (1-AC) -alkyl, (1-4C) -alkoxy or are trifluoromethyl; an unsubstituted (2-6C) -

Alkenyl radical or a (2-6C) -alkenyl radical substituted by halogen (advantageously chlorine); a (2-4C) alkynyl radical; an unsubstituted phenyl radical or one through one or two substituents substituted phenyl and these substituents halogen (advantageously chlorine), are (l-AC) -alkyl, (1-4C) -alkoxy or trifluorocethyl and

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_ 12 - ΊΖ Case 130-3866

R _{9 is} hydrogen or one of the meanings of R is, or

wherein R and R. together with the a-C-atom attached to them form an unsubstituted one (3-7C) -cycloalkylidene or one substituted by halogen, advantageously chlorine, or (1-4C) -alkyl (3-7C) -cycloalkylidene ring can form,

wherein X 0, S or -NR ₅ ,

R is an unsubstituted (1-8C) -alkyl radical, one by one (1-3C) -alkoxy, (1-3C) -thicalkyl or halogen (advantageously chlorine or fluorine) substituted (1-4C) -alkyl radical; (3-6C) alkenyl; (3-6C) alkynyl; Tetrahydrofur-2-yl-.T.ethyl, tetrahydro-2H-pyran-2-yl-rcethyl or (5-6C) -cycloalkyl,

where R. and R_ either have one of the meanings of R or R, and R- can together with the N-Atoc bound to them Piperidine, pyrrolidine, morpholine or N-methylpiperazine ring form.

The subject matter of the invention accordingly includes a method for combating weeds on the spot, which is characterized in that an effective weed-killing amount is available at the relevant location or site a compound of formula I applies.

The compounds of formula I exhibit a wide range of unkrautvertilgender efficacy against both monocotyledon Unkäuter as Apera spica venti, Alopecurus myosuroides, Echinochloa crus-galli, Avena fatua or Agrostis alba, as well as against dicotyledonous weeds such as Amaranthus re_tr £ flexus, Capsella bursa-pastoris , Chenopodium alba , Galiun aparine , Senecic vulgaris or Stellaria media , such as treatments in greenhouses after the pre- and post-emergence (procedure) have shown.

The amounts of this test compound correspond to 0.2; 1.0 and 5.0 kg of active Active substance per hectare of the treated surface.

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- 13 - W Case 130-3866

The determination of the herbicidal effect is made after a 28-day treatment time. While the test is being carried out, the driving or Greenhouse kept at a temperature of 20 ° up to 24 ° C and exposed to daylight for 14 to 17 hours per day. On the other hand, however, show Active substances have no significant or perceptible damaging effect or disadvantage under the greenhouse test conditions mentioned compared to arable fruit, such as grain, e.g. wheat, barley, rye or maize, carrots, sunflowers and soybeans, whereby this test was carried out with quantities of 5.0 kg per hectare of active substance at the location of the grain production.

Accordingly, the compounds are also suitable for selective monitoring in the control of weeds in arable farming, such as in cereals, e.g. B, wheat, barley, rye and corn, carrots, sunflower and soybeans.

The amount of a compound of the formula I which must be used in order to Achieving the desired effect in order to be perceived depends on the plant in question, on the location and area to be treated and on other variables, such as on the compound used, on the method of application , treatment conditions, etc.

However, in general, complete weed control can be satisfactory can be obtained when the compound is in an amount ranging from about 0.5 to 6 kg per hectare is used, especially between 1 to 4 kg per hectare of the treated area.

The connections are beneficial after post-emergence Procedure used.

For selective herbicidal use, such as in the aforementioned agriculture, the amount of the compound should be chosen so that a maximum of Weed destruction is ensured, but with a minimum of

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29U598 / ft

- 14- 'Π Case 130-3866

disturbance or damage to the grain culture. Generally will obtain satisfactory results for selective weed control, if the connection is in a narrow range of 0.5 to 4 kg per hectare, advantageous between 1.0 and 3 kg per hectare is used.

The connection is beneficial after post-emergence the weeds, but especially after emergence of both the weeds as well as applied to grain.

In general there is a fairly rapid onset of activity of the compounds to observe.

The compounds can be used as such, but generally are especially used as herbicidal compositions in conjunction with suitable carriers, diluents, extenders! or tools used. Such compositions also form part of the present invention.

The herbicidal compositions can be in solid or liquid form. Solid forms, e.g. as dust and granulate forms, can be produced by mixing or impregnating solid herbicidal carriers or Extenders such as diatomaceous earth, kaolin, chalk, talc, limestone or celulose powder, with the connections.

Examples of auxiliaries which are contained in the compositions can be taken from the range of wetting and dispersing agents, e.g. condensation products of formaldehyde with naphthalene sulfonate and Alkyl benzene sulfonates, strength-imparting agents, binders such as dextrin, and emulsion stabilizers such as aromonium caseinate. Such Aids are suitable for incorporation with e.g. wettable forms of powder compositions or for use together with suitable solvents, e.g. hydrocarbons such as benzene, toluene, xylene, tetrahydronaphthalene, alkylated naphthalenes, kerosene, aromatic petroleum

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- 15 - "" ^ Case 130-3866

carbon fractions (e.g. the commercial product Shellsol AB with a boiling point in the 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 of trichlorethylene, to enulsified Form concentrations.

The herbicidal compositions can, in addition to the compound of the formula I contain as active ingredient, other active agrochemical agents, such as other herbicides.

Concentrated forms of the compositions generally contain between 2-80%, advantageously between 5 and 70% percent by weight of the compound of the formula I as the active ingredient.

Application forms of the compositions generally contain between 0.01 up to 10 percent by weight of the compound of formula I as active ingredient.

Specific examples of herbicidal compositions are given below listed.

In the compounds of the formula I, the ring A advantageously contains at least a substituent.

The compounds of the formula Ia are new and form part of the present invention.

The compounds of the formula Ia correspond to the formula Ia

Yes,

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Ai

- 16 - Case 130-3866

where Y _la> Y _2a , Y ₃₃ . R ₁₃ , R ^, R ₃₃ and X ₃ R ₄₃ (R ₅₃ not included) have the meanings of Y., Y-, Y-, R. » R- »^ 3

and XR. (R _r included) have 4 5

with the proviso that

α) if Y, Y "and Y. are hydrogen, and both 'la 2a 3a

OR ₃₃ and also X _a ^R _Aa ^c ₂ ^H 5 ° ° ^der - ~ ^C 3 ^H 7 ° ^{And R} ia ^CH 3 * ^C 2 ^H 5 * nC H, JJ-CH, rC, H, allyl or benzyl mean, then

R is not hydrogen or (2-5C) -alkyl,

^ et

ß) if Y _n , Y_, Y_ and R stand for hydrogen, and

both 0R "and also XR. (2-5C) -alkoxy mean then 3a «a

R is different from phenyl, or la

V) if Y ₁ , Y- and R are hydrogen and Y are methyl, and both OR and also XR, CJO, then R is different from !! ethyl, or

(f) if Y ₁ , Y ₀ and Y for hydrogen and R for Me-

X3 t- & J3 fc «

thoxjTnethyl stand, and both OR and also X R, CXO then R is different from !! ethyl.

