Field of the invention

This invention relates to new fungicidal compositions.

Prior Art

US Patent No 292701 4 discloses phosphonates and phosphinates having herbicidal activity. In WO 941 8837 and WO 9304585, it is disclosed that certain phosphonates can enhance the activity of specified herbicides. We have now found that such compounds can also be used with advantage in association with fungicides used to combat phytopathogenic fungi.

Description

The invention provides a fungicidal composition which comprises a mixture of

(a) a fungicide used to combat phytopathogenic fungi and

(b) at least one phosphonate or phosphinate of formula I

O

»1 . (I)

where

R ¹ is C .20" ^a " ^< Vl _» C5.20" ^a "<oxy or optionally substituted phenyl R2 IS benzyl, Cg_2cr ^a| _< optionally interrupted by NH or 0, dι-Cβ-20" ^a " ^< vlamιno or the group

CH ₂ CH ₂

and

R ³ is C6_2Cr ^{al k} y ^| -

Phosphonates of formula I wherein R ¹ is Cg-C20-alkoxy and R^ is Cg-C20-a"<yl are known. They are made for example according the disclosure in DE 1 ,963,014.

Phosphinates of formula I wherein R ^ is Cg-C20-alkyl and R^ is phenyl are new and form part of the invention. They are made by catalytically induced addition of olefins to phenyl monoalkylphosphonites which are preferably prepared as described in DE patent 1 96 041 95.

Also the ethane-1 ,2-diphosphonic acid tetraalkyl esters of formula I wherein R ¹ is Cg-C20 ^-a " oxy and R^ is the group

O

CHoCHo- P ( O R ^J I are new and also form part of the invention. They are made by addition of the appropriate phosphonates to a dialkyl vinylphosphonate in the presence of basic catalysts such as sodium methylate or sodium hydride.

Alkyl- or dialkylaminoalkylphosphonic acid dialkyl esters of the formula

O

R ³ R ⁵ NC H ₂ (CH ₂ ) _X P (O R ³ ) ₂ wherein R ³ is as defined above and R^ is R ³ or hydrogen and x is 0 or 1 are also new and also form part of the invention. They can be prepared according to two different methods. Compounds wherein x is 0 are made according to the following equation

0 0

R ³ R ⁵ NH + HCHO + H P (OR ³ ) _: R ₃ 3 ^J _R R5°NC H ₂ (CH ₂ ) _χ - (OR ³ ) ₂ H ₂ 0

Compounds wherein x is 1 and made according to the following equation:

0 n

R 3 ^3J oR ^D 5rN H + CH2= CH — P (OR ^J ) ₂ ^► R ^3J R RR5=°>lN> C H ₂ (CH ₂ ) _χ P (OR ^J ) ₂ + H ₂ 0

(R5 being preferably hydrogen)

The addition of the amine is made in the presence of basic catalysts such as sodium methylate or sodium hydride according to the process described by A. N. Pudovik et al., Doklady Akad. S.S.S.R. 80365( 1 951 ), (A 50, 4143( 1 956) .

Component (a) is generally a compound selected from

(i) a conazole steroid demethyiation inhibitor,

(II) a steroid reduction inhibitor based on a 1 -[3-(4-tert-butylphenyl}-2- methylpropyl] group which is attached via the N-atom to pipeπdine or 2,6-dιmethylmorphohne (in) a dithiocarbamate fungicide

(iv) a phthalimide fungicide in which a chloroalkylthio group is attached via the N-atom to the optionally hydrogenated phthalimide group (v) an anilide fungicide (vi) an mbc fungicide. (VII) a carbamate fungicide

(VIII) a copper compound fungicide (ix) a tin compound fungicide (x) a strobiluπn type fungicide, (xi) a 2-anιlιnopyπmιdιne fungicide (xn) a compound which causes systemic activated resistance, or

(XIII) a fungicide selected from the group consisting of chlorothalonil, dimethomorph, fenpiclonil, fluazmam, hymexazol, nuaπmol, pencycuron, pyπfenox, thicyofen, probenazole, pyroquilon, tπcyclazole, quaternary ammonium compounds, fludioxonil, 5-chloro- 2-methyl-4-ιsothιazo!ιn-3-one, 2-methyl-4-ιsothιazolιn-3-one (and mixtures of these two), furmecyclox, 3-ιodo-2-propynyl butyicarbamate, quinoxyfen and sulfur.

