CS196257B2 - Fungicide - Google Patents

Abstract

1449394 Phosphite mono esters and their salts PEPRO SOC POUR LE DEVELOPPEMENT ET LA VENTE DE SPECIALITES CHIMIQUES 12 Dec 1974 [14 Dec 1973 23 Oct 1974] 53752/74 Heading C2P [Also in Division A5] Phosphite mono-esters and their salts of the general Formula I in which R is a linear or branched chain alkyl radical containing from 1-18C atoms which is unsubstituted or substituted by halogen or nitro; an alkenyl, alkinyl, alkoxy alkyl, or alkenoxy alkyl radical, each of which is unsubstituted or substituted by halogen and the hydrocarbon portion of each radical contains from 1-8 C atoms; a cyclohexyl radical; an optionally substituted aryl radical, or aryl alkyl radical; or a heterocyclic radical optionally attached to the oxygen atom through an aliphatic chain, preferably tetrahydro urfuryl, M represents a hydrogen atom, an ammonium cation, ammonium substituted by from 1-4 alkyl or hydroxy alkyl radicals containing from 1-5 C atoms or by 1 or 2 cyclohexyl radicals or a phenyl radical, or a cation of a metal comprising an alkali metal, an alkaline earth metal, or a polyvalent metal, n is an integer equal to the valency of M are prepared, e.g. by (i) transesterifying a dialkyl phosphonate with phosphorous acid in accordance with the equation: (ii) hydrolysing a phosphorous acid dichloride with water in accordance with the equation or (iii) hydrolysing or saponifying an 0,0-dialkylphosphonate in accordance with the equation Several specific compounds which have been prepared are mentioned such compounds including sodium o-methyl phosphonate, sodium o-n-hexadecyl phosphonate, ammonium o-ethyl phosphonate, o-methyl phosphonate, o-cyclohexyl phosphonate, diethyl ammonium o, ethyl phosphonate, tetramethyl ammonium o-methyl phosphonate, calcium o-ethyl phosphonate, and iron o-ethyl phosphonate. The products have fungicidal properties.

Description

The present invention provides a fungicidal composition based on phosphonic acid monoesters (or phosphonates) and salts thereof. These compounds are sometimes also called monoalkyl 1- (aryl-) phosphonates. In particular, the invention relates to a composition which is suitable for use against parasitic fungi on plants and which contains as an active ingredient at least one compound of the general formula:

where

R is an optionally halogenated C 1 -C 8 alkyl, C 2 -C 5 alkoxyalkyl, alkenyl or alkynyl, phenyl, benzyl or tetrahydrofurfuryl radical.

M represents a hydrogen atom, an ammonium cation, an ammonium cation substituted by 1 to 4 alkyl or hydroxyalkyl groups containing 1 to 5 carbon atoms or substituted by 1 to 2 cyclohexyl residues or a phenyl residue, or a metal cation from the group consisting of alkali metals, preferably sodium and potassium, alkaline earth metals, preferably magnesium, barium, calcium and polyvalent metals such as preferably zinc, manganese, divalent and trivalent copper, iron, nickel, aluminum and n are integers equal to M.

Some of these compounds are already known. V. V. Orlovskl et al. 'described in' Z. Z. obšč. chim. St. 42, p. 1924 (1972) for the preparation of numerous monoalkyl phosphite salts and especially monoethyl phosphite with metal or more or less substituted ammonium cations, although they do not mention the fact that these compounds have fungicidal properties.

It has now been found that the compounds of the invention exhibit excellent fungicidal properties, particularly with respect to various powdery mildew types such as grape powdery mildew, tobacco mildew and hop mildew.

These compounds can be prepared by the following general procedures (cf. Houben-Weyl, Vol. XII / 2).

First, phosphonates can be prepared by transesterification of dlalkyl phosphonate with phosphorous acid [E. E. Nifantev, L.P. Levitan,

For C2H6O3NaP

I - alkali metal salts and ammonium salts

4.54% H, 23.45% P

4.63% H, 23.3% P

C, se

t.

according to Chemical Abstracts 1107e (1966)] according to the scheme (cf. Houben-Weyl, Vol. XII, p. 7) involves the hydrolysis or saponification of O, O-dialkylphosphonate according to the reaction scheme.

In particular, the O-octylphosphonate can be prepared by this process.

As far as salts are concerned, they can be prepared by at least two processes: The first of these processes is particularly suitable for the preparation of alkali metal salts and ammonium salts.

> 300 ° C, 68% yield.

C,

Ammonium salts are prepared by ...

written for ammonium O-ethylphosphonate:

0.036 mol of Ο, Ο-diethylphosphonate is calculated:

18,18 '% found:

18.18% (ROb ~ ^p ^ _u ^{+ (} ° C ⁾ 3 ^P / Cl

R0 ~ P * ^{2 H} _Z ⁰

O ^R0 \ p + M0H-- ⁵

Ro

t.

t. t

t. t.

mp 52 ° C

The O-ethylphosphonate was prepared as follows: The equimolar mixture of Ο, Ο-diethylphosphonate and phosphorous acid was heated at 150 ° C for 6 hours. In quantitative yield, a liquid having an index of no ²⁰ = 1.4211 and a density d = 1.0043 (20 ° C) is obtained.

The following compounds can also be prepared by this process: O-methylphosphonate, O-n-hexylphosphonate, O-isooctylphosphonate, ........

O-n-nonylphosphonate

The saponification is carried out with a mineral or organic base in aqueous solution. The duration of the reaction is from 1 to 4 hours at a temperature from ambient to reflux (in an aqueous medium). The compounds obtained, which are usually water-soluble liquids or solids, are isolated by removing water and any solvent.

