DE1768397A1 - Process for the preparation of thiolphosphoric acid-O-haloalkyl-S-aryl- or -aralkyl-diester-dialkylamides - Google Patents

Description

1768397 FARBENFABRIKEN BAYER AG

LEVERKUSEN-Bayerwerk PATINT-AiTIlLUNC

0 MAY 7, ₁₉₆₈ i

Process for the production of thiolphosphoric acid-O-balogenalkyl-S ~ aryl- or aralkyl-diester-dialkylamides

The present invention relates to a new process for the preparation of thiolphosphoric acid-O-haloalkyl-S-aryl or -aralkyl-diester-dialkylamides, which can be used as fungicides, bactericides, insecticides and acaricides.

It is already known (see K.A. Petrov, N.A. Bliznjuk and V.A.Savostenok,, Z.obsc. Chim. 31, 1361 (1961)) that Thiolphosphoi acid-OjS-diester-dialkylamides from 0,0-dialkyl-phosphorous acid-diester-chlorides and sulfenic acid dialkylamides in the sense of the following equation (I) can be prepared:

(RO) ₂ P-Cl + R'S-NR ^ * RO-P-NRg + RCl (I)

SR '

In the above formulas, R and R ″ denote ^{an alkyl radical, R 1} denotes an alkyl or aryl radical.

In the production of thiolphosphoric acid-O-haloalkyl- S-aryl- or -aralkyl-diester-dlalkylamides this has

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However, the process has the disadvantage that the starting materials required as starting materials halo in the alkyl radical OjO-Dialkylphosphorigsäure-diester-Chloride only with difficulty are accessible.

It is also known (cf. German Auslegeschrift 1.080.109) that thiolphosphoric acid O.S-dialkylester dialkylamides can be obtained according to the following equation (II):

0 0

RO-P-NRg + HaI-R ¹ »RO-P-NHJ + NaHaI (II)

SNa SH '

R, H 'and R "mean in the last-mentioned formulas Alkyl reete.

However, this process is for the preparation of thiolphosphoric acid-O-haloalkyl-S-aryl or -aralkyldiester-dialkylamides because of the low reactivity of the halogen atom in the aryl or aralkyl halides to be converted not applicable. In addition, the thiolphoephoreic acid-O-haloalkyleeterdialkylamides required as gelatinous products very difficult in the form of their alkali salts or not accessible at all because these are haloalkyl compounds React with calibration itself or with identical neighbor molecules and thus give rise to uncontrollable side reactions.

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It has now been found that thiolphosphoric acid-O-haloalkyl-S-aryl- or -aralkyl-diester-dialkylamides of the general formula (III)

R ₅ R ₃ R ₁ 0 R ₆ -C- (G) _n -GOP-SR ₇ (III) ti I. ·

Hal Rj Ro

can be obtained with very good yields and in excellent purity if 2-Dialkylauiino-dioxaphospholan- or phosphorinane derivatives of constitution (IV)

(IV)

with sulfenic acid halides of structure (V)

HaI-SR ₇

implements.

In the aforementioned formulas, the symbols R ₁ to R _{6 represent} hydrogen atoms, alkyl or haloalkyl radicals; R _{7 represents} an optionally substituted aryl or aralkyl group; Rg and Rg represent straight-chain ^ or branched lower alkyl or alkenyl radicals, while Hai represents a halogen, preferably chlorine or

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Bromine atom and η has the value zero or 1. The smooth and uniform course of the invention

Procedure is surprising. It couldn't go ahead will see that the above-mentioned 2-dialkylamino-dioxaphospholan or phosphorinane derivatives with sulfenic acid halides with splitting of the heterocyclic ring and formation of thiolphosphoric acid-O-haloalkyl-S-aryl- or aralkyl-diester-dialkylamides would react.

Compared to the above-mentioned known, for production Some of the compounds in question are only conditionally suitable or not at all suitable for the methods according to the invention Process through a number of essential advantages. Above all, this includes easy accessibility the starting materials, uniform course of the reaction, good yields and the very simple method of implementation.