If the ring A is three times substituted, it is advantageously trichloro substituted. The ring A is preferably mono- or di-substituted.

Examples of substituted alkyl radicals in the meaning of Y are CF and CH-CH-Cl. Examples of substituted alkoxy radicals in the meaning of Y ₃ are -OCF ₃ , -OCHF ₂ , -OCF Cl, -O-CH -CH Cl or -O-CF -CHF. As an example of a substituted alkenyl radical in the meaning of Y is -CH = CCl. An example of a substituted thioalkyl radical in the meaning of Y_ is -SCF.

Such radicals are also suitable examples of the corresponding groups as Substituents in each phenyl or phenoxy group in the meaning of Y-.

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- 17 - '' Case 130-3866

If R _{1 is} an unsubstituted alkyl group, they advantageously contain 3 to 6 carbon atoms. If R ₁ and R are the same and are unsubstituted alkyl radicals, then they are advantageously n-propyl, jH-propyl or n-butyl.

If R and R »are different from one another and R« is hydrogen or a primary (1-AC) -alkyl radical, then R is advantageously branched in the α-position and is in particular _i_-propyl, sec- butyl, 3-pentyl, 2-pentyl, 3-hexyl, cyclohexyl or cyclopentyl.

The particularly preferred meaning of X in the compounds of the formula I.

is 0 and -NR .. R. and R_ in dei 5 4 5

rests is a (2-6C) -alkyl radical.

is 0 and -NR. R and R mean an unsubstituted alkyl

A particularly preferred class of compounds of the formula I are those To name compounds of the formula Ib,

Ib)

where Y .. ^{1 is} hydrogen or chlorine,

Y ₃ ¹ chlorine, bromine, (1-5C) -alkoxy, (3-5C) -alkenyloxy or

(1-5C) -alkyl, R. ^{1 is} an unsubstituted (3-6C) -alkyl radical or (3-6C) -CyC-

loalkyl, R- * hydrogen or an unsubstituted (1-4C) -alkyl radical,

X ¹ 0 or NR 'and

R ', R' and R 'each independently represent an unsubstituted (2-4C) -alkyl radical.

If Y 'and Y ₃ ^{1 are} chlorine, the two chlorine atoms are advantageously in the 2- and 4-positions.

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- 18 - 'Case 130-3860

The compounds of formula I can be obtained

a) in the event that compounds of the formula Ic are to be prepared

^R · »

^Y 3
wherein Y, Y, Y-, R, R, R, and X have the meanings given above

have and

R ″ has the meaning given above for R, with the proviso that R ″ stands for hydrogen when X is O or NR means, where R has the meaning given above,

if you have a compound of formula II

"7 ^^ \ · il ^ ^U1

II,

R "1

wherein Q _{1 is} chlorine or OR,

and Y, Y, Y, R, R "and R have the meanings given above,
with a compound of the formula III

R, XM III,

wherein X and R have the meanings given above,

implements, and

where M is either hydrogen,

if X is 0 or NR,

or M is an alkali metal cation (advantageously sodium) when X is sulfur,

or
b) in the event that compounds of the formula Id) are to be prepared

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- 19 - Case 130-3866

R ₁ ¹ "O OR"

¹ W ^ ³

wherein Y, Y, Y, R and XR have the meanings given above, and either R '"is an unsubstituted (l-lOC) -alkyl radical and R'"

Mean hydrogen, or

and R ^Ml both stand for phenyl radical,

R "'and R ^Ml both represent the phenyl or a substituted one

if you have a compound of formula IV

Q,

'2ΛΥ7 _R , "

* 3

where Y, »Y-» * »» R. " ¹ and R" ^{1 have} the meanings given above

and Q ₉ for halogen (e.g. chlorine or bromine, advantageous for bromine)

stands,

with a compound of the formula V,

Na-O-P V,

wherein X, R and R. have the meanings given above, implements, or c) in the event that compounds of the formula Ie are to be prepared

-C — P ^ Ie,

^y 2 ^ y i-

^Y 3

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- 20 - 4 ^ Case 130-3866

29Λ4598

where R "" and R "" have the meanings of R and R with the proviso that both R "" and R "" do not mean phenyl or substituted phenyl,
X "represents O or NR

and Y, Y, Y, R, R and R have the meanings given above own,

by mono- or di-substitution of a compound of the formula VI

VI,

wherein R, is hydrogen, phenyl or substituted phenyl

and X ", Y ₁ , Y", Y-, R_ and R have the aforementioned meanings 1 2. J j 4

own,
with one or two compounds of the formula VII

R ₇ Q ₃ VII,

where R has the meaning given above for R, with the proviso that P. is not phenyl or substituted phenyl and Q stands for a removable group, such as bromine, iodine, mesyl

oxy or tosyloxy, (CH ^ SO- or CH or with a compound of the formula VIIa

Q ₃ -R ₈ - Q ₃ Vila,

wherein R is unsubstituted or by halogen, advantageous Chlorine, or (2-6C) -alkylene radical substituted by (1-4C) -alkyl stands

and Q has the meaning given above, or

d) in the event that compounds of the formula If are to be prepared

Y ₁ /. S ₁ '"" 0 OK,

"3

wherein X ", Y, Y, Y, R_ and R, have the meanings given above

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21 - \ Λ Case 130-3366

29-598

and κ "represents methyl, phenyl or substituted phenyl, if you have a compound of formula VIII

wherein Q 1 is halogen (e.g. iodine, chlorine or bromine) and Y, Y, Y and R "'" has the meanings given above, with a compound of the formula IX

R-O-P IX,

wherein R., R, and X "has the meanings given above, implements.

The aforementioned conversions or reactions can be carried out by methods known per se.

If Q in process a) is chlorine, the reaction is advantageously carried out in such a way that 2 mol of a compound of the formula III are mixed with 1 Reacts mol of a compound of the formula II.

If in the process according to a) the compound of formula II with a Amine or alcohol is reacted, the reaction is advantageous in the presence a tertiary amine such as pyridine or triethylamine and mostly carried out in the presence of catalytic amounts of an acylation accelerator such as para-dimethylaminopyridine.

In general, the compound of the formula II, which is usually dissolved in a solvent, such as, for example, in CH "C1", 1,2-dichloroethane, benzene, toluene, xylene, glyme (1,2-dimethoxyethane), diglyme [ CH (OCH CH) OCH] or in an excess of R, XH, at a temperature of 0 to 30 ³ C to a mixture of the amine or alcohol reaction product, the tertiary amine and a suitable acylation accelerator, and the reaction carried out stirring at 20 to 140 ⁰ C, preferably at room temperature, over a period of 1 to 18 hours completed. In the event that an amine is reacted, ethers and hydrocarbons are used as advantageous reaction media.