The O-ethyl phosphonate is prepared as follows: One equivalent of sodium hydroxide in an aqueous-alcoholic solution is added dropwise to the aqueous-alcoholic solution of O, O-diethylphosphonate with stirring. After standing for two hours, the alcohol and water were removed by distillation under reduced pressure on a water bath. The solid residue was recrystallized from anhydrous alcohol.

<2 RO-P-OH> 1 |

O

O-n-decylphosphonate

O-n-dodecylphosphonate, O-n-hexadecylphosphonate, O-cyclohexylphosphonate, O-phenylphosphonate and O-benzylphosphonate.

Esters of the invention can also be obtained (see Houben-Weyl, Vol. XII / 2, p. 6) by hydrolyzing phosphorous dichloride with two equivalents of water according to the reaction scheme.

RO-P-OH 12 HCt

II

O

V. _t ^R (^ -P ^ C ^ M + ^R0H

II

O

This procedure

Sodium O-methylphosphonate m.p.

Sodium O-n-propylphosphonate, m.p. 195 to O-Sodium sopropylphosphonate, m.p. 132 to O-n-butylphosphonate, sodium O-n-octylphosphonate, sodium O-n-dodecylphosphonate, sodium O-n-hexadecylphosphonate, prepare the following salts:

125 ° C

196 ° C

133 ° C

178 ° C

Mp 167 ° C

Mp 100 ° C

6 in 25% aqueous ammonia solution. After 1 hour of standing, the solution was evaporated under reduced pressure in a water bath. Initially the gummy and colorless residue crystallizes. Crystallization from ethanol-acetone gave colorless needle crystals.

Yield: 87%, mp 99-100%.

For C2H10NO3P calculated:

% C, 18.90;% H, 7.87;% N, 11.02.

24.41% P

П Й 1 Ο7ΟΤΊ ГУ

% C, 18.93;% H, 7.90;% N, 11.10.

24.29 Ψο P

Other alkali metal salts, the properties of which and, if appropriate, the particular conditions of preparation are given in the following table, are obtained by changing the saponification base and / or the alkyl moiety in the process described above.

В 25 7

О tí

О í ч от от от от О О С С С С С С С С С С <<<<<

ID

СО Ш СО О тЧ тЧ со гН еэг-^ сч ^ со гЧ со оо счгп tjT σί со ч ^ со о СЧ гЧ r-Η гЧ СЧ СЧ

о ио ад ад о ш ад ад сч о ч < ч <къч * от CD СЧ ~ СО 00 о сч ад СО ' СЧ СЧ ^ гЧ со со о о со Ч <СП от со ч <от Сч ^{1 1} от гН ч · сч сч ад гЧ гЧ ад гч тч сч ^нн

м 4— ¹ ЬОЙ со > £ >> р л я £ 1 2 сх . л * 2 Рч N N 'СО N о Й 0 d О ř- ( х> ч -О r-t

CD CM O

C \ CD СО 00 CD CM * t <rH tH CM

CO CO 00 O. CD CD CO ю * cd σΓ cm cm cm тН СО 00 CD with CD-ROM * cm r-T cm CM

CO XM CD CD CD CD C C 1 R o o co co CM .00 CM

TMч t> cd TM CD. tH CD CT ^ O * CD co CD * 00 rH in 00 oo CD CD 'rH rH' rH CD O OOO CM n co σι ω CD CD 00

CD * CD * CD * CD * CD * CD * CD * CD * CD * CD * CD * CD * CD * CD

O eo

ta á % o the δ % o of £ ΰ % of T O £ Τ ’o 5 OF T <ω

'Honors

Да N >>

СО 00 сл о

CM * О * X г * 41 * О * СО * Ш * тН гЧ

О) О 00 СП гЧ * СО * х СО * X σΓ о? X СО гЧ оо сл о σ

X

41 * ш * оо * сл

) О) О со о о см со оо * со со * сл оо со гЧ СМ СМ _л см * ь> * со * сл ю X о * см * со * СМ гЧ см тН СМ см

см О) Q Ю Ю m СО * 00 * со М> NO ’ со ш см ю Q □ N О о 00 * ю * со * см * сл * СО сл * ts СО * гЧ * о * со * см сл * сл * ÍN 41 * 1 * * со * сл * СМ * О * оо * сл * Ю * 0 * 0 со * со гЧ гЧ СМ гЧ СМ гЧ см см

О К Z Dm о Z Z дм о Z Z Дч о

СО

СО

СО

СО

о Q 'Honors да ω 1П со * ю f Honors With д * а й ® М- » Рч М-Д W) Λ

Дм Дч Дч л Дч Дч й it О О Z ^ ч О ьо о of OF of of а со о ČM 14 о of of оз X <М о X X CÓ о со о <3 А ьо ω

СН = С — СН2—0 — Р — О- NH4 ⁺ СзНвЫОзР 1.1. 69 ° С> 74 Н 5.84 5.84 || soluble N 10.20 10.24

О, .. .. Р 22.60. ·, 22.53

tx гЧ СО СМ

СП СП г> * t + гЧ

СП 00 СП СП тН! + Со о т-to to * t + * со * Xt> гЧ

СП СО тН 'Ф СО ХГ 1П vfi со * Гх * со * гЧ

CD Ср СО СП

_СМ-0Э СМ л 00 00 * Гх Гх * * * It ОО гН

ОЗ ”ф со

Г \ 00 _л Γγ хН О со * Гх * Гх * 00 тН

О Гх tx О гЧ * ΙΌ Гх * 00 * гЧ хл * со * г »* со * гН

О to to 00 ^ СО ^ СО _л си СМ * Гх * Гх * со * 00 гЧ о Ж Z to

О Z Z to О Z Z to o Z Z to

o CD

oo Гх

honors 4tí CJ 0 o Í5 0 - < ω 0 xt < 00 \ ΗΗ 00 O with it CM rH 5 r4 _t . CD 4-J + - · Д • w +4 • sorry ~ N O t4 + - »

