1-Azabutadienes and fungicides containing these compounds

Abstract

1-Azabutadienes of the formula ##STR1## where R.sup.1 and R.sup.2 are each phenyl, biphenyl, naphthyl or pyridyl, and these radicals may be substituted, or are each alkyl which is unsubstituted or substituted, R.sup.3 is substituted or unsubstituted phenyl or a radical OR.sup.4, where R.sup.4 is hydrogen, alkyl or an aromatic or aliphatic acyl group, or R.sup.3 is a radical NHR.sup.5, where R.sup.5 is hydrogen, substituted or unsubstituted phenyl, or the carbamide group, and fungicidal agents containing these compounds.

Description

The present invention relates to 1-azabutadienes and fungicides containing these compounds.

We have found novel 1-azabutadienes of the formula I ##STR2## where R.sup.1 and R.sup.2 are identical or different and are each phenyl, biphenyl, naphthyl or pyridyl, and these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each straight-chain or branched C.sub.1 -C.sub.8 -alkyl which is unsubstituted or substituted by unsubstituted or substituted phenyl, and

R.sup.3 is unsubstituted or substituted phenyl or a radical OR.sup.4, where R.sup.4 is hydrogen, straight-chain or branched C.sub.1 -C.sub.6 -alkyl or an aromatic or aliphatic acyl group, or R.sup.3 is a radical NHR.sup.5, where R.sup.5 is hydrogen, unsubstituted or substituted phenyl or the carbamide group CONH.sub.2, which have a very good fungicidal action.

In formula I, R.sup.1 and R.sup.2 independently of one another are each, for example, 1-naphthyl, 2-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, p-biphenyl, phenyl, halophenyl, e.g. 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl or 4-bromophenyl, halo-C.sub.1 -C.sub.4 -alkylphenyl, e.g. 2-trifluoromethylphenyl, 3-trifluoromethyllphenyl or 4-trifluoromethylphenyl, C.sub.1 -C.sub.4 -alkylphenyl, or 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, C.sub.1 -C.sub.4 -alkoxyphenyl, e.g. 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl or 2,4,6-trimethylphenyl or C.sub.1 -C.sub.8 -alkyl, in particular C.sub.1 -C.sub.4 -alkyl, e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl or 2,2-dimethylpropyl, benzyl, halobenzyl, e.g. 4-chlorobenzyl or 4-fluorobenzyl, C.sub.1 -C.sub.4 -alkylbenzyl, e.g. 4-methylbenzyl, 2-chlorobenzyl, 2-fluorobenzyl, 2-methylbenzyl or 2-phenylethyl, halophenylethyl, e.g. 4-chlorophenylethyl or 4-fluorophenylethyl, or 3-phenylpropyl.

Particularly preferred compounds are those in which R.sup.1 is an unsubstituted or substituted phenyl ring, for example phenyl or halophenyl, e.g. 4-chlorophenyl, 4-fluorophenyl, 2-chlorophenyl or 2-fluorophenyl, and R.sup.2 is 2,2-dimethylpropyl or 3,3-dimethylbutyl or unsubstituted or substituted phenyl, for example phenyl or halophenyl, e.g. 4-chlorophenyl, 4-fluorophenyl, 2-chlorophenyl or 2-fluorophenyl.

R.sup.3 is, for example, hydroxyl or the group OR.sup.4, where R.sup.4 is an aliphatic or aromatic acyl radical, for example C.sub.1 -C.sub.4 -alkyl-CO, acetyl, propionyl, butyryl, benzoyl or halobenzoyl, e.g. 4-chlorobenzoyl, or unsubstituted or substituted C.sub.1 C.sub.6 -alkyl, in particular C.sub.1 -C.sub.4 -alkyl, such as methyl, ethyl, propyl or butyl, benzyl or halobenzyl, or

R.sup.3 is a radical NHR.sup.5, where R.sup.5 is hydrogen, the carbamide group CONH.sub.2 or unsubstituted or substituted phenyl, for example phenyl or nitrophenyl, e.g. 4-nitrophenyl or 2,4-dinitrophenyl.

