CA1274521A

CA1274521A - Benzyloxyalkylazoles and fungicides containing these compounds

Info

Publication number: CA1274521A
Application number: CA000493090A
Authority: CA
Inventors: Karl Roeser; Ernst Buschmann; Eberhard Ammermann; Ernst-Heinrich Pommer; Hubert Sauter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1984-10-17
Filing date: 1985-10-16
Publication date: 1990-09-25
Also published as: DE3437919A1; JPS6197268A; EP0178587A3; EP0178587A2

Abstract

ABSTRACT OF THE DISCLOSURE: Benzyloxyalkylazoles of the formula

Description

1~74S~
O.Z 0050/37398 ~enzyloxyalkylazoles and fung;c1des conta;n;ng these compounds The present ;nvent;on relates to novel benzyloxy-alkylazoles, fung;c;des containing these compounds, and processes for their preparation~
It has been disclosed that azole compounds, eg. 2,2-dimethyl-4-~1,2,4-triazol-1-y~-5-phenylpentan-3-one, can be used as fungicides (German Laid-Open Application DOS

2,638,470).
It is an ob ject of the present invention to provide novel compounds and fungicides whose activity is superior to that of the known compounds, particularly at low concen-trations, or wh;ch can be put to an alternative use when signs of resistance appear.
We have found that this object ;s achieved, and that benzyloxyalkylazole compounds of the formula I
v ~(C 2)m ~ ~ Ir R N
n where R is halogen, alkyl, alkoxy, haloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted pyridyl, ZO aralkyl, alkylthio or hydrogen, n is an integer from 1 to 5, m is an integer from 1 to 8, Y is a C=O or HCOH group and Z is a CH group or an N atom, haYe a very good fungici-dal action.
Preferred compounds are those in which R is halogen, lower alkyl of 1 to 4 carbon atoms, haloalkyl of 1 or 2 carbon atoms and 1 to 3 halogen atoms, and hydrogen.
In formula I, R is, for example, halogen (fluorine, chlorine, bromine or iodine), preferably fluorine, bromine or chlorine, in particular 4-chloro, 4-fluoro, 2-chloro, 2-fluoro, 3-fluoro, 2-bromo, 4-bromo or 2,4-dichloro, lower alkyl of 1 to 4 carbon atoms, preferably methyl, ethyl, n-propyl, n-butyl or tert.-butyl, in particular methyl or tert.-butyl, alkoxy where alkyl is of 1 or 2 carbon atoms, ~1, .

lZ7~5Z~
- Z - 0.Z. 0050/37398 preferably methoxy, or haloalkyl, in particular haloalkyl in which alkyl ;s of 1 or 2 carbon atoms and which contains 1 to 5, preferably 1 to 3, halogen atoms, eg. fluorine, chlor;ne or bromine, preferably f(uor;ne or chlorine. An example of halomethyl is tr;fluoromethyl.
R may furthermore be unsubstituted or subst;tuted aryl, for example unsubstituted or halogen-substituted phenyl, preferably phenyl, 4-chlorophenyl or 4-fluorophenyl. Finally, R may also be unsubstituted or substituted pyridyl, in particular unsubstituted or halogen-subst;tuted pyr;dyl, aralkyl ~benzyl), alkylthio (of 1 to 4 carbon atoms, eg. methylthio) or hydrogen.
n may be an integer from 1 to 5, preferably 1 or 2.
m is an ;nteger from 1 to 8, preferably 2, 3, 4, S or 6.
Y is a C=O or HCOH group.
In formula I, Z is an N atom or a C-H group.
The compounds of the formula I can be prepared according to one of the schemes stated below:

Scheme A (intermediate) ~ 2)m ~ O ~ ~CH2~m-Hal Rn Rn Scheme B (intermediate) ~ Hal ~ HO-~CH2)m-OH ~ ~ (CH2)m-~H
Rn Rn ~ _~^~ ~ (CH ) -Hal halogenation ~ ~ 2 m Rm ' . ,, ~ ' 127~S~l