If, for example, 2-diethylamino-dioxaphcspholane-1,3,2 is used with 4-chlorophenylsulfenic acid chloride within the meaning of present invention, the course of the reaction is represented by the following formula (VI):

C ₉ H ₁ - / -Λ, CICH ₉ CH ₉ O _n

^{2 5} + eis- / Vci - * ^{2 2} .

^G 2 ^H 5 ^ = ^ (C ₂ H ₅ J ₂ N

(VI)
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In the case of the implementation of 2-dimethylamino-dioxaphoaphorinane-1,3,2 with 4-chloro, henylsulfenic acid chloride the reaction proceeds according to the following equation (VII)

CH ₀ O _{d k} ClCH ₀ CH ₀ GH ₀ O i?

CH ₉ PN (CH,) ο + ClS-T ^X ) -C1 / ~ ^b

? / ^{3 2} \ y (j

CH ₂ O

(VII)

The 2-dialkylamino-dioxaphospholane to be used as starting materials for the process according to the invention or phosphorinane derivatives and the sulfonic acid halides in question are replaced by those given above Formulas (IV) and (V) are clearly defined.

Preferably, however, the symbols R ^ to Rg mean Hydrogen atoms or optionally halogen-substituted lower alkyl radicals having 1 to 4 carbon atoms; R- stands preferably for a single or multiple halogen atoms, lower alkyl and / or nitro groups substituted aryl, especially phenyl, or optionally one or more times by halogen and / or lower alkyl radicals substituted benzyl radical; Rg and Rq are preferably straight-chain or branched lower alkyl or alkenyl groups with 1 to 4 · C atoms, while Hai is mainly a chlorine or Bromatam is. η has the value zero or 1.

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Ala examples of those to be used according to the invention 2-dialkylamino-dioxaphospholane or -phosphorinane derivatives are mentioned in detail:

2-dimethylamino-, 2-dimethylamino-4-methyl- _t 2-dimethylamino-4-chloromethyl-, 2-dimethylamino-4 »5-dimethyl-, 2-diethylamino-, 2-diethylamino-4-methyl- _J 2- Diethylamino-4-chloromethyl-, 2-diethylamino-4,5-dimethyl- _t 2-diallylamino-, 2-diallylamino-4-methyl-, 2-diallylamino-4-chloromethyl-, 2-diallylamino-4,5-dimethyl -dioxaphoβpholan-1,3,2,

2-dimethylamino-, 2-dimethylamino-4-methyl-, 2-dimethylamino-4,5 * 6-trimethyl-, 2-dimethylamino-5 »5-dimethyl-, 2-diethylamino-, 2-diethylamino-4-methyl -, 2-diethylamino-4,5,6-trimethyl-, 2-diethylamino-5,5-dimethyl-, 2-diallylamino-, 2-diallylamino-4-methyl-, 2-diallylamino-4 _t 5 »6- trimethyl, 2-diallylamino-5,5-dimethyl-dioxaphosphorinane-1,3,2.

Sulfenic acid halides can, for example are used as external materials:

Phenyl-, 4-chloro-phenyl-, 4-nitro-phenyl-, 2-nitrophenyl-, 2,4-dichloro-phenyl-, 4-bromo-phenyl- and Benzyl sulfenic acid chloride or bromide.

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The 2-dialkylaminodioxaphospholan to be used as starting substances or phosphorinane derivatives can by customary methods, even on an industrial scale, easily from the corresponding ones described in the literature 2-chloro-dioxaphospholanes or -phosphorinanes are produced.

The sulfenic acid halides still required are also obtained in a known manner from the mercaptans in question or disulfides by the action of halogenating agents, e.g. B. sulfuryl chloride, elemental chlorine or bromine readily accessible.