Conazoles are defined in ISO standard 257 as compounds based on imidazole or 1 ,2,4-tπazole and containing a halogenated phenyl group. Examples include prochloraz (and its metal complexes - especially the zinc, manganese or copper complex), propiconazole, flusilazole, hexaconazole, tebuconazole, difenoconazole, bromuconazole, cyproconazole, diniconazole, fenbuconazole, imtbenconazole, furconazole, tetraconazole, myclobutanil, penconazole, fluquinconazole,

azaconazole, imazalil, tπflumizole, epoxiconazole, tπticonazole, metcoπazole and the fungicide having the code No SSF 109.

Examples of type (ιι) fungicides include fenpropimorph and fenpropidin.

Examples of type (in) fungicides include mancozeb and thiram.

Examples of type (iv) fungicides include folpet, captafol and captan. Examples of type (v) fungicides include a) 3',5'-dιchloroaπιlιde fungicides in which the ani no nitrogen comprises a ring carrying two oxo substituents, in positions adjacent the nitrogen, e.g. iprodione, vinclozolin or procymidone, or b) acetanilide fungicides, e.g. metalaxyl or ofurace, c) sulfanilide fungicides, e g dichlofluanid, d) benzanilide fungicides, e.g flutolanil, and e) heteroarylanilide fungicides, e.g. thifluzamide.

Examples of type (vi) fungicides include carbeπdazim, benomyl and thiophanate- methyl.

Examples of type (vn) fungicides include diethofencarb and propamocarb.

Examples of type (VIII) fungicides include Bordeaux mixture, oxine-copper, copper oxychloπde and copper naphthenate.

Examples of type (ix) fungicides include tπbutyltin oxide and tnbutyltin naphthenate.

Strobiluπn type fungicides (type (x) fungicides) are methyl esters or N-methyiamides of arylacetic acid in which the acetic acid also carries a methoxymethylene or methoxyimino substituent. The aryl group is usually a 2-substιtuted phenyl group and/or can be separated from the acetic acid by a linking group such as oxygen. Examples of such compounds are those disclosed in a wide number of patent applications, including EPs 1 78808, 1 78826, 203606, 203608, 206523, 21 2859, 22691 7, 229974, 242070, 242081 , 24301 2, 243014, 243014, 244077, 251082, 25321 3, 254426, 256667, 260794,