Finally, R.sup.3 is furthermore unsubstituted or substituted phenyl, for example phenyl, halophenyl, such as 4-chlorophenyl or 4-bromophenyl, or C.sub.1 C.sub.4 -alkylphenyl, such as 4-methylphenyl.

R.sup.3 is particularly preferably hydroxyl and derivatives derived therefrom which can be obtained by alkylation or acylation.

1-Azabutadienes of the formula I can be obtained, for example, by reacting an aldehyde II ##STR3## with a compound of the formula H.sub.2 N-R.sup.3 in the presence or absence of a catalyst and of a suitable solvent. Waterremoving agents, such as molecular sieves, such as magnesium sulfate, sodium sulfate or calcium chloride, may be used as catalysts, as well as acids, such as sulfuric acid, hydrochloric acid or acetic acid, or basic compounds, such as sodium hydroxide, potassium hydroxide, potassium carbonate or potassium acetate. Examples of solvents are lower alcohols, such as methyl alcohol or ethyl alcohol, and their mixtures with water, as well as propyl alcohol, isopropyl alcohol, butanol, sec-butanol or tert-butanol, ketones, such as acetone, ethers, such as diethyl ether, tetrahydrofuran or methyl tert-butyl ether, and methylene chloride, aromatic hydrocarbons, such as toluene or xylene, and dimethylformamide and dimethyl sulfoxide.

Method 1

5,5-Dimethyl-2-formyl-1-(p-chlorophenyl)-hex-2-ene (compound 136a)

79 g (0.79 mol) of 3,3-dimethylbutyraldehyde are added to a solution of 10.5 g of 50% strength by weight aqueous NaOH in 500 ml of methanol, after which 123 g (0.73 mol) of p-chlorodihydrocinnamaldehyde are added dropwise at 34.degree. C. The mixture is stirred for one hour and then neutralized with dilute sulfuric acid, the solution is evaporated down and the residue is then subjected to fractional distillation.

Bp. 119.degree.-122.degree. C/0.01 mbar, yield 115.9 g (59% of theory)

Method 2

1-(o-Chlorophenyl)-3-(p-fluorophenyl)-2-formylprop-1-ene

71.7 g (0.51 mol) of 2-chlorobenzaldehyde are added to a solution of 4 g of 50% strength sodium hydroxide solution in 300 ml of methanol while cooling, at a rate such that the temperature does not exceed 20.degree. C. 70.0 g (0.46 mol) of p-fluorodihydrocinnamaldehyde are then added dropwise at 25.degree.-30.degree. C. in the course of 4 hours. Stirring is continued for one hour at 30.degree. C., the mixture is neutralized with dilute sulfuric acid and evaporated down and the residue is distilled.

Bp. 164.degree.-184.degree. C./0.3 mbar; yield 97.8 g (77% of theory)

Method 3

4,4-Dimethyl-2-formyl-1-(p-chlorophenyl)-pent-1-ene (compound 63a)

134 g (0.95 mol) of 4-chlorobenzaldehyde are added to a solution of 15.8 g of 50% strength sodium hydroxide solution in 500 ml of methanol, after which 90 g (0.79 mol) of 4,4-dimethylpentanal are added dropwise at 35.degree. C. in the course of 3 hours. Stirring is carried out for three hours, after which the mixture is neutralized with dilute sulfuric acid and evaporated down and the residue is distilled.

Bp. 117.degree.-120.degree. C./0.4 mbar; yield 83.5 g (39% of theory)

PREPARATION EXAMPLE 1

compound 136

4.2 g (0.06 mol) of hydroxylammonium hydrochloride, dissolved in a methanol/water mixture, and 4.1 g (0.03 mol) of potassium carbonate were added to a solution of 7.5 g (0.03 mol) of the aldehyde from method 1 in 100 ml of methanol. After a reaction time of one hour at 25.degree. C., the mixture was evaporated down and the product was extracted with methylene chloride. Yield 6.8 g (85% of theory), mp. 78.degree. C.