The claimed process can be carried out in the presence or absence of solvents or diluents will. Practically all inert organic solvents can be used as such. Have proven particularly effective optionally chlorinated aliphatic or aromatic hydrocarbons such as dichloride than or ethane, Di-, tri- and tetrachlorethylene, chloroform, carbon tetrachloride, gasoline, benzene, chlorobenzoi, toluene and Xylene, further ether, e.g. B. diethyl and di-n-butyl ethers, Dioxane, tetrahydrofuran and lower aliphatic ketones and nitriles, for example acetone, methylethyl-, methylisopropyl and Methyl isobutyl ketone, aceto- and propionitrile.

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The reaction according to the invention can be carried out within a relatively wide temperature range, which varies depending on the nature of the starting materials to be converted. H In general, one works between -20 and +50 C, preferably at -10 to +30 C.

To carry out the process according to the invention, per mole of the 2-dialkylamino-dioxaphospholane or -phosphorinans 1 mole of sulfonic acid halide used. It has proven to be expedient to use the latter - diluted with one of the above-mentioned solvents - in the specified temperatures with stirring and possible cooling of the reaction mixture to the solution of the 2-dialkylamino-dioxaphoepholane or -phosphorinane derivatives to drop. After the addition is complete, the mixture is stirred another 1 to 3 hours, then it washes until it is neutral and the solvent is removed under reduced pressure away. ·

The products of the process are mostly colorless to yellowish oils, some of which can be distilled in a vacuum. If this is not the case, the compounds obtainable according to the invention can be "etched" for purification, ie freed from the last volatile impurities by prolonged heating under reduced pressure to slightly to moderately elevated temperatures. However, since the substances obtained in the reaction already in high purity, \ their continued use is possible without prior isolation and / or purification,

109883 / 18S1

Surprisingly, the process products stand out in comparison to those previously known from the literature ■ Active ingredients of an analogous constitution and the same direction of action due to a significantly better, above all fungitoxic, but also bactericidal, insecticidal and aecaricidal effectiveness with only low warm-blooded animals and phytotoxicity the end. The effect sets in quickly and lasts for a long time. Thus, the subject matter of the invention represents a significant enrichment of the technology.

Due to their properties mentioned above, the process products can be used successfully in crop protection will.

The active ingredients that can be prepared according to the invention have particularly

another strong fungitoxic effect against phytopathogens

g mushrooms. Also diseases can be fought by bacteria Z caused it. The good compatibility for t warm-blooded animals and higher plants permits their use as pesticides ^F ge ^ s fungal and bacterial t | \ diseases. They do not damage cultivated plants in the concentrations required to combat fungi and bacteria. Fungi-toxic agents in plant protection are used _; uses to combat fungi from the most diverse ■ ^: classes, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfect !.

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The active ingredients obtainable according to the invention have a broad spectrum of activity. They can be applied against parasitic fungi and bacteria on above-ground parts of plants, trachemomycosis-causing fungi that cause the Attack plants from the ground, seed-borne and soil-dwelling fungi and bacteria.

The products of the process have proven their worth above all in combating rice diseases. So they show one excellent action against the fungi Piricularia oryzae and Pellicularia sasakii, due to which they are common Combating these two diseases can be used. That means a significant port step since so far Against these two fungi, remedies of different chemical constitution were required. Surprisingly show the active ingredients not only have a protective effect, but also a curative effect.

However, the compounds which can be prepared according to the invention also act against other fungi and bacteria, such as rice or attacked other KuIttir plants, such as cochliobolue myiäbeanus, Mycosphaerella musicola, Ceroepora personata, Botrytis cinerea and Alternaria species, Fuearium species, Verticillium alboatrium, Phialophora cinerescens, Xanthomoner oryzae.