- 3 - O.Z. OûSO/37398 Scheme C (intermediate) (CH ) Ha~ m ~CHZ)m~
Rn Rn Scheme D

t ~ ttH2)~-Hal b~se reduction OH -i f reguired ~ O ~ ~CHz) Rn 2~
The starting compounds of the formula II may be prepared by a conventionaL process by a) alkylating a mono-(alkali metal) salt of an alpha, omega-glycol w;th an appropr;ate benzyl halide and conver-t;ng the result;ng alcohol to the bromide, for e~ample by means of N-bromosuccinimide/triphenylphosphine ~Scheme 3) or b) alkylating a phenol with an alpha,omega-dihalo-alkane (Sche0e A).
The intermediates below can be prepared in this manner:
Rn . m X Physical data, bp

4-Cl 2 C~
4-Cl 2 Br 116C/0.1 mbar 15 4-Cl 3 Cl 108C/0.4 mbar 4-Cl 3 Br 4-Cl 4 Cl lZ74SZl - 4 - O.Z. 0050~37398 m X Ph sical data bo R n -- -- . Y
4-Cl 4 8r 4-Cl 5 Cl 155-170C/0.4 mbar 4-Cl 5 8r

5 4-C~ 6 Cl 4-Cl -6 Br 4-C~ 7 Cl 4-C~ 7 Br 2-C~ 2 C~
10 2-Cl 2 Br 2-Cl 3 C~
2-Cl 3 Br Z-C~ 4 C~
2-Cl 4 8r 1S 2-Cl 5 Cl 2-Cl 5 9r 2-C~ 6 C~
2-Cl 6 8r r 2-Cl 7 C~
20 2-Cl 7 Br 2,4-dichloro 2 Cl 111C/0.5 mbar 2,4-dichloro 2 8r 2,4-dichloro 3 Cl 2,4-dichloro 3 Br 25 2,4-dichloro 4 Cl 140C/0.5 mbar 2,4-dichloro 4 9r 2,4-dichloro 5 Cl 2,4-dichloro 5 8r 2,4-d;chloro 6 Cl 30 2,4-dichloro 6 Br 2,4-d;chloro 7 Cl 2,4-dichloro 7 8r 4-tert.-butyl 2 Cl 4-tert.-butyl 2 8r 112 - 119C/0.3 mbar 35 4-tert.-buty;1 3 Cl 140C/0.5 mbar 4-tert.-butyl 3 8r 4-tert.-butyl 4 Cl 14~C/0.5 mbar 127~S2~

- 5 - O.Z. ooso/37398 Rn- m ~ Physica~ data, bp 4-tert.-butyl 4 Br 4-tert.-buty~ 5 Cl 155C/0.4 mbar 4-tert.-buty~ 5 8r 4-tert.-butyl 6 Cl 160C/0.4 mbar 4-tert.-butyl 6 Br 4-tert.-butyl 7 Cl 4-tert.-butyl 7 3r 4-F 2 Cl 10 4-F 2 8r 88C/0.5 mbar 4-F 3 Cl 4-F 3 8r 4-F 4 Cl 4-F 4 Br 15 4-F 5 Cl 4-F 5 8r 4-F 6 Cl 4-f 6 Br 4-F 7 Cl 20 4-F 7 Br 2,4,6-trichloro 2 Cl 2,4,6-trichloro 2 Br Z,4,6-tr;chloro 3 Cl 2,4,6-trichloro 3 8r 25 2,4,6-trichloro 4 Cl 2~4,6-trichloro 4 8r 2,4,6-trichloro 5 Cl 2,4,6-trichloro 5 Br 2,4,6-trichloro 6 Cl 30 2,4,6-tr;chloro 6 8r Z,4,6-trichloro 7 Cl 2,4,6-trichloro 7 Br 4-methyl 2 Cl 4-methyl 2 Br 94C/0.4 mbar 35 4-methyl 3 Cl gsC/~.5 mbar 4-methyl 3 Br 4-methyl 4 Cl ~ z74521