PREPARATION EXAMPLE 2

compound 139

5.0 g (0.019 mol) of the oxime from Example 1 were dissolved in 50 ml of tetrahydrofuran, and 3.0 g of pyridine and 0.1 g of 4-(N,N-dimethylamino)-pyridine were added, followed by the dropwise addition, at 50.degree. C., of 2.2 g (0.03 mol) of acetyl chloride dissolved in 20 ml of tetrahydrofuran. After a reaction time of 72 hours at 25.degree. C., the mixture was evaporated down, the residue was taken up with methyl tert-butyl ether, the solution was washed with dilute NaHCO.sub.3 solution and the organic phase was dried and evaporated down.

Yield 4.3 g (78% of theory), IR bands: 2958, 1769, 1492, 1366, 1204 cm.sup.-3

The following compounds can be prepared in a similar manner.

TABLE 1__________________________________________________________________________ ##STR4##No. R.sup.1 R.sup.2 R.sup.3 m.p. (.degree.C.)/IR__________________________________________________________________________ (cm.sup.-1)/(NMR)1 n-C.sub.3 H.sub.7 phenyl OH2 n-C.sub.3 H.sub.7 4-ClPh OH3 n-C.sub.3 H.sub.7 4-FPh OH 91-934 n-C.sub.3 H.sub.7 4-FPh NHCONH.sub.2 1525 n-C.sub.3 H.sub.7 4-MePh OH6 n-C.sub.3 H.sub.7 2-ClPh OH7 n-C.sub.3 H.sub.7 2-FPh OH8 n-C.sub.3 H.sub.7 2,4-Cl.sub.2 Ph OH9 n-C.sub.3 H.sub.7 3-pyridine OH 118-12110 n-C.sub.3 H.sub.7 3-pyridine OMe11 n-C.sub.3 H.sub.7 3-pyridine OEt12 n-C.sub.3 H.sub.7 3-pyridine OCOMe 0.9-2.6(9, m); 2.2(3, s); 6.8-8.7(6, m)13 n-C.sub.3 H.sub.7 3-pyridine OCOPh 0.9-2.7(9, m); 6.8-8.7(11, m)14 n-C.sub.3 H.sub.7 4-pyridine OH15 n-C.sub.3 H.sub.7 2-pyridine OH16 n-C.sub.3 H.sub.7 1-naphthyl OH17 n-C.sub.3 H.sub.7 2-naphthyl OH18 n-C.sub.3 H.sub.7 4-biphenyl OH19 n-Bu phenyl OH20 n-Bu 4-ClPh OH21 n-Bu 4-FPh OH22 n-Bu 4-MePh OH23 n-Bu 2-ClPh OH24 n-Bu 2-FPh OH25 n-Bu 2,4-Cl.sub.2Ph OH26 n-Bu 3-pyridine OH27 t-Bu Ph OH28 t-Bu 4-ClPh OH 108-11029 t-Bu 4-ClPh OMe30 t-Bu 4-ClPh OEt 2959, 1490, 1092, 105531 t-Bu 4-ClPh OCOMe 2961, 1769, 1490, 120332 t-Bu 4-ClPh OCOPh33 t-Bu 4-ClPh NHPh34 t-Bu 4-FPh OH35 t-Bu 4-FPh OCOMe36 t-Bu 4-MePh OH37 t-Bu 2-ClPh OH38 t-Bu 2-FPh OH39 t-Bu 2,4-Cl.sub.2Ph OH40 t-Bu 3-pyridine OH 17841 t-Bu 3-pyridine OCOMe 0.8-2.7(14, m); 6.9-8.7(6, m)42 t-Bu cyclohexyl OH 8843 t-Bu cyclohexyl OMe 2930, 2852, 1448, 105944 