Depending on their intended use, the new active ingredients

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L '- a ■ -. -

be converted into the usual formulations, such as r solutions, emulsions, suspensions, powders, pastes and Granules. These are produced in a known manner, e.g. by mixing the active ingredients with extenders, d, h. liquid solvents and / or solid carriers, optionally using surface-active agents Agents that are emulsifying and / or dispersing agents, e.g. in the case of using water as an extender optionally organic solvents as auxiliary solvents can be used. The main liquid solvents that can be used are: aromatics (e.g. xylene, Benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water; as solid carrier substances: natural rock flour (e.g. kaolins, clays, talc, chalk) and synthetic minerals (e.g. finely divided silica, silicates); as emulsifier: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters,

Polyoxyrithylene fatty alcohol ether, (e.g. alkylaryl polyglycol ether, Alkyl sulfonates and aryl sulfonates) as dispersants e.g. lignin, sulfite waste liquors and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

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The formulations generally contain between 0.1 and 95 percent by weight active ingredient, preferably between 0.5 and 90 ^.

The active ingredients, as such, in the form of research _'t. mulierun ^ s or the application forms prepared from them, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders! Pastes, IBeliche ι. Powders, dusts and granules can be used. They are used in the customary manner, for example by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can vary over a wide range will. Generally they are between 0.0001 and 10 ^, preferably between 0.01 and 1 #.

The unexpected superiority as well as the excellent Effect of the compounds that can be produced according to the method when used are a multitude of different ones Felts and bacteria can be seen from the following test results:

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: ■■■■ * ti

Example A. Piricularia test)

} liquid active ingredient preparation Pellicularia test)

Solvent: 1 part by weight of acetone Dispersant: 0.05 part by weight of sodium oleate

other additives: 0.2 parts by weight gelatin

Water: 98.75 parts by weight

The amount of active substance necessary for the desired concentration of active substance in the spray liquid is mixed with the specified amount of solvent and diluted the concentrate with the necessary amount of water, which contains the additives mentioned.

With the spray liquid obtained in this way, 2 × 30 hot plants about 2 to 4 weeks old are sprayed to runoff. These remain in a greenhouse at temperatures of 22 to 24 ^° C. and a relative humidity of about 70 pounds until they have dried. Thereafter, a part of the plants ml inoculated with an aqueous suspension of 100,000 to 200,000 spores / from Pirlcularia oryzae and in a tree at 24 to 26 ⁰ C, the other part ■ it a drawn on Malzagair culture of Pellicularia infected sasakil and set up at 28 to 30 ⁰ C and 100 t relative humidity in each case.

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5 to θ days after the inoculation, the infestation is determined in all the leaves present at the time of inoculation with Firicularia as a percentage of the untreated, but also inoculated control plants. In the case of the plants infected with Pellicularia sasakii, the infestation on the leaf sheaths is determined after the same time in relation to the untreated, but also infected control. 0 1 * means none and 100 ^ that the infestation is just as high as in the control plants.

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Test for curative effect

In the test described above with a liquid active ingredient preparation the curative effect of the process products is determined in addition to the protective effect. the Testing for curative effect differs in certain points from the test procedure described above, which is only one A statement about the protective effect is provided, insofar as the active ingredients do not take place before, but only 16 hours applied after the inoculation. Substances that have an effect on this type of experiment show are able to kill the fungus after infection and thus have a curative effect.

The active ingredients tested, the concentrations used and the results obtained are shown in Table 1 below:

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Table 1 Piricularia (a) and Pellicularia (b) tests

Active ingredient (constitution) Infestation in i »of the infection of the untreated control at an active ingredient concentration (in $) of

*) 0.05 (a) 0.05 (b)

Cl-CH ₀ -CH ₀ -O

^Ls -O- ^ci pr. 0 cur. 33

12th

Cl-CH ₀ -CH ₀ -O v ^ "

pr. 0 cur. '0

Cl 0

CH ^ -CH-CH-O-P CH,

Cl pr. 0 cur. 13th

Cl

CH ₅ -CH-CH-OP CH,

SQ-OH ₃ pr. 0 cur. 21

17th

Cl-CH ₀ -CH-O CH,

; pn (ch ₃ ) ₂ pr. 0

*) pr. = protective cur. = curative

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. Table 1 (Portposition) Piricularia (a) and Pellicularia (b) test

Active ingredient (constitution)

Infestation in 1 »of the infection of the untreated control at an active ingredient concentration (in ^) of

*) Q, 05 (a)

0.05 (b)

Cl-CH ₂ -CH-O

ι
CH,

pr. 0

50

CH,
Cl-CHp-CH-O.

pr. 0

.O " ^CH2 " ^S ^ PN- (CH ₃ ). Cl-CH ₂ -CH ₂ -O

pr. 0

^ Vs. S.