- 6 - 0.Z. 0050/3739 Rn m X Physical data, bp 4-methyl 4 Br 4-methyl 5 Cl 4-methyL 5 8r 5 4-methyl 6 Cl 4-methyl -6 9r 4-methyl 7 Cl 4-methyl 7 Br C/0.3 mbar 4-Br 2 8r 123-135 10 3-CH3 2 Br 92C/0.4 mbar - 2-CF3 2 - ar 88C/0.7 mbar Z-Br 2 3r 116-125C/0.4 mbar 3-f 2 Br 80C/0.5 mbar 4-CF3 3 Cl 95C/0.4 mbar 15 4-CF3 4 Cl 125C/0.5 mbar 4-CF3 5 Cl 140C/2.5 mbar 4-CF3 6 Cl 130C/0.5 mbar The compounds of the general formula I contain one or more centers of asymmetry; in the case of Y = CHOH, they conta;n two or more centers of asymmetry and can therefore occur as enant;omer m;xtures and/or d;astereomer m;xtures.
In the synthes;s accord;ng to the ;nvention, the compounds are usually obta;ned in the form of m;xtures of stereo-;somers; the pure ;somers can be obtained from these by su;table separation operations. The present invention em-braces both the ;nd;vidual ;somers and mixtures of these.
The ;somers of the novel alcohols of the formula I
may also be prepared d;rectly by selective synthesis, for example by reduction of the novel ketones of the formula I with the aid of su;table reduc;ng agents.

4.2 9 (0.14 mole) of an 80X strength suspension of NaH in paraffin was suspended ;n 100 ml of dry d;methyl-formamide, and 23.4 9 (0.14 mole~ of 1-~1,2,4-triazol-1-yl)-3,3-dimethylbutan-3-one, dissolved ;n 50 ml of dry d;methyl-formamide, ~ere added dropwise. When evolut;on of gas had d;ed down, stirring was cont;nued for a further hour, after - .
:

12745.Zl

- 7 - O.Z. 0050/37398 which a solution of 21 9 ~0.14 mole) of 3-benzyloxy-1-bromo-propane, dissolved in 50 ml of dry dimethylformamide, was added dropwise. Stirring was continued for 4 hours at 70C, the mixture was left to cool and then poured into a mix-ture of 500 ml of water and 500 ml of methylene chloride, the phases were separated, the aqueous phase was extracted w;th methylene chloride, the combined organic phases were dried and the solvent was evaporated under reduced pressure.
The crude product W25 distilled to give 22.6 9 ~51X of theory) of 7-benzyloxy-2,2-dimethyl-4-~1,2,4-tr;azol-1-yl~-heptan-3-one.. IR: 1717, 1502, 1276, 1139, 1103 ~compound No. 1).

15.0 9 ~0.048 mole) of compound No. 1 were dis-solved in 50 ml of isopropanol, and a solution of 0.61 9 ~0.016 mole) of sodium borohydride in isopropanol was added. The mixture was stirred overnight at room tempera-ture, after which it was poured onto water, the aqueous phase was extracted with ethyl acetate, the extracts were dried and the solvent was evaporated under reduced pres-sure. The residue was distilled to give 12.0 9 ~80X of theory) of product No. 2 ~7-benzyloxy-2,2-dimethyl-4-~1,2,4-triazol-1-yl)-heptan-3-ol). IR: 2956, 2869, 1138, 1100, 1075.
The compounds listed below can be prepared in a similar manner. The substances which are not characterized by physical data serve to illustrate the w;de range of possible syntheses. A and B are the two diastereomers.

lZ7(~S~l

- 8 ~ 0.~. 0050/~7~98 N~. ~h m Y Z Physical data IR bands _ _ _ 3 H 2 C~O N
4 H 2 C~O C~
05 S ~ 2 HCOH (A) N
6 H 2 HCOa (A) C~
7 ~ 2 HCOH (B) N
8 H 2 ~COE (B) CH