t-Bu cyclohexyl OEt 2929, 2852, 1448, 105645 t-Bu cyclohexyl OCOMe 2930, 2853, 1773, 1366, 120246 t-Bu cyclohexyl OCOPh <5047 t-Bu cyclohexyl NHPh 12348 t-Bu cyclohexyl 4-BrPh 2928, 2852, 1612, 1481, 82549 n-pentyl Ph OH50 n-pentyl 4-ClPh OH51 n-pentyl 4-FPh OH52 n-pentyl 4-MePh OH53 n-pentyl 2-ClPh OH54 n-pentyl 2-FPh OH55 n-pentyl 2,4-Cl.sub.2PH OH56 n-pentyl 3-pyridine OH 12057 n-pentyl 3-pyridine OMe 0.9-3.9(16, m); 6.5-8.6(6, m)58 n-pentyl 3-pyridine OEt 0.9-4.2(18, m); 6.5-8.6(6, m)59 n-pentyl 3-pyridine OCOMe 0.9-2.6(16, m); 6.4-8.7(6, m)60 n-pentyl 3-pyridine OCOPh 0.9-2.8(13, m); 6.7-8.7(11, m)61 n-pentyl 3-pyridine NHPh 0.9-2.7(13, m); 6.4-8.6(11, m)62 ##STR5## Ph OH63 ##STR6## 4-ClPh OH64 ##STR7## 4-FPh OH65 ##STR8## 4-MePh OH66 ##STR9## 2-ClPh OH67 ##STR10## 2-FPh OH68 ##STR11## 2,4-Cl.sub.2Ph OH69 ##STR12## 3-pyridine OH70 n-Hexyl Ph OH71 n-Hexyl 4-ClPh OH72 n-Hexyl 4-FPh OH73 n-hexyl 4-MePh OH74 n-hexyl 2-ClPh OH75 n-hexyl 2-FPh OH76 n-hexyl 2,4-Cl.sub.2Ph OH77 n-hexyl 3-pyridine OH78 ##STR13## Ph OH79 ##STR14## 4-ClPh OH80 ##STR15## 4-FPh OH81 ##STR16## 4-MePh OH82 ##STR17## 2-ClPh OH83 ##STR18## 2-FPh OH84 ##STR19## 2,4-Cl.sub.2Ph OH85 ##STR20## 3-pyridine OH86 Ph Ph OH87 Ph 4-ClPh OH88 Ph 4-FPh OH89 Ph 4-MePh OH90 Ph 2-ClPh OH91 Ph 2-FPh OH92 Ph 2,4-Cl.sub.2Ph OH93 Ph 3-pyridine OH94 Ph n-Bu OH95 Ph t-Bu OH96 Ph n-pentyl OH97 Ph ##STR21## OH98 Ph ##STR22## OMe99 Ph ##STR23## OEt100 Ph ##STR24## OCOMe101 Ph ##STR25## OCOPh102 Ph ##STR26## NHPh103 Ph ##STR27## ##STR28##104 4-ClPh ##STR29## NHCONH.sub.2 0.9-4.1(13, m); 6.0-7.5(6, m)105 Ph n-hexyl OH106 Ph ##STR30## OH107 Ph ##STR31## OMe108 Ph ##STR32## OEt 2956, 2867, 1052, 698109 Ph ##STR33## OCOMe 2956, 2866, 1770, 1366, 1204110 Ph ##STR34## OCOPh 2956, 2907, 1749, 1257, 1245111 Ph ##STR35## NHPh 2955, 2904, 2865, 1600, 1495112 Ph CH.sub.2CH.sub.2 ##STR36## 145-148113 Ph ##STR37## NHCOCH.sub.2 2955, 2907, 1692, 1582, 698114 Ph CH.sub.2CH.sub.2Ph OH 3026, 2925, 1495, 1452, 698115 Ph CH.sub.2CH.sub.2Ph OMe 2935, 1495, 1452, 1047, 698116 Ph CH.sub.2CH.sub.2Ph OEt 2931, 1495, 1453, 1051, 698117 Ph CH.sub.2CH.sub.2Ph OCOMe 3026, 1766, 1453, 1204, 700118 Ph CH.sub.2CH.sub.2Ph OCO Ph 1746, 1451, 1257, 1246, 700119 Ph CH.sub.2CH.sub.2Ph