PO-CH ₅ -CH ₉ -Cl

CIU

C1-CH-CH ₂ -CH ₂ -O _N "

Cl

P-N

.CJH,

CH, pr. 0

pr. 0

\ 2

Cl-CH-CHo-

CH ₃ OIL

*) pr. = protective effect cur. = curative effect

- 16 -

pr. 0

109883/1861

50

Example B.

Bacteria test / Xanthomonas oryzae

Solvent: 4 parts by weight of acetone

Dispersant: 0.05 part by weight of sodium oleate

Water: 0.2 parts by weight gelatin

other additives: 95.75 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount Amount of solvent and dilute the concentrate with the specified amount of water, which contains the additives mentioned.

30 rice plants about 30 days old are sprayed with the spray liquid until they are dripping wet. The plants remain until the A btrocknen in a greenhouse at temperatures of 22 to 24 ⁰ C and a relative humidity of about 70 "ß>. Thereafter, the needles are dipped in an aqueous Balcteriensuspenaion of Xanthomonas oryzae and the plants were inoculated by pricking the _t leaves. the plants are after inoculation in a room at 26 to 28 ° C and OEO $ relative humidity.

10 days after the inoculation, the percentage of all untreated but also inoculated leaves of the control plants is determined for all leaves injured by the sting, inoculated and previously treated with the preparation. 0 $> means no infestation, 100 # means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in Table 2 below P9883 / 1 86 1

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Tabel

Bacteria test / Xanthomonas orycae

Active ingredient (constitution)

Infestation in # of the infestation in the ■ untreated control

a V ^r irkstoffkonzentration tn $>) of

0.05

Cl-CH ₂ -CH ₂ -O 0

^G 2 ^H 5 25

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Example 1;

ClCH ₀ CH ₀ O 0

P-S- / 'VCi

(CH ₃ J ₂ IT

A solution of 33.7 g (0.25 mol) of 2-dimethylamino-1,3-dioxaphospholane in 100 ml * 2 Di chlorine than is added dropwise with stirring and external cooling at -5 to ⁰ ° C with 44.7 g ( 0.25 mol) of 4-chloro-phenylsulfenic acid chloride, dissolved in 50 ml of dichloromethane. After one hour of reaction, the mixture is washed with dilute sodium bicarbonate, soda or alkali metal hydroxide solution until it reacts neutrally, then dried over sodium sulfate and freed from the solvent under reduced pressure. A pale yellowish oil with the refractive index n'i remains as a residue. 1.5641 «The yield is 72.0 g (91.6% of theory).

Analysis:

C ₁₀ H ₁₇₁ Cl ₀ NO ₀ PS (Iiol weight 314.2) 10 14 dd ρ _{s C1 N}

Calculated: 9.9 '!'·>', 10.2 ,'■>; 22.6 '/ -; 4.4 ^r / ^;

Found: £ 10.0; 10.3 #; 22.9 > \ 4.3 tf.

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Example 2:

ClCH ₂ GH ₂ O _x ? ,,

* * ^ / Vci

p-S- / V

In a manner analogous to Example 1, 4-9 »0 g is obtained (0.3 mol) 2-diethylaminodioxaphospholane-1,3,2 and 58.8 g (0.3 mol) 4-chloro-phenylsulfenic acid chloride 101.5 g (98.8 # of theory) of a pale yellowish oil with the refractive index η £ 1.5559.

Analysis;

C ₁₂ H ₁₈ Cl ₂ NO ₂ PS (molecular weight 342.2)

PS Cl N Calculated: 9.1 ⁰ M $ 9.4 > \ 20.7 "/>; 4.1 #;

Found: 9.1 </ °) 9.6 '/ ■>; 21.0 #; 3.9 9 ».