260832, 267734, 270252, 273572, 274825, 278595, 280185, 280383, 291196, 307101, 307103, 310954, 312221, 312243, 329011, 331061, 331061, 331966, 335519, 337211, 341845, 342459, 348766, 350691, 354571, 363818, 370629, 373775, 374811, 378755, 379098, 382375, 383117, 384211, 385224, 385357, 386561, 386681, 387499, 389901, 393428, 393861, 398692, 400417, 402246, 405782, 407873, 407891, 414153, 420091, 422597, 426460, 429968, 430471, 432503, 433233, 433899, 438726, 439785, 459285, 460575, 463488, 463513, 464381, 468684, 468695, 468775, 471261, 471261, 472224, 472300, 473980, 474042, 475158, 477631, 480795, 483851, 483985, 487409, 489660, 498188, 498396, 499823, 503436, 508901, 509857, 513580, 525516, 528245, 528681, 531821, 532022, 532126, 532127, 534216, 535980, 538097, 544587, 546387, 547825, 548650, 554767, 554957, 564928, 564984, 567828, 571326, 579071, 579124, 579908, 581095, 582902, 582925, 583806, 585751, 590610, 596254, 596692, 600835, 602514, 606924, 611760, 617011, 617014, 619301, 622355, 623604, 624570, 625520, 627411, 628540, 634405,644183, 647631, 656351, 656352, 658542, 658542, 658543, 658547, 662477, 667343, 669315, 673923, 691332, 704430, 711759, 731095 and 738716 and WOs 90/07493, 90/10006, 92/18487, 92/18494, 93/08183, 93/07116, 93/08180, 93/15046, 93/16986, 93/22921, 94/00436, 94/05626, 94/08968, 94/10159, 94/11334, 94/14322, 94/14761, 94/17060, 94/19331, 94/22812, 94/22844, 94/26700, 94/26705, 95/01328, 95/01329, 95/01330, 95/01973, 95/04728, 95/05367, 95/05368, 95/06033, 95/14015, 95/14674, 95/17376, 95/20569, 95/21153, 95/21154, 95/21156, 95/21833, 95/24383, 95/24396, 95/25095, 95/25729, 95/29896, 95/30639, 95/31448, 95/33164, 95/34526, 96/01256, 96/01258, 96/04239, 96/06072, 96/07633, 96/07636, 96/10556, 96/11183, 96/14305, 96/16026, 96/16029, 96/16030, 96/16044, 96/16047, 96/17851, 96/20164, 96/20570, 96/22983, 96/25398, 96/25406, 96/31463, 96/35669, 96/35690, 96/37477, 96/37480, 96/38408, 96/38411, 96/38425, 97/00011, 97/00012, 97/00611, 97/00612, 97/00856, 97/00859, 97/00866, 97/01530, 97/01537, 97/01544, 97/01545, 97/03563, 97/03948, 97/03950, 97/05103, 97/05120, 97/06133, 97/06677, 97/06678, 97/06679, 97/06680, 97/06681, 97/06682, 97/06683, 97/06684, 97/07096, 97/07099, 97/07103 and 97/11606.

Specific compounds are those having the having the common name kresoxim- methyl and azoxystrobin.

Examples of type (xi) fungicides include pyπmethanil, mepanipyπm and cyprodinil.

An example of a type (xiii) fungicide is that having the code number CGA 2425704, which is sold under the trade name "Bion" and is S-methyl benzo-1 ,2,3- thιadιazole-7-carbothιoate.

The names quoted for these compounds are the non-proprietary common names and the chemical structure can be found for example by reference to the "Pesticide Manual" , tenth edition, 1 994, published by the British Crop Protection Council. Of the compounds whose common names are not mentioned in the Pesticide Manual the full chemical names are as follows: epoxiconazole 1 -[3-{2-chlorophenyl)-2-(4-fluorophenyl)oxιran-2-ylmethyl]-

1 H-1 ,2,4-trιazole kresoxim-methyl methyl (E)-methoxιmιno[α-(σ-tolyoxy)-σ-toly]acetate azoxystrobin methyl (E)-2-{2-[6-(2-cyaπophenoxy)pyrιmιdιn-

4-yloxy]phenyl}-3-methoxyacrylate quinoxyfen 5,7-dιchloro-4-quιnolyl 4-fluorophenyl ether

The invention is particularly useful for fungicides of high melting point and/or low solubility in organic solvents. It is particularly applicable to fluqumconazole and azoxystrobin, and especially fluqumconazole.

We have found that phosphonates of formula l, which have little or no activity in their own right considerably enhance the fungicidal activity of fungicides and especially fluqumconazole and azoxystrobin.

The weight ratio of component a) to b) is generally between 10: 1 and 1 : 10, preferably between 3: 1 and 1 :5.

The compound of formula I can be added to conventional formulations of component a). It may be desirable to also add small quantities of solvent and/or surfactant especially a non-ionic surfactant, and other additives such as fatty acids to improve the emulsifiabi ty of the compound of formula I.