NHPh 3025, 1602, 1494, 1258, 697120 Ph CH.sub.2CH.sub.2Ph ##STR38## 144-146121 Ph CH.sub.2CH.sub.2Ph NHCONH.sub.2 3463, 1693, 1582, 696122 4-ClPh Ph OH123 4-ClPh 4-ClPh OH124 4-ClPh 4-FPh OH 152-154125 4-ClPh 4-FPh OCH.sub.3 3.7-3.9(5, m); 6.8-7.9(10, m)126 4-ClPh 4-FPh OEt 1.1-4.2(7, m); 6.7-7.9(10, m)127 4-ClPh 4-FPh OCOMe 2.2-4.0(5, m); 7.0-8.2(10, m)128 4-ClPh 4-FPh OCOPh 88129 4-ClPh 4-FPh NHPh 142-144130 4-ClPh 4-FPh ##STR39## 195-197131 4-ClPh 4-FPh NHCOCH.sub.2 163-164132 4-ClPh 4-MePh OH133 4-ClPh 2-ClPh OH134 4-ClPh 2-FPh OH135 4-ClPh 2,4-Cl.sub.2Ph OH136 4-ClPh ##STR40## OH 78137 4-ClPh ##STR41## OMe 2958, 2900, 1492, 1052, 797138 4-ClPh ##STR42## OEt 0.9-4.1(16, m); 3.7(2, s); 5.9-7.8(6, m)139 4-ClPh ##STR43## OCOMe 2958, 1769, 1492, 1366, 1204140 4-ClPh ##STR44## OCOPh 2958, 1748, 1491, 1244, 707141 4-ClPh ##STR45## NHPh 0.9-3.8(13, m); 5.8-7.4(11, m)142 4-ClPh CH.sub.2 ##STR46## 154143 4-ClPh CH.sub.2 NHCONH.sub.2 118144 4-ClPh ##STR47## OCOOEt145 4-ClPh ##STR48## OH146 4-ClPh ##STR49## OMe147 4-ClPh ##STR50## OEt148 4-ClPh ##STR51## OCOMe149 4-ClPh ##STR52## OCOPh150 4-ClPh ##STR53## NHPh151 4-ClPh ##STR54## ##STR55##152 4-ClPh ##STR56## NHCONH.sub.2153 4-FPh Ph OH154 4-FPh 4-ClPh OH155 4-FPh 4-FPh OH156 4-FPh 4-MePh OH157 4-FPh 2-ClPh OH 3280, 1506, 1432, 1219158 4-FPh 2-ClPh OCH.sub.3 1508, 1218, 977, 761, 532159 4-FPh 2-ClPh OEt160 4-FPh 2-ClPh OCOMe 2.1-3.9(5, m); 6.9-8.2(10, m)161 4-FPh 2-ClPh OCOPh 1691, 1510, 1213, 710162 4-FPh 2-ClPh ##STR57## 1508, 1235, 1036, 749163 4-FPh 2-ClPh ##STR58##164 4-FPh 2-ClPh ##STR59## 1508, 1232, 1037, 758165 4-FPh 2-ClPh ##STR60## 1603, 1507, 1258, 751166 4-FPh 2-ClPh ##STR61## 188167 4-FPh 2-ClPh phenyl168 4-FPh 2-ClPh ##STR62## 78169 4-FPh 2-ClPh NHCONH.sub.2170 4-FPh 2-ClPh OCH.sub.2Ph171 4-FPh 2-ClPh OCOOEt172 4-FPh 2-FPh OH173 4-FPh 2-FPh OH174 4-FPh ##STR63## OH 0.9-3.7(13, m); 5.3-7.8(6, m)175 4-FPh ##STR64## OMe 2958, 1508, 1224, 1051176 4-FPh ##STR65## OEt 2959, 1508, 1223, 1052177 4-FPh ##STR66## OCOMe 2958, 1769, 1509, 1222, 1204178 4-FPh ##STR67## OCOPh 2957, 1748, 1509, 1245, 708179 4-FPh ##STR68## NHPh 70180 4-FPh ##STR69## ##STR70## 161181 4-FPh ##STR71## NHCONH.sub.2 53182 4-FPh ##STR72## phenyl183 4-FPh ##STR73## ##STR74## 2958, 1507, 1481, 1222184 4-FPh ##STR75## OH185 4-F Ph ##STR76## OMe186 4-FPh ##STR77## OEt187 4-FPh ##STR78## OCOMe188 4-FPh ##STR79## OCOPh189 4-FPh ##STR80## NHPh190 4-FPh ##STR81## ##STR82##191 4-FPh ##STR83## NHCONH.sub.2192 2-ClPh Ph OH193 2-ClPh 4-ClPh OH194 2-ClPh 4-FPh OH195 2-ClPh 4-MePh OH196 2-ClPh 2-ClPh OH197 2-ClPh 2-FPh OH198 2-ClPh 2,4-Cl.sub.2Ph OH199 2-FPh Ph OH200 2-FPh 4-ClPh OH201 2-FPh 4-FPh OH202 2-FPh 4-MePh OH203 2-F Ph 2-ClPh OH204 2-FPh 2-FPh OH205 2-FPh 2,4-Cl.sub.2Ph OH__________________________________________________________________________ ##STR84## TABLE 2__________________________________________________________________________ ##STR85##No. R.sup.1 R.sup.2__________________________________________________________________________ 1a n-C.sub.3 H.sub.7 phenyl 2a n-C.sub.3 H.sub.7 4-ClPh 3a n-C.sub.3 H.sub.7 4-FPh 4a n-C.sub.3 H.sub.7 4-FPh 5a n-C.sub.3 H.sub.7 4-MePh 6a n-C.sub.3 H.sub.7 2-ClPh 7a n-C.sub.3 H.sub.7 2-FPh 8a n-C.sub.3 H.sub.7 2,4-Cl.sub.2 Ph 9a n-C.sub.3 H.sub.7 3-pyridine10a n-C.sub.3 H.sub.7 3-pyridine11a n-C.sub.3 H.sub.7 3-pyridine12a n-C.sub.3 H.sub.7 3-pyridine13a n-C.sub.3 H.sub.7 3-pyridine14a n-C.sub.3 H.sub.7 4-pyridine15a n-C.sub.3 H.sub.7 2-pyridine16a n-C.sub.3 H.sub.7 1-naphthyl17a n-C.sub.3 H.sub.7 2-naphthyl18a n-C.sub.3 H.sub.7 4-biphenyl19a n-Bu phenyl20a n-Bu 4-ClPh21a n-Bu 4-FPh22a n-Bu 4-MePh23a n-Bu 2-ClPh24a n-Bu 2-FPh25a n-Bu 2,4-Cl.sub.2Ph26a n-Bu 3-pyridine27a t-Bu Ph28a t-Bu 4-ClPh29a t-Bu 4-ClPh30a t-Bu 4-ClPh31a t-Bu 4-ClPh32a t-Bu 4-ClPh33a t-Bu 4-ClPh34a t-Bu 4-FPh35a t-Bu 4-FPh36a t-Bu 4-MePh37a t-Bu 2-ClPh38a t-Bu 2-FPh39a t-Bu 2,4-Cl.sub.2Ph40a t-Bu 3-pyridine41a t-Bu 3-pyridine42a t-Bu cyclohexyl43a t-Bu cyclohexyl44a t-Bu cyclohexyl45a t-Bu cyclohexyl46a t-Bu cyclohexyl47a t-Bu cyclohexyl48a t-Bu cyclohexyl49a n-pentyl Ph50a n-pentyl 4-ClPh51a n-pentyl 4-FPh52a n-pentyl 4-MePh53a n-pentyl 2-ClPh54a n-pentyl 2-FPh55a n-pentyl 2,4-Cl.sub.2PH56a n-pentyl 3-pyridine57a n-pentyl 3-pyridine58a n-pentyl 3-pyridine59a n-pentyl 3-pyridine60a n-pentyl 3-pyridine61a n-pentyl 3-pyridine62a ##STR86## Ph63a ##STR87## 4-ClPh bp 117-120.degree. C./0.4 mbar64a ##STR88## 4-FPh65a ##STR89## 4-MePh66a ##STR90## 