Example 3:

CH,

egg

In a manner corresponding to that described in the preceding examples, by reacting 35.5 g (0.2 mol) of 2-dimethylamino-5,5-dimethyl-dioxaphcsphorinane-1,3,2 with 35.9 g (0.2 mol) of 4-chloro-phenylsulfenic acid chloride the Connection of the above constitution in the form of a weak

τ. i, ,, "109883/1861

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Al

yellowish oil with the refractive index n £ 1.5460, The yield is 61.4 g (86.2% of theory).

Analysis: C ₁₅ H ₂₀ Cl ₂ NO ₂ PS (molecular weight 356.3)

P S Cl N

Calculated: 8.7 #; 9.0 #; 19.9 #; 3.9 %; Found: 8.7 'M 9.0 #; 20.0 ^C / S; 3.9

The following connections can be established in an analogous manner:

Constitution refractive index

CH ₃ CH ₃ Cl-CH - CH-O

^P ~ ^S "\

-Cl nV 1.5482

CH ₃ CH ₃ Cl-CH - OH-O

^ PS- ^ VCH, 4f 1.5362

CH ₃

Cl-CH ₉ -CH-O 9 _iF - _p ,

^d ^ PS- / Vci n ^ 1.5556

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constitution

Refractive index

CH ₃ CH ₃ Cl-CH - CH-O 0

"p-

(CH ₃ ) ₂ N

1.5288

CH, "

Cl-CH ₉ -CH-O

P-SCH,

1.5418

1.5421

Cl-CH ₀ -CH-O O

1.5410

Ci-CII ₂ -CH ₂ -OO

P-S-CH

2 \ - 1.5542

Cl-CH ₀ -CH ₀ -OO

i> -: s-y W

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constitution

Refractive index

CH

Cl-CH-CH ₀ -CIi ₀ -O 0 ^{2 2} \ "

(CH ₃ ) ₂ N

n ²² 1.5489

CH-

l-6h-

Cl-CH-CH ₀ -CH ₀ -O. "

η ²² 1.5393

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Claims (4)

is claims; 1. Process for the preparation of thiolphosphoric acid-Q-haloalkyl-S ~ aryl- or -aralkyl-diester-dialkylamides of the general formula R _K R, R ₁ 0
i5 i3, 1 " R, - C- (C JCOP-SH ₇
Hal R ₄ R ₂ NR ₈ R ₉ ^ characterized in that 2-dialkylamino-dioxaphospholane or phosphorinane derivatives of the general formula ^R 4 CO ^ß 5R ₆ with sulfuric acid halides of the formula Hal-SR ₇ converts, with in the aforementioned formulas R | to R ₆ stand for Waseerytoi'fntome, alkyl or haloalkylreete, R _{7 is} an optionally substituted aryl or Aralkyl group means
R _& and Rq straight-chain or branched lower alkyl or represent alkenyl radicals, while Hai represents a halogen, preferably chlorine or 3roi.iatom stands and
η the value zero or. Has. * _ΛΠ O U _k i _LJii . : I ₄ - 109883/186 1 2. Fungicidal, bactericidal, insecticidal and acaricidal agents, characterized by the content of thiolphosphoric acid-O-halo-alkyl-S-aryl- or -aralkyldieeter-dialkylamides according to claim 1. 3. A method for combating felts, bacteria, insects and mites, characterized in that one thiolphosphoric acid-O-haloalkyl-S-aryl or -aralkyl-diester-dialkylamides according to claim 1 on fungi, bacteria, insects, mites or their habitat. 4. Process for the production of fungicidal, bactericidal, Insecticidal and acaricidal agents, characterized in that thiolphosphoric acid-O-haloalkyl-S-aryl- or -aralkyl-diester-dialkylamides according to Claim 1 with extenders and / or surface-active agents Means mixes. Le A 11 444 - 25 - 109883/1861