ω о

Ф CD

ύΗ

Z со

2:

V 'о x-ó- = o о

i ⁴ О

198257

8

II - Substituted. ammonium salts

a) Alkanolammonium and alkylamine salts Preparation of monoethanolammonium salt of O-ethylphosphonic acid

0.05 mol of O, O-dimethylphosphite is poured into an aqueous solution of 1 equivalent of monoethanolamine. The reaction is carried out for 1 hour at 50 ° C. Evaporation of water yields a water-soluble oily liquid.

Yield 35% n _D ²⁰ = 1.4595.

Calculated for C 4 H 14 NO 4 P:

28.1% C, 8.2% H, 18.1 o / o P found:

% C, 28.16;% H, 8.2%;

Similar compounds were prepared using the same procedure, the properties of which are shown in the table below. In all cases, yields are greater than 85%.

со о fa> о honor

Х2

cd>

\ <- I й 'СО>

N

CD сб 44 44 4- » 'СО 'Honors г 4 '' СО 'Honors О д О о Я о -к * о о 4- » О ω О см 2 1Л g. Л М < «> 5 . л + · * N W 4- »Ь4 . О .о -ч ч н Ή Ч

Д 1 д ω д о | \ _и 1 ю ♦ чм Д д д д д ΪΕ еч ω о no .. č О

19.6 2 5'7

- S ‘ > ф я Й TJ о л О д ф гЧ Й о О А Р <о ΰ а N3 > | -Ч О 0 О й 9 > Ф Й СО 'Й > о · - <) t-1 Л cl й ч ~ » й ^ £> 0) V4 О > »Ř4 'Й- > ё а> 44 Ф ⁴ д се '>? о > и < й N Й> 1 Л 1 N 1

<0 со со CD О 00 со стГ со Tfl во со ю Ю гЮ □ СП о сГ з-Г

СО гЧ гЧ СМ со 10 О

00 ^ со σΓ оГ со xt <з-Ч

СО СО 0О

10 ^ 0 о оо θ 'θ' CM 00 з-ЧгЧ СМ

О К Z Р- »

О i Ос

Another method for preparing alkylammonium salts involves reacting the ammonium halide with di. o (/ го; _г -Р _{% п} * alkylphosphorite according to reaction scheme «Θ ©> R0-P-0 NHR + RX

II P

O (cf. Orlovsky et al., J. Organ. Chim., USSR, 1972, vol. 42, pp. 1924-27).

The following compounds can be prepared by this procedure:

- O-ethylphosphonic acid monoethylammonium salt - O-ethylphosphonic acid diethylammonium salt - O-ethylphosphonic acid triethylammonium salt

b) Quaternary ammonium salts

Preparation of tetramethylammonium salt of O-methylphosphonic acid

0.05 mole of O, O-dimethylphosphite is added to an equivalent amount of trimethylamine in acetone solution. The reaction mixture is maintained at 50-60 ° C for 2 hours. Evaporation of acetone gave a highly hygroscopic water-soluble solid. Yield 77%.

For C5H16NO3P calculated:

35.5% C, 9.47% H, 8.28 θ / ο N,

18.35 ° / o P n до 1о7рпл ·

H, 9.22; N, 8.22.

18.48% P

The same O-ethyl and O-1-isopropyl derivative is obtained in the same way, replacing O, O-dimethylphosphite with O-methyl-Q-ethyl and O-methyl-O-isopropylphosphite. The reaction is carried out in acetone / tril at 70-100%. The solids obtained are recrystallized from acetone.

O-ethylphosphonic acid tetramethylammonium salt yield 94%, mp 134%.

For CsHiaNOsP calculated:

% C, 39.4%;% H, 9.84;% N, 7.65.

16,95% P found ·

C 39.38, H 9.40, N 7.80, P 16.90

Tetramethylammonium salt of O-isopropylphosphonic acid

Yield 92%, mp 153%.

For C7H20NO3P calculated:

H, 10.15; N, 7.11.

15.7% P found:

H, 10.26; N, 7.13.

15.9% P

III - Salts of divalent metals

The metal halide is reacted with di-alkylphosphorite according to the reaction scheme η Θ Θ 1 (ROL-Ρζ + MX → R RO JOM + W ^Z Ό O (cf. Orlovsky et al., Organ. Chim., Vol. 42, 1924-1972).

O-ethylphospho is thus prepared. Calcium.

A mixture of 11 g (0.01 mol) of calcium chloride and 2.8 g (0.02 mol) of O, O-diethylphosphonate is heated with stirring at 110 to 130% for 2 hours. The mixture was then cooled to give a precipitate which, after filtration and washing, afforded white crystals having a melting point above 420%. Yield 96%.

For С4Н120бРгСа calculated: 18.6% C, 1.5% H found: 19.12% C, 1.98% H

By substituting the starting salt, the following salts can be prepared in a similar manner:

Barium O-ethylphosphonate

Zinc O-ethylphosphonate

Zinc O-ethylphosphonate

To a suspension of 0.1 mole of magnesium oxide in 100 ml of distilled water are added

0.2 mol of O, O-diethylphosphite. The exothermic reaction is carried out with stirring at 50 ° C for 2 hours. After filtration, water was evaporated from the filtrate to leave a white solid which was washed with acetone and dried.