2-ClPh67a ##STR91## 2-FPh68a ##STR92## 2,4-Cl.sub.2Ph69a ##STR93## 3-pyridine70a n-hexyl Ph71a n-hexyl 4-ClPh72a n-hexyl 4-FPh73a n-hexyl 4-MePh74a n-hexyl 2-ClPh75a n-hexyl 2-FPh76a n-hexyl 2,4-Cl.sub.2Ph77a n-hexyl 3-pyridine78a ##STR94## Ph79a ##STR95## 4-ClPh80a ##STR96## 4-FPh81a ##STR97## 4-MePh82a ##STR98## 2-ClPh83a ##STR99## 2-FPh84a ##STR100## 2,4-Cl.sub.2Ph85a ##STR101## 3-pyridine86a Ph Ph87a Ph 4-ClPh88a Ph 4-FPh89a Ph 4-MePh90a Ph 2-ClPh91a Ph 2-FPh92a Ph 2,4-Cl.sub.2Ph93a Ph 3-pyridine mp 94.degree. C.94a Ph n-Bu95a Ph t-Bu96a Ph n-pentyl97a Ph ##STR102##98a Ph ##STR103##99a Ph ##STR104##100a Ph ##STR105##101a Ph ##STR106##102a Ph ##STR107##103a Ph ##STR108##104a 4-ClPh ##STR109##105a Ph n-hexyl106a Ph ##STR110##107a Ph ##STR111##108a Ph ##STR112##109a Ph ##STR113##110a Ph ##STR114##111a Ph ##STR115##112a Ph CH.sub.2CH.sub.2113a Ph ##STR116##114a Ph CH.sub.2CH.sub.2Ph115a Ph CH.sub.2CH.sub.2Ph116a Ph CH.sub.2CH.sub.2Ph117a Ph CH.sub.2CH.sub.2Ph118a Ph CH.sub.2CH.sub.2Ph119a Ph CH.sub.2CH.sub.2Ph120a Ph CH.sub.2CH.sub.2Ph121a Ph CH.sub.2CH.sub.2Ph122a 4-ClPh Ph123a 4-ClPh 4-ClPh124a 4-ClPh 4-FPh125a 4-ClPh 4-FPh126a 4-ClPh 4-FPh127a 4-ClPh 4-FPh128a 4-ClPh 4-FPh129a 4-ClPh 4-FPh130a 4-ClPh 4-FPh131a 4-ClPh 4-FPh132a 4-ClPh 4-MePh133a 4-ClPh 2-ClPh134a 4-ClPh 2-FPh135a 4-ClPh 2,4-Cl.sub.2Ph136a 4-ClPh ##STR117## bp 119-122.degree. C./0.01 mbar137a 4-ClPh ##STR118##138a 4-FPh 2-ClPh bp 164-184.degree. C./0.3 mbar139a 4-ClPh 2,2-(CH.sub.3).sub.2 -n-propyl bp 120.degree. C./0.01 mbar140a 4-FPh 2,2-(CH.sub.3).sub.2 -n-propyl bp 85.degree. C./0.1 mbar141a 4-ClPh CH.sub.2CH.sub.2CH(CH.sub.3).sub.2CH.sub.3 bp 120.degree. C./0.1 mbar142a 1,1-(CH.sub.3).sub.2 -n-ethyl CH.sub.2CH.sub.2CH(CH.sub.3)CH.sub.3 bp 110-130.degree. C./0.3 mbar143a 1,1-(CH.sub.3).sub.2 -n-ethyl 4-ClPh bp 120.degree. C./0.4 mbar144a 4-FPh 3-pyridine bp 155.degree. C./0.1 mbar145a 4-ClPh 4-FPh mp 84-85.5.degree. C.146a 4-ClPh 2,4-dichloro-Ph mp 130.5-131.5.degree. C.__________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereaIs. Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosorium species in cereals, Septoria nodorum in wheat. Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in vegetables and fruit.