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- 22 - ^^ Case 130-3866

If it is implemented in the method according to a) the compound of formula II with an alkali metal thiolverbindiing, the reaction is carried advantageously at a temperature of 0 to 30 ⁰ C in an ether or a hydrocarbon as solvent, such as in glyme, diglyme, Benzene, toluene, xylene or in CH Cl, preferably in the presence of a phase transfer catalyst, such as, for example, benzyl-trimethylammonium bromide, or in a dipolar solvent, such as, for example, dimethylformamide. Process a) is particularly suitable for the preparation of compounds of the formula I ₁ in which either X is S or XR, part of a primary alcohol R, OH or an amine of the formula HNR R, in which the α-carbon atoms of R, and R are unbranched.

A suitable process b) is carried out in a solvent such as glyme or toluene, expediently under the condition of the reflux temperature or in dimethylformamide or HMPT (hexamethylphosphoric triamide) or in a solvent mixture at room temperature, for example in toluene / HMPT. However, the reaction can be carried out of a solvent at temperatures of 20-120 ⁰ C in the absence. A suitable reaction time, with or without a solvent, is between 0.5 and 18 hours. Process b) is advantageously used for the preparation of compounds of the formula I in which R. and R are phenyl or substituted phenyl or in which R is unsubstituted (l-10C) -alkyl and R is hydrogen. In such cases, Q "advantageously stands for bromine.

In process c), in which, if desired, a compound of the formula Ie, in which R "" represents hydrogen or R "" and R "" are connected is to be carried out, the reaction is advantageously carried out so that the compounds of the formula VI and those of the formulas VII or VIIa are in a molar ratio of 1: 1. In the event that one is desired Compound of formula Ie is prepared wherein R "" is different from hydrogen and is different from R ″ ″, the reaction is advantageously carried out in two stages; in a first stage the connection is the Formula VI with one of the compounds of the formula VII (in a 1: 1 molar ratio

030021/0736

ratio) and, in a second stage, the reaction product obtained in this way reacted with another compound of formula VII.

In process c), in which, if desired, the compound of the formula VI is reacted with one mole of a compound of the formula VII or VIIa, the reaction is mainly carried out in the presence of a base, such as, for example, sodium hydride, and in a solvent, such as glytne, dimethylformamide, dimethylsulphoxide ( DMSO), ICIPT or toluene or in a solvent mixture such as toluene / HMPT. The suitable reaction temperature is from 0-80 ⁰ C and the appropriate reaction time of 1/4 to 18 hours. The separation of the obtained reaction products from remaining unreacted compound of the formula VI is carried out of the latter mainly by chromatography or by selective hydrolysis, for example by treatment with an ethanolic-aqueous (9: 1) 5% Kaliurahydroxydlösung at 20-80 ⁰ C for 2 to 18 hours.

If desired, instead of sodium hydride, a stronger base, such as Sodium amide, can be used to lower the reaction temperature and / or shorten the response time.

In process c), in which, if desired, the compounds of the formula VI are to be dialkylated (as described above), the reaction is advantageously carried out in the presence of at least two equivalents of a strong base, such as sodium methylsulphine carbanion, dissolved in DMSO or DMSO / toluene or of sodium amide in an organic solvent, as previously described, or in liquid ammonia.

If the reaction is carried out in an organic solvent, a suitable reaction temperature is from -10 ° to 45 ° C for 5 to 60 minutes, anschli.essend, if necessary, while is stirred for 30 minutes to 24 hours at 25 to 70 ⁰ C. . Any mixture of the disubstituted product with the monosubstituted product can be separated chromatographically.

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ZH

Case 130-3866

29U598

Is used as a base for the case that sodium llethylsulphinylcarbanion, this carbanion is to be freshly prepared, by reaction of sodium hydride with an excess of dried Dimethylsulphoxyd at 70 ⁰ C. bath temperature under nitrogen atmosphere and stirring for 45 to 60 minutes. In the event that sodium amide is used as the base, the reaction is advantageously carried out in the presence of an equivalent amount of hexamethyldisilazane. The latter method is particularly useful when steric hindrance occurs.

The process according to d) is expediently carried out by heating a mixture of the reactants, generally advantageously in the presence of potassium iodide and at temperatures from 60 to 200 ^° C. The reaction is then advantageously brought to an end by stirring the reaction medium for 5 minutes to 8 hours and a temperature of 60 to 210 ° C, preferably for 30 minutes at about 160 ⁰ C.

However, in the event that the compound of the formula VIII is diphenylchloromethane or para-nitrobenzyl halide, the reaction is expediently carried out in the absence of potassium iodide, but using a compound of the formula VIII in which Q is chlorine or bromine. If R is methyl, Q is advantageously iodine. If R _{1 is} phenyl or substituted phenyl, Q is advantageously chlorine.

The compounds of the formula I obtained can be prepared by known methods isolated and cleaned.

Processes a), b), c) and d), provided they are used for the preparation of compounds Serving the formula Ia are also part of the present invention.

In order to indicate in the process claims that the processes according to a), b), c) and d) are used to prepare the new compounds of the formula Ia, see above

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Case 130-3S6C

29U598

the substituents in the corresponding formulas are rait "a", e.g. R,

1.3

X 'etc. denotes,
a

The starting compounds used in the above processes are either known or can be prepared from suitable starting compounds by known methods. For example, the Compounds of the formula VI conveniently obtained by means of processes b) or d) will.

It should be noted that the mutual transformation of a compound of Formula I can be converted into another compound by a known method.

It should also be noted that the compounds of the formula I are asymmetrical Have centers if R and R are different from one another, or if XR, and OR are different from one another; any of these connections therefore comes in the optically active, diastereomeric or racemic Shape before. It should be noted that the present invention is not limited to any one of these forms.

In the following examples, the parts are parts by weight and the temperatures are given in degrees Celsius.

Example 1 (method a)

Process for the preparation of dijrt-hexyl α-isopropyl-4-chlorobenzylphosphonic acid

4 »04g (0.015ml) a-Isopropyl ^ -chlorobenzylphosphonic dichloride, dissolved in 12 ml of chloroform are added dropwise over 10 minutes at 10-25 ° with stirring to a mixture consisting of 3.06 g (0.03 ml) of 1-hexanol, 3.5g pyridine and 0.77g (0.0063 mol) 4-dimethylaminopyridine, added and

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ORIGINAL INSPECTED

, 26th

- / b - Case 130-3S6G

29U598

the whole mixture was stirred for 18 hours at room temperature.

The reaction product is then unloaded onto ice and extracted with ether and the ether extract one after the other with water, twice with IN KaOH, Water, 6N H SO, water and one saturated with sodium chloride aqueous solution (here called "Brine") washed, then with magnesium sulfate dried and the ether evaporated. The residue will

20th

purified by chromatography to give the title product with n = 1.4898.

Example 2 (method a)

N, N-diethyl-a- (2-butyl) -4-chlorobenzylphosphonic acid amide ethyl ester

6.18g (0.02 mol) o- (2-butyl) -4-chlorobenzylphosphonic acid monoethyl ester monochloride, dissolved in 5ml 1,2-dimethoxyethane, are cooled to a mixture of 4.7g (0.064 mol) diethylamine, 2.45g (0.02 mol) 4-dimethyiaminopyridine and 5 ml of 1,2-dimethoxyethane were added and the reaction mixture was stirred for 24 hours at room temperature.