Yield: 100%, m.p. above 300'C.

For C4H12MgO6P2 calculated:

% C, 19.83;% H, 4.96;% Mg; 10.02%;

% C, 19.90;% H, 5.22;

25.60% P

The table below lists the characteristics (appearance, m.p., water solubility) and analyzes of other metal alkyl phosphonates obtained in the same manner as in the previous example. Unless otherwise indicated, yields are greater than 70%; most of the yields being quantitative. For manganese salts, the metal oxide is replaced by carbonate as the starting material.

6 - 2 & 7

Ф

О CD 00 b ю со <3 со с C0 и о СМ см

©. CD rH. WHAT. CD CM CM CM

CD CO b © b rh what in co b b what CM rH cdm · what © -. CD CD CD r r-Γ cd b o CO CM

CO © CD O ©. rH From b oo b b co CM. rH

CM 1D ID O ι oo oo oo co * CM * CM CM

CM CM

CD. CD CD CD. cd L0 cm

CM CM

Ή CD © b ^ ^ ^ ^ oo oo b b b r r r r r r r r r

CM ~ b CD 00 cm CD 00 CM CD CD © b 0M.CM ^ UD oo ь b oo CM rH sf CD CO CO 00 CD 1П co uo b cd CM b CD © co rH UD CD ^ ©. and in CM CM rH CM

W) b0 o M S to o E. S o. 00 Honors o M S.to ω E o ta

-m

VB honors it a

>

Φ _

tí

M (Λ 0 & n About M

4tí

M what 3 to N O M '3 M

4M

CO to N O w 'ω _ & n' 3 3 + J co 0 & N O f-l

МЙ> φ

Mtí

4- »

What the

with <a 9 я E E CM E CM eq CM cm CM CD CM what the ем (T E it O CM O <o o % % the 00 the 00 0 <o O bO <0 o 00 it O 00 WITH Aš it O bO 3 it about it X — 4 Ϊ 2 p. S p . with о with eM :: 5 O E ω я <0 E it Ed 5 о O O O

Ьф bo

S S

b0 bo s p

Q.

Pi

1 E bO E i l Ο- •O the CM Ι - ω E l N . 1 O E O E o CM E o 1 it O Ю E E E E O o o O

198257

д 'СО 'Honors 44 4Ú Г— < О О О Я 4- »сл я я 4- »сл Я чО О 00 fa й я • fa N Я λίΗ 40 Д Я 44 О ч 44 4-1 4ti ti я Я * я 5 я 'Я Я 'Я г-Н > φ 4- » > 'со ф Д > Ф 2 'ι-Μ fa 4- * fa, Q fa Λ

'СО 'со ев _ 'СО Я Я л '2 я 4-J W 4-> ел За § 4-1 сл Я Я 4ч сЛ я fa fa. • 2 fa fa N Honors й я N й О Р 44 Μ 4_ι 3 о о Д ⁰ ч £ CD '' Д См чо s я - 'я ~ я ^Q 2 я ^м > Я ω Д > '(0 ω Д ř> S φ φ > With д ф д farQ faD fa я- farQ 4-1

N 04 / ¢ 4 еч 4 ⁴ fa СО fa СО fa it fa со fa СО о о . О о О я я Я Я я no о no О ω со £ Й Д а д а д Д δ 00 ω СО О  со Р со и

X-cLaO

AND

CD t + CD t + tx ^ OO rH ~ LO ~ co * to * o * o * CM rH CM

CM rH tx CD co CM ~ LO CO * to * co * o * CM rH CM

ιη to

Ф> ω '> S>

O O O CM

LO CD ^ 10 ~ CO 'rH to * CD * o * CM rH rH

CD 'CM O

LO CD 00 ~ XF rH what * co * co * CM rH rH tx 00 rH rH CD tx 00 ~ CD * CO * CO * CO *

00 ^ 00 tx CD to tx * CM rH rH

O tx 00 C O O tx CO rH o O CO rH what * to * т-T cd * oo * to CM CM CM CM t □ SSft

Xf — 4 Tl я Я —ι о N cd 4t Й <* ph s> o ^p o 3 δ «2 vCd ^ S Cd) N 4? 4- » SI § '« tí > p g <a > f-4 Ф z and> z ф ca to> to-Q to4D to Д

C /> > - <N ca J-4 N to'ca Ό 4tí Ό N 0 ^ 4tí 'CD 4tí O o> N ω > • r * 4 Й 4- »ω ω • гЧ> Й Z G it no й N 1—4 ω ca Ф O ω to Й > Gí >

СбШбОбРгИп Zn 21.03 21.19

P 20.06 20.03

§

198257

IV - Salts obtained by double cation exchange

a) Synthesis through barium salt

Zinc O-n-butylphosphonate

0.05 mol of O-n-butylphosphonate and 0.05 mol of barium hydroxide are dissolved in 150 ml of distilled water. Barium O-n-butylphosphonate is precipitated. A solution of 0.05 mol of zinc sulfate heptahydrate in 20 mL of distilled water is then added to precipitate barium sulfate which is separated by filtration or centrifugation. The clear filtrate was evaporated to dryness to give a highly viscous liquid, which was dried under reduced pressure. This liquid is water soluble.

Yield: 82%.

For CetooOePZZn calculated:

C, 28.31; H, 5.89; Zn, 19.17.

18.28% P found:

28.16 ° C, 5.96% H, 19.46% Zn,

18.28 'O / o P

Compounds whose characteristics are listed in the table below are obtained as described above, either by changing the alkyl residue or the metal. Unless otherwise stated, yields are greater than 70%.