The compounds are applied by spraying or dusting the plants with the active ingredients or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi. Either the fungi themselves, or the plants, seeds, materials or soil to be protected against fungal attack are treated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner. for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g. crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g. kaolins, aluminas, talc and chalk and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyIene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt. % of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials (wood), for example against Paecilomyces variotii,

When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are usually employed.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts. Pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 109 (Table 1) is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 136 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 139 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 159 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and i mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 168 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid. 10 parts by weight of the sodium salt of a lignin-suIfonic acid obtained from a sulfite waste liquor and 7 parts by weight of powdered silica gel. and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 174 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 109 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 136 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 139 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycoI ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.

Use example

Action on Pyricularia oryzae (protective)

Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions containing (dry basis) 80% of active ingredients and 20% of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were then set up in climatic cabinets at from 22.degree. to 24.degree. C. and a relative humidity of 95 to 99%. The extent of fungus spread was determined after 6 days. The results show that active ingredients 109, 136, 139, 159, 168 and 174, applied as 0.05 wt. % spray liquors, have a good fungicidal action (90%).

Claims

1. A compound of the formula I ##STR119## wherein R.sup.1 and R.sup.2 are each phenyl, biphenylyl, or naphthyl and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each C.sub.1 -C.sub.8 -alkyl which is unsubstituted or substituted by phenyl, halophenyl or C.sub.1 -C.sub.4 -alkylphenyl, R.sup.3 is a radical OR.sup.4, where R.sup.4 is hydrogen, C.sub.1 -C.sub.6 -halobenzoyl alkyl, ##STR120## benzoyl or halobenzoyl or R.sub.3 is a radical NHR.sup.5, where R.sup.5 is hydrogen, phenyl, nitrophenyl, or the carbamide group CONH.sub.2.

2. Compounds of the formula I as set forth in claim 1, where R.sup.2 is 2,2-dimethylpropyl, R.sup.3 is OH, and R.sup.1 is phenyl which is unsubstituted or substituted by one or two identical or different radicals selected from the group consisting of fluoro, chloro, bromo and methyl.

3. A fungicidal composition containing a carrier and a fungicidally effective amount of a 1-azabutadiene of the formula I ##STR121## where R.sup.1 and R.sup.2 are each phenyl, biphenyly, or naphthyl and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each C.sub.1 -C.sub.8 -alkyl which is unsubstituted or substituted by phenyl, halophenyl or C.sub.1 -C.sub.4 -alkylphenyl, R.sup.3 is a radical OR.sup.4, where R.sup.4 is hydrogen, C.sub.1 -C.sub.6 -halobenzoyl, alkyl, ##STR122## benzoyl or halobenzoyl or R.sub.3 is a radical NHR.sup.5, where R.sup.5 is hydrogen, phenyl, nitrophenyl, or the carbamide group CONH.sub.2.

4. A compound of the formula I as set forth in claim 1, where R.sup.1 is phenyl, R.sup.2 is 3,3-dimethylbutyl and R.sup.3 is acetyloxy.

5. A compound of the formula I as set forth in claim 1, where R.sup.1 is 4-chlorophenyl, R.sup.2 is 2,2-dimethylpropyl and R.sup.3 is OH.

6. A compound of the formula I as set forth in claim 1, where R.sup.1 is 4-chlorophenyl, R.sup.2 is 2,2-dimethylpropyl and R.sup.3 is acetyloxy.

7. A compound of the formula I ##STR123## wherein R.sup.1 is phenyl, biphenylyl, or naphthyl, and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is C.sub.1 -C.sub.8 -alkyl which is unsubstituted or substituted by phenyl, halophenhyl or C.sub.1 -C.sub.4 -alkylphenyl; R.sup.2 is biphenylyl which may be mono-to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is phenyl substituted by 1 to 3 groups selected from halogen, nitro, phenoxy, amino, haloalkyl, or alkoxy, each of 1 to 4 carbon atoms, or is naphthyl which may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is C.sub.1 -C.sub.8 -alkly which is unsubstituted or substituted by phenyl, halophenyl or C.sub.1 -C.sub.4 -alkylphenyl; and R.sup.3 is phenyl, halophenyl, or C.sub.1 -C.sub.4 -alkylphenyl.

8. A fungicidal composition containing a carrier and a fungicidally effective amount of a compound according to claim 7.