The mixture is then taken up with ether, washed with water and "brine", dried over magnesium sulphate and the ether is distilled off. The residue is purified by chromatography, the title product as a colorless oil
mere mixture.

colorless oil with η = 1.5065 is obtained. The product is a diastereo-

Example 3 (method b)

a- (3-Pentyl) -4-phenoxybenzyl-phosphonic acid diethyl ester

To 0.38 g (7.81 m mol) of a 50% sodium hydride dispersion in oil slowly and under a nitrogen atmosphere 1.07 g (7.81 mol) of diethyl phosphite admitted.

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Case 130-3866

With slight cooling one obtains, with evolution of hydrogen, a gray, thick paste, which with 2.0 g (6.0 m mol) of a- (3-pentyl) -4-phenoxybenzyl bromide is implemented.

The reaction mixture is then stirred at 80 ° for 16 hours. To After cooling, a little water is added to the product obtained and the product extracted with ether. The extract is washed with water and "brine", dried over magnesium sulfate and the ether is evaporated. - Of the The residue is chromatographed (50 g of silica gal with hexane / ethyl acetate in a ratio of 1: 1), the title product being colorless

20th
OeI with η = 1.5293 is obtained.

Example k (method c)
Monoalkylation

Process for the preparation of disethyl α-isopropyl-4-chlorobenzylphosphonate the formula

To 4.32 g of 80% sodium hydride (0.144 mol), dissolved in 270 ml of dimethylformamide, are added dropwise over a period of 45 minutes and under a nitrogen atmosphere, a mixture consisting of 34.5 g (0.131 mol) of 4-chlorobenzylphosphonic acid diethyl ester and 33.4g (0.196 mol) 2-iodopropar., added. The suspension obtained is at room temperature for 20 hours touched . The reaction mixture is then cooled slightly, 20 ml of water are added and the mixture is extracted with ether.

The ether extract is successively mixed with water, twice with IN sodium hydroxide, washed again with water and then with "brine". It is then dried with magnesium sulphate and the ether is then evaporated off. . The residue, consisting of a mixture of the title product

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- y & - Case 130-3860

29U598

tes together with the diethyl ester starting material in a ratio of 60:40 is subjected to treatment for 24 hours with stirring. This treatment is in 200ml of a 5% potassium hydroxide solution in carried out a 9: 1 mixture of ethanol / water, the title product being isolated with the aid of an ether extraction as described above becomes and after a chromatographic purification as colorless

20th
OeI with η = 1.5010 is obtained.

Example 5 (process cn c)

Monoalkylation

Process for the preparation of a-n-hexyl-2,4-dichlorobenzylphosphonic acid diethyl ester

ⁿ " ^C 6 ^H 13

31.5 ml of a 50% strength (0.355 mol) of a sodium amide suspension in toluene are added to 350ml of toluene; this mixture becomes with a moderate cooling in the course of 20 minutes under nitrogen atmosphere and stirring 105 g (0.355 mol) of 2,4-dichlorobenzylphosphonic acid diethyl ester admitted.

The orange colored suspension obtained is at 35 ° for 20 minutes stirred further, then cooled to 5 ° and then, in the course of 25 minutes at 5-15 °, 58.5 g (0.355 mol) of 1-bromohexane were added.

After removal from the cooling bath, the reaction product is used for further Stirred for 1 1/4 hours, then treated with water and extracted with ether. The ether extract is then washed with water and then with "brine" and then dried with magnesium sulphate and the ether evaporated. The yellow colored oil obtained is purified by chromatography (using a

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- 29 - * 'Case 130-3866

lkg silica gel column with hexane / ethyl acetate 7: 3), whereby the title pro-

20th
product is obtained in pure form with η = 1.5040.

at game 6 (method c)

Mono- and dialkylation

Process for the preparation of α-isopropyl-4-chlorobenzylphosphonic acid din-butyl ester and ", a-Diisopropyl-A-chlorobenzylphosphonic acid di-n-butyl ester

6.4 g (0.02 mol) of 4-chlorobenzylphosphonic acid di-n-butyl ester are in a Nitrogen atmosphere and at room temperature dropwise to 1.8 ml of a 50% strength (0.2 mol) sodium amide suspension in 24 ml benzene / HMPT (1: 1) given and the slightly warmed mixture cooled to 10 °.

In the course of 25 minutes, a solution between 10-15 ° is then grounded of 5.1g (0.03 mol) of 2-iodopropane, dissolved in 5 ml of benzene, added and, after after removal from the cooling bath, the reaction product was stirred for a further 30 minutes. The mixture is cooled again, 20 ml of water are added and then extracted with ether.

The ether extract is washed with water and "brine" over magnesium sulfate dried and then the ether evaporated. After a chromatographic purification (200g silica gel with hexane / ethyl acetate 7: 3), he

The pure title compound is kept, the unpurified one having η = 1.4942

20th
and the purified one has η = 1.5075.

Example 7 (Method c)

Monoalkylation
a- (3-Pentyl) ~ 4- (3-pentyloxy) -benzylphosphonic acid diethyl ester

Within 20 minutes, 105.8 g (0.337 mol) of 4- (3-pentyloxy) -ben-

030021/0736

Case 130-3866

zylphosphcnsäure diethyl ester at 3 ° and under a nitrogen atmosphere 18.4 g of solid sodium amide in 250 ml of absolute toluene were added. (The sodium amide is obtained by precipitating a 50% sodium amide suspension in toluene.)

Then 56 g (0.33 mol) of 3-pentyl methanesulfonate are added.

After the reaction mixture has been removed from the cooling bath, the increases Reaction temperature to 45 ° and then slowly drips with stirring until room temperature is reached. If the reaction temperature Has reached 40 °, the reaction vessel is easily washed with an ice bath chilled.

After a reaction time of 4 hours, the mixture is cooled, 50 ml Added water and then extracted with ether. The extract is then washed with water and "brine" and dried over magnesium sulfate and evacuated.

After fractional distillation of the residue, the pure titanium is obtained tel compound at a boiling point of 170 ° and 0.08 ram Hg.

Example 8 (method c)

Dialkylation

α, o-Di-ji-propyl-4- (2-butyloxy) -benzylpliosphonic acid diethyl ester

To a solution of sodium methylsulphinyl-carbanion in dimethylsulphoxide (freshly prepared by reacting with stirring and in a nitrogen atmosphere of 1.50 g (0.031 mol) of a 50% strength sodium hydride dispersion in oil In the course of 45 minutes with 15 ml of absolute dimethyl sulphoxide at a bath temperature of 70 °, 3.00 g (0.01 mol) of 4- (2-butyloxy) benzylphosphonic diethyl ester are added dropwise at 15 ° admitted. After 5 minutes and cooling to 5 °, 3.80 (0.031 mol) of 1-bromopropane are added dropwise, whereupon a white precipitate is formed. The cooling bath is shaken and

030021/0736

% Ί Case 130-3866

the mixture is stirred for 15 minutes, then water is added and the mixture extracted with ether.