CD CD rH CD ID

LD CD * <50 * ri ri

CM 00 cd t - ^ CD tD 'rH' co * cd cd oo *

CM T-H rH

CD 00 CM Ή H rH CD t> 00 СО Э H rH 00 * ID * CD * 00 * CM T-. rH rH CD CO ', 00 CO * UM

rH CM

О И N ta

О X N ta

'Honors 'Honors 4Ы (Л with ω > ф 3 3 rQ the the honor N N 'it O O f-i 4 honor 3 44 Sr-T M 4- » tí Я to 4tí N N Я-т- < Ό Ό S * 4ti N гт 44 and* £ 3 Я я .0.) 0)

я φ

· Ta ·

+ H · + + + + + + + t tí tí я d • + N 2 2 N · <

1 .x  it X о 1 к я Sž “° ем X о O ~ СЧ ж и -ω к о _м / no 1 см X о о x х ж X X. no no о no о

СНзОСНгСНз— Fé ⁺⁺ СбН1бЕе © бРг solid soluble

6 2 5’7:

о

honors д

honors д о

Ю ФЮ

О * СМ 1Л * О * о? X см см гЧ см см

о >>>

Z о Z о Дч

+, о

b) Sodium salt

Aluminum O-isopropylphosphonate

Sodium O-isopropylphosphonate was prepared. To a solution of 0.18 mole of this compound in 150 ml of distilled water, a solution of 0.06 mole of aluminum nitrate with 9 molecules of water in 30 ml of distilled water was added to precipitate aluminum O-n-propyl phosphonate. The precipitate is centrifuged, washed with water and acetone and then dried under reduced pressure to give a white solid, water-insoluble solid.

ka. J. «. : j <‘-Vl ·, ·. Yield: 60%, m.p. above 300 ° C.

For C9H24AlO9P5 calculated:

% C, 27.67;% H, 6.06;% 6.82.

C, 27.19; H, 6.28; Al, 6.90; P, 23.50

The table below shows compounds prepared similarly by the same method from sodium O-alkylphosphonate. The ferric salts are obtained by substituting aluminum nitrate with ferric nitrate.

The table also shows the characteristics of these compounds. Unless otherwise stated, yields are greater than 70%.

6 2 5 7 cd

ri

Ν

О

ОТ Ф 00 ОТ СО 00 гН ОТ см * со * со * θ ’со см со СО От от

ОТ ^ гН 'гЧ ~ СМ * СО * СО гЧ * со см со Ф ф ф

ГЧ'ОТ'ГИ'СМ 'СМ * СО * СО * г-1 * со см гЧ ОТ Ф Ф От СО

Ф ^ сз СО СМ СМ СО СМ о * to * со * to * Ф ф

М С Ч Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю Ю О Ю СМ * СО * СО * гЧ * со см от о

ОО'О СО'СО 'со со н О * to * t со * t <Ф * ь> * СМ СМ гЧ см

22,4 17,87 alcohol product contains% №ВГ2

CD X <fa

О Д <Вч CJ Д § CU

CD honors honors Honor Honors 4d 4-J CD й ω 4tí M CD 4tí 4-1 CD 4t + - · O CD 9 'CD Q 'Honors 'Honors ⁹ 'Honors 'Honors 0 'Honors 'CD 0 'Honors 0 O O O 0 '2 Oчв O 12 About what Й 4- * ω 2 ° λ <-4 Д tn 12 ABOUT WHAT ri 4-> ω 12 O ri 12 0 0 ^w t O WHAT 13 Д rQ Ttí д 13 Ό ri 13 та ri rQ . G Ό 'cd Д cd Д fa N O what 2 Д ^G fa N O 'Honors ri Honors ri fa N O 'Honors ri honors fa ri O ^U O 'Honor g & O <3 ri > 4-J S-4 > + J Her > • ř-i > 4J f-1 > 4J • CD ω CD Φ CD CD ω CD CD  . fa 4-i ri fa 4-i ri fa 4-J ri fa • U ri. fa 4J ri 4-i

еч fa

1 X - CD 1 bO X CD еч X CD ( 1 «4 1 CM X X CJ У it 1 it X X X X CD CD CD CD

19B2S7

ОН а

Ρπ

CO CN 'CO 00 ho-u * r-T CM · rH · CN

COφ CO O CO

CN 4 · * CO CO тп 'то - co * ^rH CN rH CN □ OO o)

0 rH * rH. 5 5 O * co cN o * CO rH rH

O CO «3« Φ CN 00 'rH O, · rH 05 O rH * O * O * CO * rH * O * CO CN * O * CO rH · CO iH CN rH Φ P> Φ CO rH

1П 10 co * тН CN rH CN oo rH <Φ O • Φ CO, rH UO * 10 CO Г-Г CN · rH CN

WHAT

M CN '05 -CO CN 05 rH · Ο · Φ® 00 5 ^ 0 O

O * co * r * O * CD * r * 05 * CO тН CO '' rH rH ·. 05 /

E + p <

u E Ch on φ φ φ

UZ ta Рч OZ ta QZ Дм Дм ^Ή O a • w

S r-H> Q Ό

Рч + ->

O O τί honor

Λ ta " Bye· vs % ьо Ph § σ> O 03 / O δ φ Φ and> and> j CN OF · Bye at ^{£ 3} 8 ‘ 8 TO OF ^OF O CM . CM v < Í4 O « O O CJ

+ + +  + + 4 · + + + 4 · · + : + - +. + + Φ Φ Φ- φ Φ the the·. '· Bye Bye the

it

X ω

AND

E ·· · U -

I eq

E ω í w E O ώ

⁶ · i E o

O \ E u

KJ.