The following Examples illustrate the invention.

Example 1 Into a reaction vessel, which was heated to 1 00°C, with a reflux condenser (-1 5°CΛ were simultaneously added aqueous formaldehyde ( 1 2.17 g of 37% solution) and a mixture of dι(2-ethylhexyl)amιne (36.22 g) and dι(2-ethylhexyl) phosphonate (45.96 g). The mixture was heated for 1 hour with stirring and then cooled to 20°C. The water was removed by distillation under reduced pressure to give dι(2-ethylhexyl) {[dι(2-ethylhexyi)amιno_methyl}phosphonate, as a colourless liquid (n ° = 1 .4563).

Example 2

A mixture of 2-ethylhexyl vinylphosphonate, 2-ethylhexylamιne (66.50 g) and sodium hydride (0.10 g) was stirred at 1 30°C for 6 hours. After addition of an additional amount of sodium hydride (0.10 g) and stirring for 9 hours there was obtained dι(2-ethylhexyl) {[{2-ethylhexyl)amιno]methyl}phosphonate, as a colourless liquid (n _D = 1 .4537).

Example 3

To a mixture of 2-ethylhexyl vinylphosphonate (49.9 g), dι(2-ethylhexyl) phosphonate (45.9 g) and THF (80 ml) was added at 20°C with stirring, a solution of sodium methylate in methanol until the mixture reached pH 8-9 The mixture was stirred for 1 2 hours and water ( 1 00 ml) and ethyl acetate (200 ml) added. The organic phase was separated, dried with sodium sulfate, filtered and the solvent evaporated uπαer reduced pressure to give tetra(2-ethylhexyl) ethane- 1 ,2-dιphosphonate as a colourless liquid, n ° = 1 .4488.

Example 4: A mixture of 2-ethylhexyl vinylphosphonate (49.90 g), octadecylamme (40.43 g) and sodium hydride 0.10 g was stirred at 140°C for 6 hours. Water ( 100 ml) and ethyl acetate (200 ml) were added. The organic phase was separated, dried with sodium sulfate, filtered and the solvent evaporated under reduced pressure to give

di(2-ethylhexyl) [2-(octadecylamino)ethyl]-phosphonate, as a colourless liquid, n _D ⁰ = 1 ,4541

Example 5: A mixture of tetradec-1 -ene (30.05 g) and benzoyi peroxide (0.3 g) was added dropwise with stirring to 2-ethylhexyl phenylphosphonate (38.95 g) at 1 60°C. The resulting mixture was stirred for 6 hours to give 2-ethylhexyl phenyl tetradecylphosphinate, as a colourless liquid, n _D = 1 .481 3

Example 6

In a similar manner to example 5, starting from octadec-1 -ene, there was obtained

2-ethylhexyl phenyl octadecylphosphinate, as a colourless liquid, n^ ⁰ = 1 .4729

Example Z

Wheat plants were inoculated with Erysiphe graminis (powdery mildew). One day after inoculation, they were sprayed with fluqumconazole, obtained by diluting with water to the desired concentration, a suspension concentrate comprising 50% by weight active ingredient, at a rate of 50 g fluquinconazole/ha either alone or mixed with various inactive phosphonate or phosphinate esters added at a concentration of 0.1 % v/v, together with an appropriate emulsifier.

One week after spraying, the wheat was assessed for control of disease. The results are as follows.

Example 8

In a similar manner, Example 7 was repeated with some of the phosphonates and with replacing fluqumconazole with other fungicides. The results are as follows

1 1 / 1 8

Example 8

Example 7 was repeated in tests against Puccinia recondita using azoxystrobin

Results are as follows:

Example 9

The following are typical formulations incorporating fluquinconazole and the preferred phosphonate according to the invention.

a) an SC formulation was made from the following components

lsion was made to the following composition.