The ether extract is washed with water and "brine", dried over magnesium sulfate and evaporated.

The residue is purified by chromatography (50g silica gel with hexane /

20th

Ethyl acetate 75:25) whereby the title product is obtained as an oil with η = 1.4949.

Example 9 (method c) Dialkylation

α, a-Di-n-butyl-A-chlorobenzylphosphonic acid diethyl ester

In a nitrogen atmosphere at 3 ° 8.14 g (0.031 mol) of diethyl 4-chlorobenzylphosphonate are added dropwise to 3.4 g of solid sodium aramid (produced by precipitating a 50% sodium amide suspension in toluene) in 24ml benzene / HMPT (1: 1) added.

In the course of 35 minutes, 11.4 g (0.062 mol) of n-butyl iodide are then added at 3 °. After the cooling bath has been removed, the reaction mixture is stirred further overnight at room temperature. Thereupon becomes water added, the reaction product extracted with ether, the ether extract washed with water and "Brine", dried over magnesium sulfate and then the ether evaporated.

The yellow oil obtained is purified by chromatography (100 g silica gel with hexane / ethyl acetate 8: 2) and distilled, the title compound being obtained at a boiling point of 138 ° and 0.06 mm Hg.

030021/0736

Case 130-3866

Example 1 0 (method d)

a-iA-chlorophenylJ-A-chlorobenzylphosphonic acid diethyl ester

13.6 g (0.05 mol) of di (4-chlorophenyl) chloromethane are added under a nitrogen atmosphere at 160 ° (oil bath temperature 200 °) and with stirring for 3 hours with 12.5 g (0.075 mol) of triethyl phosphite and then reacted with 160-172 ° (oil bath temperature of 200-212 °) stirred further.

The reaction product is chromatographed (250g silica gel with hexane /

20th

Ethyl acetate 7: 3), the title product with r. = 1.5508 obtained will.

If one proceeds according to the information in the aforementioned examples 1-10 and if the appropriate starting materials are used, compounds of the formula! »are also obtained in the table below are listed.

TABEL

(1) for the cases in which 1 substituent is listed, the others stand for hydrogen.

(2) for the cases in which XR = 0R, in which only 1 substituent is listed.

Dsp.
N ¹ O. ^y i, 2! ₃ ^R l «2 OR ₃ S ^ characteristic
20th
η _t boiling point or
Melting point procedure 11 4-C1 CK ₃ II OC ₂ H ₅ 1.5048 a, b, c, d 12th do do CH- do 1.5072 C. 13th do C ₂ H ₅ II do 1.5029 ABC 14th do do ^C 2 ^H 5 do 1.5112 C. 15th do nc ₃ n ₇ H do 1.5012 a, b, c 16 do HC ₃ K ₇ BC ₃ K ₇ do 1.5055 c,

030021/0736

Case 130-3866

29U598

E.g.
NO. ^Y l, 2.2 ^R l -CH ₂ C ₂ CH R ₂ / ^V 4 characteristic
20th
n_ boiling point or
'Melting point procedure 17th 4 -Cl ■ i " ^C 3 ^H 7 -CH ₂ -Q CH ₃ 1.5055 C. 18th do 1-C ₃ H ₇ 1-C ₃ H ₇ do 1.4956 C. 19th do HC ₄ H ₉ - © H do 1.4998 ABC 20th do 2-C ₄ H ₉ do H do 1.5-35 ABC, 21st do i " ^C 4 ^H 9 H do 1.4982 ABC 22nd do HC ₅ H ₁₁ H do 1.4970 ABC 23 do 2-C ₅ H ₁₁ H do 1.5-5 ABC 24 do 3-C ₅ H ₁₁ H do 1.5018 ABC 25th do 1 "C ₅ H ₁₁ II do 1.4925 a, b _# c 26th do S " ^C 6 ^H 13 II do 1.5160 «, B, c 27 do ² " ^C 6 ^H 13 H do 1.4981 ABC 28 do PcH ₂ CH = CH ₂ H do 1.51-5 a, c 29 do H do 1.5160 a, c 30th do H do 1.5415 a _# c 31 do H do 1.5178 a, c 32 H H do λ / 35 ^C C (m.p.) a, d 33 II 1-C ₃ H ₇ do 1,549Ο C.

030021/0736

Case 130-3

E.g
No. Y ^{
i, 2 ,: 1)
3 ^R i 1· ^CR _{3 /} / _R ^ (2) —Ι II do taw ^[ 2 * do
do characteristic
20th
η, boiling point or
Melting point ■ 1.5216 procedure 34 4-Cl -CH ₂ -Q-Cl H OC ₂ H ₅ do do 1.5498 a, c 35 do ₂ -c _ß " ₁₇ H do do do 1.4930 ABC 36 do 2- ^C 10 ⁿ 21 H do do
do do 1.4883 ABC 37 do II do ^C 3 ^H 7 do 1.5502 a, d 38 do ³ - ^C 6 ^H 13 do 1.5010 ABC Cl ) ci 39 do (CH ₂ ) ₂ -0- (Ö H 1.5440 ABC 40 do f ^B 3
-CH ₂ C = CH _?
Cl H a, c 41 do H
H a 42
43 do
do -CH ₂ CH = CHCl
CH ₃
-CH- (O) ^R 2 a
a, c 44
45 do
do R ₁ together ndt
1 -CH ₂ CH ₂ C.
a 46 do -CH ₂ CCl ₂ - : h ₂ a 47 do ■ i C a, c 48 do ₂ CH a, c 49 do a-c M & Mm 4

030021/0736

Case 130-3866

29U598

E.g.
Ao. ν (D
1,2,3 ^R l ^R 2 ⁰ X? characteristic
20th
n _n , boiling point or
" Melting point "E. .4962 * (Stop.) 60-62 ° /Experienced 50 4-Cl 2-methyl-
butyl H -OC ₂ H ₅ 1 .4963 1.4917 ABC 51 do 2-ethyl-
butyl II do 1 .5225 ABC, 52 do cyclohexyl H do 1 a, c 53 do 3-heptyl H do .4975 ABC 54 do 4-methy 1-
2-pentyl II do 1 1.5042 ABC 55 do 3-C ₅ H ₁₁ CH ₃ -OC ₂ H ₅ 1.5160 1.5116 ■ I 56 do do do 1.5064 57 do do do 58 do 1-C ₅ H ₁₁ -0-C ₄ H ₉ ABC 59 do ² - ^C 5 ^H ll do ABC 60 do 3-C H do ABC 61 do • ^ Jb JL. 2-OC ₄ H ₉ 62 do 2-C ₄ H ₉ - OC ₃ II ₇ - ^ 63 do do ^C 2 ^H 5 -0- CK ABC 64 2,4-Cl ₂ 2-C ₄ H ₉ GC ₃ H ₇ -OC ₂ H ₅ a, c 65 do i- ^C 5 ^H ll H do a, c 66 do 2-C ₅ H ₁₁ H do a, c 67 do 3-C ₅ H ₁₁ II do a, c 68 do H do a, c H H II H H H H

030021/0736

Case 130-3866

E.g.
Nd. "'1,2,3 58a 4-Cl 69 do 70 do 71 do 72 do 73 do 74 do 75 do 76 do 77 do 78 do 79 do 80 do 81 do 82 do 83 do 64 do 85 do 86 do

do

do do

do do

do do do do do do

do do do do do do

do

■ "Γ

Η H

H H

II Ii H II H II H H

H H H H H H

II

OR, /

3 / XR

-OH

X-OC ₃ Ii ₇ H-OC ₃ H ₇

" ⁰ YY

Own cliaf t

η boiling point or
'Melting point

-0-CH ₂ CH = CH ₂

0-CH ₂ CsCH

1.5185
57-59 ° (m.p.)