E U.

Ferric O-ethyl phosphonate

For: C 6 H 16 FeCl 3 P 3

Ferric O- (2-chloroethyl) phosphonate

Example -i

For: CeH15C13FeO9P3 wt. %

5 'wt. % W / w. % by weight,%

Exam . on peronospora grapevine (Plasmopara vlticola in vivo) found:

18.90 -% C, 3.80% H, 14.63% Fe, ... A; - - 24.2% P '·

The following examples illustrate the fungicidal properties of the following compounds:

foundQ _:

C 14.78%, H 3.019%, Fe 21.77%,

18.78% P calculated:. .

H, 3.04; H, 21.9. -% Fe, - 19,1 -% P calculated:.

% C, 18.80;% H, 4.70;

V - Iron salt

This compound was prepared as described in Chem. Ber. 90, page 811, involving the reaction of ferric chloride with 3 equivalents of ethylphosphoric acid. Filtration and washing gave a solid with a melting point above 300 ° C.

This compound was obtained by the above-described Orlovsky procedure, but using chloride instead of sodium hydroxide. ferric. Iron (III) salts of phosphonate may be prepared in this manner, for example ferric O- (2-chloroethyl) phosphonate, which decomposes at a temperature of about 135 ° C. Ammonium O-methylphosphonate Ammonium O-ethylphosphonate O-ethylphosphonate Sodium - Calcium O-ethylphosphonate τ Ammonium on-propyl phosphonate - Ammonium odsopropylphosphonate - · Ammonium on-butyl phosphonate - Ammonium on-lhexyllosphonate - O- ['(2-ethyl) -n-hexyl] ammonium phosphonate - Sodium on-octylphosphonate - · Sodium on-dodecylphosphonate - On ^: ammonium sodium hexadecylphosphonate - ammonium O-methoxyethylphosphonate - ammonium O-cyclohexylphosphonate - ammonium O-benzylphosphonate - ammonium O-tetrahydrofurfurylphosphonate.

- sodium - tetramethylammonium salt of O-methylphosphonic acid ¹⁸ .

- Dicyclohexylammonium salt of O-methylphosphonic acid - Potassium O-ethylphosphonate - Magnesium O-ethylphosphonate - Barium O-ethylphosphonate - Zinc O-ethylphosphonate - Manganese O-ethylphosphonate - Aluminum O-ethylphosphonate - O-ethylphosphonate O - ethylphosphonate - O-ethylphosphonate nickel ethylphosphonate - magnesium on-propylphosphonate - sodium O-sopropylphosphonate - calcium O-sopropylphosphonate - O-O-isopropyl aluminum phosphonate - O - O - ^; Sodium (O) -O-n-butylphosphonate - O-sec-ammonium O-sec-butylphosphonate - Aluminum O-sec-butylbutylphosphonate - One - [(2-ethyl) n-hydroxy] ] Calcium phosphonate - - - O · Sodium methoxyethylphosphonate - Magnesium O-methoxyethylphosphate - Ammonium O-propargylphosphonate - Ammonium phosphonates

(a) Precautionary treatment. .

, Leaves - rošthn vine - - (species Gamay), grown in pots, are sprayed on the underside -Sa. use smear cuts. - 'pistol with aqueous suspension - wettable - powder - having the following composition:

Test substance active deflocculant (calcium lignosulfate) Y wetting agent;

(sodium alkyaryl sulfonate) filler. (aluminum silicate).

in the desired dilution containing the test drug at the desired dose. Each test is repeated three times.

After 48 hours, the plants are infected by spraying the lower surfaces of the leaves with an aqueous suspension - fungal spore, at a concentration of 80,000 units / ml.

The pots were then placed in an incubator at -20 ° C and 100% relative humidity for 48 hours.

The test result is determined 9 days after infection.

It is found that under these conditions at a dose of 0.5 g / liter, compounds 1 to 9, 11 to 22, 24, 26 to 30, 32 to 38 and 40 to 42 provide complete protection, while the - 23, 25 , 31 and 39 offer good protection.

It is also found that none of the test compounds is at least phytotoxic.

196267

(b) 'post-infection' treatment

The procedure is as in (a), except that the plants are first infected and then. only treats with a twisted-active substance; after 9 days after infection, the test result is determined.

Under these conditions, it was found that at a dose of 1 g / liter of compound 1-8, 10-29, 31, 32, 36 and 40-42, the development of peronospora on vine plants was completely stopped.

(c) Symmetric root absorption test

Several vines (Gamay species), individually planted in pots containing vermiculite and nutrient solution, are sprayed with 40 ml of a solution containing 0.5 g / l of test substance. After 2 days, the vine is infected with an aqueous suspension containing 100,000 spores. / ml peroriospora (Plasmopara viticola). The infected plants are then kept in a room at 20 ° C and 100% relative humidity for 48 hours. The degree of infestation is determined after 9 days compared to control plants which have been sprayed with 40 ml of distilled water.

Under these conditions, it is found that compounds 1 to 18, 20 to 35 and 37 to 42 at a dose of 0.5 g / liter, upon root absorption, provide complete protection of the vine leaves against peronospora, clearly demonstrating the systemic nature of these compounds.

Example 2

Test against vine peronospora in the wild

Groups of 5 vines (Gamay) are sprayed every 8 days with an aqueous solution containing 200 g / h of active substance and, in one case, with a wettable powder:

- Active substance. (compound) - calcium lignosulfate '(detlocating agent) - sodium alkylarylsulfonate - silicon dioxide (anti-lump) - kaolin (filler)

Perúnospora (Plasmopara viticola) appears from July 24th. The natural infection is considerable. In August, the bushes are sprayed so that the leaves are kept moist. The fungal infestation is considerable and in September the fungus is still supported by particularly wet weather.