1.4920

1.4921

74-76 ° (£ np.)

procedure

a, b, c c

a, b, c a, b, c

a, b _f c

c
ABC

a, b, c a, b, c c

ABC

a, c

c
c

b, c
b, c

030021/0736

-X-

Case 130-386b

294 * 598

tep.
Ko. γ (D
1,2,2 ^R l ^R 2 OR, / (2)
V ^XR 4 do characteristic
n _n boiling point
¹ OdJ Schrelzpunki Ver
travel 87 4-Cl XC ₃ H ₇ ** -0-CH ₂ CM ₂ OCH ₃ do 1.5049 ABC 88 do do II -CCK ₂ CH ₂ OC ₂ H ₅ do ABC 89 do do H -CCH ₂ CH ₂ SC ₂ H ₅ do ABC 90 do do K -0-CH ₂ CH ₂ O-XC ₃ H ₇ do ABC 91 do do H -OCu ₂ -Q do ABC 92 do do H -OCH ₂ -Q do ABC 93 do do H -OC ₂ H ₅ Z-SC ₂ H ₅ do a 94 do do H -OC ₂ H ₅ Zn-SC ₄ H ₉ do a 95 do do H -OC ₂ H ₅ ZN (CH ₃ J ₂ do ABC 96 do do H -OC ₂ H ₅ ZN (C ₂ H ₅ J ₂ do ABC, 97 do do H -OC ₂ H ₅ ZN (JIC ₃ H ₇ ) 2 do ABC 98 do do H -OC ₂ H ₅ ZN (XC ₃ H ₇ ) ₂ do C. 99 do do H -OC ₂ H ₅ Z-NJi] do ABC 100
LOl do do H -OC ₂ H ₅ Z-IG> ABC L02 do do H -OC ₂ H ₅ ZN (nC ₄ H ₉ ) ₂ ABC L03 H do H - ° ^C 2 ^H 5 1.4911 ABC 104 3-Cl do H 1.5013 ABC 105 2-Cl do II 1.5023 a, c 106 2,4-Cl ₂ do H 1.5133 a, c 107 2,6-Cl ₂ do H 1.5159 a, c 108 3,4-Cl ₂ do H 1.5152 ABC 109 3,5-Cl ₂ do H 1.5125 ABC 110 4-CH ₃ do H (Sdp.) 107 ⁰ ZO.04mm ABC 111 4-OCH ₃ do H 1.4998 ABC 112 > ■ <) do H 1.5082 ABC 1Ϊ3 4-KO ₂ do H 40-42 ° (adapt.) a, c 114 4-0- (O) -Cl do II 1.5372 ABC 115 4-Br JC ₅ H ₁₁ H (Sdp.) 16 3 70.03 m ABC 116 4-F GO H 1.4828 ABC 4-CN do H 1.5088 ABC

030021/0736

Case 130-38ϋό

Ex. No.

(D

1,2,3

^R l ^R 2 3-C ₅ II ₁₁ II do H do II do H do II do H do H do H do H do H do H do H do H do H do II do H do H do H do H do H do H do II do H do H do H do II do II

characteristic

nj »boiling point or
Melting point

procedure

117 118 119 120 121 122 123 124 125 126 127 128

130

4-COOC ₂ H ₅ 4-CON (CH)

4-COCH

4-OCH = CCl ₂

4-OCF ₃

4-SCF ₃

4-OCF ₂ CHF ₂

4-OCHF ₂

4-OCF ₂ Cl

4-SO ₂ CF ₃

4-SO ₂ CH ₃

4-CH = CCl ₂

4-CH = N-OCH.,

«Ο 2-NO ₂

5-0-®- CF, Cl ^ό

3-Cl, 4-OCH.

3-0- (o) -ci 4-0- (O) -NO ₂

4-O- (O) -Cl Cl

4-0- (O) -CF ₃

4-0- (O) -CN

4-0- / O) -CN

3-Cl, 4-0- (O) -CN 3-Cl _x 4-O- (ÖVcN

OC ₂ H ₅ do

do do

do do do do

άο do

do do

do do

do do do

do do

do do

dö

do do do

do do

1.4618

1.4762

1.5364

1.5482

1.5004

3, c

a, c

ABC

a, c

ABC

ABC

ABC

ABC

ABC

b, c
a

ABC

3 / b / C

ABC

i, b, c

a, b, c a, b, c a, b, c

a, b, c a, b, c

030021/0736

-X-

Case 130-3866

E.g.
Ko. ν (1)
1,2,3 ^R l ^R 2 OR ⁽²⁾ characteristic
η boiling point or
^D '»melting point driver 144 H 3-C ₅ II _n H -OC ₂ H ₅ 1.4930 ABC 145 4-tC ₄ H ₉ do H do 1.4905 ABC 146 3-KO ₂ do H do 1.5122 ABC 147
148 4-0CH-
f
4-0-s ^ vXV »/ do
do H
II do
do 1.4992
1.4902 ABC
ABC 149 4-0 (CH ₂ J ₉ CH ₃ do H do 1.4833 ABC 150 do H do away 151 ⁴ O do H do away 152 4-H (C ₂ H ₅ J ₂ do H do 1.5118 a _f b, c 153 4-CkX. do H do 1.4918 ABC 154
155 4-SC ₂ H ₅
9
4-SC ₂ H ₅ do
do H
H do
do (Sap.) 157 ° / O.O3 only Jig away 156 4-0-C H do 1.5010 ABC 157 do UC ₄ H ₉ - ~ ^C 4 ^H 9 do 1.4907 C. 158 do HC ₃ H ₇ H i-0C, H_ 1.4808 b, c 159 4-CH ₃ do HC ₃ H ₇ -OC ₂ H ₅ C. 160 4-HC ₅ H ₁₁ do do do C. 161 4-CH ₃ - (O) do do do C. 162 4-CH ₂ OCH ₃ do do do C. 163 4-OCH ₃ do do do 1.5035 C. 164 4-0-C do do do 1.4939 C. 165 do do do -oX "- 1.4875 C. 166 do do do 1-OC ₃ H ₇ 1.4854 C. 167 Cl do do (M.p.) 61-62 ° C. 168 4-CX ^ / ¹ dc do do 1.5058 c.

030021/0736

Case 13 {-38r> 6

29U598

E.g. Ko.

(D

1,2,3

R.