At the end of October, the number of peronospore-infected areas in each parcel was determined on the leaves that were effectively treated.

It is found that under these conditions, the plants, based on one plot of land, are characterized by 136 sponge infested areas, while on plots where the plants consist of 50 wt. % wt. % wt. % wt. % 39 wt.

ly treated with compounds Nos. ^2, 3, .4, 21, ^22, 26, 31 and 39, the contamination .houbou completely absent. ·, ·. '

In addition, only a few areas sponge-sponge, per plot, are found on the shoots that have not yet been present when the plants have been treated, sufficiently confirming the systemic character of the test compounds found in the greenhouse tests.

Example 1 a d 3

Tobacco test

Groups of 5 tobacco plants. (.PB 91) is .o? saves 15 June with a wettable powder containing 160 g / liter of maneb (80%), 300 g / liter of sodium O-ethylphosphonate and 300 g / liter of magnesium O-ethylphosphonate (50%). For control purposes, one group is left untreated.

After 48 hours, the plants are artificially infected with peronospora tobacco and gently sprayed with water. This treatment is then repeated once a week.

On August 12, an assessment is made with counting the fungus infested areas in each group. The results are shown in the table below:

Substance Number of sponge infested sites in each group

Control group48 maneb4

Sodium O-ethylphosphonate2

O-ethylphosphonate

magnesium1

Other tests show that the two compounds of the invention are also effective against this fungus in post-plant treatment and have a systemic effect.

Example 4

Tests on seedlings Avocado

The seedling Avocado (Persea indica) is planted in soil infested with Phythophtora cinnamomi and then sprayed with a solution containing 3 g / liter of aluminum O-ethylphosphonate. Several plants are left untreated as a control. After 20 days, it is found that, under these conditions, the roots of the control plants are completely destroyed, while 90% of the roots of the treated plants are healthy.

Example 5

Pineapple test

The young pineapple plants are infected with the fungus Phytophthora parasltica, followed by infestation. hours sprayed with solution

198257 containing 0.5 g / l of calcium O-ethylphosphonate. After 30 days, the treated plants are found to completely suppress fungal growth while the control plants are infested.

Example 6

The strawberry plant (Surprlse des Halles) test is treated by immersion for one hour in an aqueous solution containing 0.2% calcium O-isopropylphosphonate, dried and then planted on a soil infested with Phytopthora cactorum on 14 June. Immediately thereafter and every 8 days thereafter until 18 July, the plants are sprayed with the same solution, corresponding to a total use of 0.5 g of active ingredient per plant.

Seedlings treated with immersion in water and sprayed with water are used as control plants.

Under these conditions, on July 24, it was found that the protection of the treated strawberry plants was perfect while 76% of the control seedlings had died.

Example 7

The test on Jamaican pepper plants of Yama wonder, which have already been planted in the wild, is transplanted into pots on June 27 with phytophthora rot (Phytophthora capsici) artificially infested. Immediately after transplanting and then once every 8 days until 18 July, the plants are sprayed with an aqueous solution containing zinc O-ethylphosphonate so that each plant is treated with a total of 0.5 g of active ingredient.

Water-sprayed plants serve as a control.

Under these conditions, it was found that by the end of August none of the 10 treated plants had been infected, whereas the control plants had all died by 25 July.

All these examples convincingly demonstrate the remarkable fungicidal activity of the compounds according to the invention, namely the systemic action against peronospora, which prevents and stops the growth of grapevine peronospora and, on the other hand, against certain phytophoric infections.

However, it has also been found that the compounds of the present invention are highly active against other types of parasitic fungi such as Gulgnardia bidwelli in grapevine, Pseudoperonospora humuli, Bremla lactucae, Phytophthora infestans, Peronospora sp., Phytophthora palmivora and other fungi of Phytophthora sp., in mild and tropical climates, such as tobacco, and especially useful and ornamental plants, as well as onions, green peppers, tomatoes, beans, soybeans, citrus, cacao, coconut, rubber.

The compounds according to the invention are therefore particularly suitable for the preventive or curative treatment of plants infected with fungal infections, in particular diseases caused by fungi of the Phycomycetes and Ascomycetes classes in said vegetable species, but more generally also for agricultural, horticultural, plant and ornamental plants, for use in the winery.

The compounds according to the invention can advantageously be used in mixtures with one another or in mixtures with other known fungicides, such as metal dithiocarbamates (maneb, zinc, mancozeb), basic salts or hydroxides of copper (oxychloride, oxysulfate), (tetrahydrojphthalimides (captan, captafol, folpel) ), N- (1-butylcarbamoyl) -2-benzimidazoles, methylcarbamate (benomyl), 1,2-di- (3-methoxy or ethoxy) -carbonyl-2-thloureidobenzenes (thiophonates), methyl 2-benzimidazylcarbamate, etc., either to complement the range of activity of the compounds of the invention or to increase their persistence.

It has also been found that the compounds of the invention may be mixed with other fungicidal, protiperonosporous phosphorus derivatives, in particular 2-hydroxy-1,3,2-dloxaphospholanes, 2-hydroxyethylphosphorates and phosphorous acid and its salts.

The doses in which the compounds of the invention are used may vary within wide limits depending on the virulence of the fungus and the climatic conditions. Dosages in the range of 0.01 to 5 g / liter of active ingredient are generally suitable.

For practical application, the compounds of the invention are rarely used as such. Instead, they are generally used in compositions which generally contain a carrier and / or a surfactant in addition to the active ingredient of the invention.