OR

(2)

I ^

XR

characteristic

_n ²⁰ boiling point or
D »melting point

procedure

169 17O

171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 166 187 188

4-OnC ₄ H ₉

4-0-0d

4-0- (δ) -Cl

4-Cl

4-0 - {_ do do do do do

4-CkX

4-0-Iv-C ₃ H ₇

4-0- (

4-0

4-

nC ₃ H. do

do do 12-C ₄ H,

do

do do

do do do do do do do do do

do do

do

do do

do

do
do
do
do

-OC ₂ H ₅

do
i-OC, H.

1.4954
1.5065

100-102 °
1.4982

1.5468
1.5176
1.4894
1.4891

0-IV-C ₃ H ₇

H ₅ ZK (C ₂ H ₅ ) ₂
H ₅ / -K (11-C ₃ H ₇ )

-OC ₂ H ₅

do
do

a, b, c a, b, c a, b, c

ABC

b, c

ABC

ABC

ABC

ABC

ABC

ABC

ABC

ABC

ABC

1.5031

030021/0736

tf / f case 130-3805

Example 189

4-chlorobenzylphosphonic acid diethyl ester (compound of formula VI)

To 0.95 g (0.032 mol) of an 80% sodium hydride dispersion in 25 ml of 1,2-dimethoxyethane are added under a nitrogen atmosphere and reflux temperature in the Over the course of 25 minutes, 4.37 (0.032 mol) of diethyl phosphite were added and stirring was continued for a further 11/2 hours. For the chilled mixture 4.64 g (0.029 mol) of 4-chlorobenzyl chloride in toluene are added dropwise at room temperature, and the whole thing over 3 hours under Reflux cooled.

After adding a further portion of 0.03 g of sodium hydride dispersion at 45 ° and 2.0 g of diethyl phosphite under reflux temperature, the reaction is carried out with stirring for 18 hours and at a temperature of 80 ° to the end. After the reaction product has cooled, a little water is added and the mixture is extracted with ether.

The ether extract is washed with water and "brine" and dried over magnesium sulfate and then evaporated.

The residue is purified chronographically (100g silica gel with hexane / Ethyl acetate 1: 1), the title product as a colorless oil with a Boiling point of 140-149 ° and 0.1mm Hg is obtained.

EXAMPLES OF HERBICIDAL PREPARATIONS Example A (wettable powder)

25 parts by weight of a compound of the formula I, 5 parts of a condensation product of formaldehyde and naphthalene sulphonate, 2 parts of an alkylbenzenesulphonate, 5 parts of dextrin, 1 part of ammonium caseinate and 62 Parts of diatomaceous earth are mixed until a homogeneous mixture is obtained and then ground until the particle size for the most part is less than 45 microns on average.

030021/0736

29-598

Example B (emulsion concentration)

25 parts by weight of a compound of the formula I, 65 parts of xylene and 10 Share a mixture of the reaction product of an alkyl phenol with Ethylene oxide and calcium dodecylbenzenesulfonate are mixed until a homogeneous solution is obtained. The resulting emulsion concentration is diluted before use.

Example C (granules)

5kg of a compound of the formula I are dissolved in 25 liters of methylene chloride. The solution is then added to 95 kg of granulated attapulgite (with a mesh diameter of 2 4/28 mesh per inch). The solvent is then removed under reduced pressure.

030021/0736

Claims (9)