Carrier in this context means an inorganic or organic, natural or synthetic substance with which the active substance is mixed in order to facilitate its use in the treatment of plants, seeds or soil, or its transport or handling. The carrier can be a solid (clay, natural or synthetic silicates, resins, waxes, solid fertilizers) or a liquid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, liquefied gases).

The surfactant may be an ionic or non-ionic emulsifier, dispersing or wetting agent, such as polyacrylic and lignin sulfonic acid salts, ethylene oxide condensates with fatty alcohols, fatty acids, or fatty amines.

The compounds of the present invention can be used in compositions prepared as wettable powders, soluble powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.

The wettable powders of the present invention may be prepared containing 20 to 95 wt. % of the active ingredient, and usually contain, in addition to a solid carrier, up to 5% by weight of active compound; % wetting agent, 3 to 10 wt. % dispersing agent and optionally up to 10 wt. % of at least one stabilizer and / or other additives such as penetrating agents, adhesives, or anti-agglomerating agents, dye, etc.

An example of a wettable powder composition is:

- Active ingredient 50% - Calcium lignosulphate (deflocculating agent) 5% - Anionic wetting agent 1% - Silica (anti-clump) 5% - Kaolin (filler) 319%

Water-soluble powders are obtained by mixing 20 to 95 wt. · Active ingredient, up to 10 wt. and the remainder being a water-soluble filler, mostly salt.

Examples of compositions of the soluble powder include: - active ingredient 70% - anionic wetting agent 0.5% - silica, (anti-agglomeration) 5% - sodium sulphate (soluble filler) 24, 5%

Also included within the scope of the invention are aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or an emulsifiable concentrate of the invention with water. These emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency similar to that of mayonnaise.

The compositions according to the invention may contain other additives, for example protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants, as well as other active substances known for their pesticidal properties, in particular acaricides or insecticides.

Claims (23)

1. A fungicidal agent against fungal infestations, characterized in that, in addition to the inert carrier and the usual additives, it contains, as active ingredient, at least one compound of the general formula p-o II J _n o / ^l where: R is an optionally halogenated alkyl radical of 1 to 8 carbon atoms, alkoxyalkyl, alkenyl. or a (C 2 -C 5) alkynyl, phenyl, benzyl or tetrahydrofurfuryl radical, M represents a hydrogen atom, an ammonium cation, an ammonium cation substituted by 1 to 4 alkyl or hydroxyalkyl groups containing 1 to 5 carbon atoms or 1 to 2 cyclohexyl or phenyl radicals, or a metal cation from the group comprising alkali metals, preferably sodium and potassium, metals alkaline earths, preferably magnesium, barium, calcium and polyvalent metals such as preferably zinc, manganese, divalent and trivalent copper, iron, nickel, aluminum, and n is an integer equal to a valence M. 2. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) VYNALEZU 1 wherein M is an ammonium cation substituted with 1 to 4 alkyl or hydroxyalkyl radicals containing 1 to 5 carbon atoms, or 1 to 2 cyclohexyl radicals or phenyl radicals. 3. A composition according to claim 1, wherein the active ingredient is a compound of the formula (1) wherein M is an alkali metal cation, 4. The composition of claim 1, wherein:. The composition of claim 1, wherein M is an alkaline earth metal cation. 5. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein M is a metal cation. groups including zinc, manganese, divalent and trivalent copper, divalent and trivalent iron, nickel and aluminum. 6. A composition according to any one of claims 1 to 4, wherein the active ingredient is a compound of formula (I) wherein R is optionally halogenated or nitrated (C1-C8) alkyl, optionally halogenated alkenyl or alkynyl, alkoxyalkyl a radical, an alkenoxyalkyl radical, wherein the four kinds of radicals each contain from 1 to 5 carbon atoms. . 7. A composition according to claim 6, characterized in that it contains a compound of the formula (I) as active ingredient 1, wherein R is an alkyl radical, a halogenated C1 -C4 alkyl radical, an allyl, propargyl, allyloxy or alkoxyalkyl radical containing 2 to 3 'carbon atoms. 8. A composition according to claim 7, wherein the active ingredient is a compound of formula (I) wherein R is ethyl. 9. A composition according to claim 7, wherein the active ingredient is a compound of formula (I) wherein R is an isopropyl moiety. 10. A composition according to claim 8, wherein the active ingredient is sodium O-ethylphosphonate. 11. A composition according to claim 8, wherein the active ingredient is calcium O-ethylphosphonate. 12. A composition according to claim 8, wherein the active ingredient is aluminum O-ethylphosphonate. 13. A composition according to claim 8, wherein the active ingredient is magnesium O-ethylphosphonate. 14. A composition according to claim 8, wherein the active ingredient is zinc O-ethylphosphonate. 15. A composition according to claim 8, wherein the active ingredient is cuprous O-ethylphosphonate. 16. A composition according to claim 8, wherein the active ingredient is copper (I) -ethylphosphonate. 17. A composition according to claim 9, wherein the active ingredient is sodium O-isopropylphosphonate. 18. A composition according to claim 9, wherein the active ingredient is calcium O-isopropylphosphonate. 19. A composition according to claim 9, wherein the active ingredient is aluminum O-isopropylphosphonate. 20. A composition according to claim 9, wherein the active ingredient is magnesium O-isopropylphosphonate. 21. A composition according to claim 9, wherein the active ingredient is zinc O-isopropylphosphonate. 22. A composition according to claim 9, wherein the active ingredient is O; copper (I) isopropylphosphonate. 23. A composition according to claim 9, wherein the active ingredient is cuprous O-isopropylphosphonate.