2944593 SANDOZ-PATENT-GMBH Case 130-3866 Lörrach Phosphonic acid ester derivatives claims 1. A method of combating weeds on the spot, characterized in that one is at the relevant location or at the relevant Substitute an amount of a compound of the formula having herbicidal activity - P ^ ^J sets in, where Y is hydrogen or halogen (advantageously chlorine, bromine or Fluorine, preferably chlorine), Y ₂ hydrogen, halogen, (advantageously chlorine, bromine or fluorine, preferably chlorine), (I-10C) -alkyl, (I-IOC) -alkoxy, (! 1-7C) -cycloalkyl or (3-7C) -cycloalkoxy ^{and Y} 3 hydrogen, halogen (advantageously chlorine, bromine or Fluorine, preferably chlorine), nitro, cyano, (i-lOC) -alkyl, (l-lOC) -alkoxy, (2-10C) -alkoxy-alkyloxy, (2-lOC) -alkenyl, (2-10C) -alkenyloxy or (l-lOC) -thioalkyl, each alkyl or alkenyl radical or part of these alkyl or alkenyl radicals being unsubstituted or are substituted by halogen (advantageously chlorine and / or fluorine); also Y ~ benzyl, phenyl or phenoxy and each of these Phenyl radicals or some of these phenyl radicals 030021/0738 ORIGINAL INSPECTED Case 130-3866 are substituted or are substituted by one or two substituents and the substituents of the phenyl rusts mentioned are halogen (advantageously chlorine, bromine or fluorine, preferably chlorine), nitro, cyano, (1-6C) -alkyl, (1-6C) -alkoxy, ( 1-6C) -thioalkyl, and each of these alkyl radicals or parts of these alkyl radicals are unsubstituted or substituted by halogen (advantageously chlorine and / or fluorine); Y-, ^ai -ich -CONR R, -COR, -COOR, ο ^{J x} y ρ ρ -S - R, -SO-R, -NR R, P 2p χ y » -CH = N-OR, -CH " Z ₁ z. or means, or the two radicals Y "and Y, if they are attached to adjacent C- Atoms in ring A are bonded, together a methylenedioxy- or can form ethylenedioxy, wherein R and R, independently of one another, are each (l-lOC) -alkyl or χ y (3-10C) -Alkenyl, or R and R together with the N atom attached to them form a pyrrolidine, piperidine, Morpholine or N-methylpiperazine ring, wherein R is in each case phenyl, an unsubstituted (l-10C) -alkyl radical or one substituted by chlorine and / or fluorine (l-lOC) -alkyl radical and Z and Z "each independently represent 0 or S, an unsubstituted (l-10C) -alkyl radical or one which is substituted by halogen (advantageously chlorine or fluorine) (l-10C) -alkyl radical; an unsubstituted (3-7C) cycloalkyl radical or a (3-7C) -cycloalkyl radical substituted by halogen (advantageously chlorine); a (1-4C) -Alkyl radical, which is replaced by a (1-3C) -alkoxy group is substituted by a phenyl or a phenoxy radical, and the phenyl or phenoxy radicals are unsubstituted or substituted by or 2 substituents are substituted and these substituents 030021/0736 29U598 ~ ³ ~ Case 130-3366 Halogen (advantageously chlorine), (1-4C) -alkyl, (1-4C) -alkoxy or trifluorir.ethyl; an unsubstituted (2-6C) -alkenyl radical or a (2-6C) -alkenyl radical substituted by calogen (advantageously chlorine); a (2-4C) alkynyl radical; an unsubstituted phenyl radical or a phenyl radical substituted by one or two substituents and these substituents are halogen (advantageously chlorine), (1-AC) -alkyl, (1-4C) -alkoxy or trifluoromethyl and R "is hydrogen or one of the meanings of R ₁ owns, mean, or wherein R and R together with the a-C atom bonded to them form an unsubstituted one (3-7C) -cycloalkylidene or one substituted by halogen, advantageously chlorine, or (1-4C) -alkyl (3-7C) -Cycloalkylidenrir.g can form, wherein X is 0, S or -NR, R is an unsubstituted (1-8C) -alkyl radical, one by one (1-3C) -alkoxy, (1-3C) -thioalkyl or halogen (advantageous Chlorine or fluorine) substituted (1-4C) -. \ Lkylrest; (3-6C) alkenyl; (3-6C) alkynyl; Tetrahydrofur-2-yl-diethyl, tetrahydro-2H-pyran-2-yl-methyl or (5-6C) -cycloalkyl, where R, and R_ either have one of the meanings of R "or R, and 5 3 4 R ₁ . can together with the N atom bound to them form a piperidine, pyrrolidine, morpholine or N-methylpiperazine ring. 2. The method according to claim 1, characterized in that there is a compound of the formula Ib Ib) used, 030021/0736 29U598 - 4 - H Caso 130-3866 where Y 'is hydrogen or chlorine, Y 'chlorine, bromine, (1-5C) -alkoxy, (3-5C) -alkenyloxy or (1-5C) -alkyl,
R 'is an unsubstituted (3-6C) -alkyl radical or (3-6C) -CyC- loalkyl,
R 'is hydrogen or an unsubstituted (1-4C) -alkyl radical, X ¹ 0 or NR 'and R ', R' and R_ ', independently of one another, each have an unsubstituted one (2-4C) -alkyl radical. 3. The method according to claim 1, characterized in that the location of the Control in arable farming and especially in cereal cultivation. 4. Compounds of the formula Ia Yes, and XR (R eingeschlosY with ₁ Y ₁ Y ₁ R ₁ R ₁ R and XR, (including R) with the proviso that α) if Y,, Y. and Y_ are hydrogen, and both la 2a 3a 0R ₀ and also X RCH _C O or i-C_H_O and R, CH_, CH-, 3a a 4a 2 5 - 3 7 la J / 5 nC »H, £ ~ C, H, HH ₁ mean allyl or benzyl, then R is not hydrogen or (2-5C) -alkyl, β) if Y,, Y ", Y_ and R" are hydrogen, and la 2a 3a 2a both OR. and also XR. (2-5C) alkoxy, then 3a 4a R is different from phenyl, or χ) if Y ₁ , Y "and R" for hydrogen and Y. for methyl la 2a 2a 3a stand, and both OR. and also X R, C.H.O mean 3a a 4a 2 5 then R is different from methyl, or γ wherein 2a Y
3a V R ₁
la 0 OR Y ^Y 2a « > - I.
C.
^R 2a -P X R.
a 4a sen) ^Y 3a ' ^R la' ^R 2a- ' ^R 3a ^U the Meanings of 030021/0736 - 5 - Case 130-3866 (J ") if Y ₁ , Y ₀ and Y for hydrogen and R for Me- Xa Za j3 za thoxymethyl stand, and both OR. and also XR, C ₀ HO each a 4a ζ j then R is different from methyl. 5. Herbicidal composition containing one of the claims 1, 2 and 4 named compounds in connection with a herbicidal carrier or solvent or wetting agent. 6. A process for the preparation of compounds of the formula Ia according to claim 4, that one a) if compounds of the formula Ica are to be produced wherein Y, Y ", Y_, R-, R, and X have the meanings given in claim 4, and R- "has the meaning of R according to claim 4, za za with the proviso that R- "stands for hydrogen, if X O or NR. means, a 5a ' a compound of the formula Ha ^R la O Cl __ , H ^ Ha, wherein Q. is chlorine or OR_, and Y, Y, Y-, R R_ "and R- the aforementioned Be Xa ζ3 j3 X ^ t za Yes have interpretations, with a compound of the formula IHa R, X M IHa 4a a 030021/0736 - 6 - Case 130-3866 implements, wherein X and R have the meanings given in claim 4, and either M is hydrogen if X 0 or NR _C 'a 5a is,
or M is an alkyl metal cation when X is S, el and in which R has the meaning given in claim 4, or ^ a b) if compounds of the formula 0 OR.
^3a Ida are to be produced wherein Y ₁ , Y ₁ Y, R "and XR are the la 2a 3a J3 a 4a mentioned in claim 4 Have meanings and
either R '"is an unsubstituted (l-lOC) -alkyl radical and R "" 'signify hydrogen, or both R' "and R '" signify phenyl or substituted phenyl mean, a compound of formula IVa R "' C Q. IVa, γ --— \ "T" / ι ^L
2a γ I -
3a wherein Y,, Y ", Y_, R ₁ "'and R "'" are the aforementioned Be-Ia 2a 3a la 2a have interpretations
Q means “halogen
with a compound of the formula Va and Q "means halogen, Na - o - p: T Va, X R.
a 4a 030021/0736 Case 130-3866 where converts, or X, R- and R. have the meanings given above, a yes 4a c) if compounds of the formula Iea Y ₁ ^ / ^ "la O OR, la R ₄ a 4a Iea are to be produced, in which and R "" and R ^{IIU have} the meaning of R. and R, with the proviso that not both R ₁ "" phenyl or A & mean substituted phenyl, X "represents O or NO a 5a Y,, Y-, Y-, R-, R. and R. the aforementioned Be-Ia Za 3a 3a 4a 5a have meanings by mono- or disubstituting a compound of the formula VIa, R, 0R 3a Via, 4a 3a wherein R, hydrogen, phenyl or substituted phenyl beoa indicates and X ", Y ₁ , Y-, Y-, R- and R, have the meanings mentioned above, with one or two compounds of the formula Vila R, Q ₃ VIIa), wherein R, has one of the meanings of R, with the proviso 7a la that R ₁ does not represent phenyl or substituted phenyl, ie and Q. is a removable group, or with a compound of the formula Vllaa) ^R 8a - ^Q 3 VII aa), 030021/0736 - 8 - Q Casi 130-3866 wherein R _ft denotes an unsubstituted or a (2-6C) -alkylene radical which is substituted by halogen or (1-4C) -alkyl and Q- has the meaning given above, or d) if compounds of the formula Ifa ^R - 0 OR κ ^ 3a Ifa) C "R ₇ a 4a are to be produced wherein X ", Y, Y, Y, R and R have the meanings given above own and R '"" represents methyl, phenyl or substituted phenyl, a compound of the formula Villa ^Y 3a where Q is halogen, and Y,, Y ", Y- and R, '" "have the meanings given above la 2a 3a la owns, with a compound of the formula IXa) ^ OR
R "- 0 - P <7 ^Yes IXa), A - j < 4a in which R_, R. and X "have the meanings given above 4a Zen, implements. 030021/0736 - 9 - «Case! 130-3866 7. Means for controlling weeds, containing a compound of Formula I according to claim 1 as an active substance. 8. Agent for combating weeds, containing a compound of the formula Ia according to claim A as an active ingredient. 9. Means for combating weeds, comprising a formulation according to Claim 5. 030021/0738