9 H 3 C~O C~
lo lo a 3 ~COH (A) C~ 1496, 1123, 1113, 1080, 742 11 H 3 HCOH (A) N 2956, 2869, 1275, 1136, 1101 12 H 3 ~CO~ (B) CH 2953, 2868, 1100, 1081, 745 13 H 4 C-O N 2935, 2860, 1716, 1501, 1102 14 ~ 4 C~O. C~
}5 15 H 4 HCO~ (A) N 2954, 2867, 1275, 1136, 1102 16 H 4 ~COH ~A) CH
17 ~ ~ HCO~ (B) N 2965, 2946, 1517, 1141, 699 18 H 4 HCO~ (B) ca 19 ~ 5 C-O N
20 H 5 C-O C~
21 H 5 HCO~ (A) N
22 ~ 5 HCOH (A) CH
23 a 5 . HCOH (B) N
24 a 5 HCOH (B) ca 25 a 6 C~O N
26 ~ 6 C'O C~
27 8 6 HCO~ (A) N
28 H 6 HCOH (A) C~
29 ~ 6 ~CO~ (B) .N 2963, 2939, 2859, 1518, 1142 30 30 a 6 NCOa (B) ca 31 H 7 C~O N
32 a 7 C-O ca 33 a 7 HCOH (A) N
34 a 7 aCOH (A) C~
35 35 a 7 ~cOu ( B) N
36 a 7 ~COH (B) C~
37 a 8 c-o N

39 ~ 8 ~CO~ (A) N
40 40 ~ 8 HCOH (A) ca 41 ~ 8 ~COH (B) N
42 a, 8 C~OH (B) C~
43 2-C1 2 C'O N
-~2~4S~l - 9 -O. Z. oo50/37398 NO. Rn~ m Y ZPhysi ca l data IR bands 44 2-C1 ` 2 C-O C~l -45 2~1 2 ~COId (A) N
0546 2-C1 2 ~ oa (A) ca 47 2~1 2 aco~ (B) M
48 2-C1 2 ~CO}l (B) ca 49 2-C1 3 C~O N
2-Cl 3 C'O ca 1051 2--C1 3 ~COE (A) N
52 2-C1 3 ~coa (A) C~
53 2--C1 3 HCO~ (B) N
54 2-C1 3 acoa (B) ca 2--C1 4 C-(3 N

57 2-C1 4 acoa (A) N
58 2-C1 4 HCOI~ (A) ca 59 2-Cl 4 aco~ (B) N
2-C1 4 acoa (B) ca 62 2-C1 5 C-O ca 63 2--C1 5 aco~ tA) N
64 2-C1 5 acoa (A) CH
2--C1 5 aco~ (B) N
2566 2-C1 5 acoa (B) ca 68 2-C1 6 C-O C~l 69 2-C1 6 acoa (A) N
2-C1 6 aco~ (A) CH
3071 2-C1 6 acoa (B) ~t 72 2-C1 6 acoa (B) ca 74 2-C1 7 C-O ca 2-C1 7 HCO~l (A) N
3576 2-C1 7 HCOH (A) CH
77 2-C1 7 acoa (B) N
78 2-C1 7 HCO}I (B) ca 79 2-C1 8 ~:-0 N
2-Cl 8 C-O CH
4081 2-C1 8 EICOIl (A) N
82 2-C1 8 HCO~ (A) C~
83 2-C1 8 ~coa (B) N
84 2-C1 8 acoa (B) ca SZl - 1 o o . z . 0050/ 37398 No. Rn m Y Z Ph~s;cal data IR bands 2, 4-C12 2 C-O N
86 2,4-C12 2 C~O ca C5 87 2,4 - C12 2 aco~ (A) N ~p. - 220-C/0.15 ~b.
88 2,4-C12 2 ~CO~ (A) ca 89 2,4-C12 2 ~coa ( 8) N
2,4-C12 2 acoa (B) ca 91 2,4-C12 3 C-O N
92 2,4-ca2 3 C-O ca 93 2,4 - C12 3 ~coa (A) N
94 2,4 - Ca2 3 ~COH (A) C~
2,4 - C12 3 HCOa ( B) N
96 2,4-ca2 3 ac~ ~B) C~
lS 97 2,4-C12 4 C-O N
98 2,4-C12 4 C-O ca 99 2,4-C12 4 acoa (A) N 2955, 2868, 1473, 1135, 1096 100 2,4-ca2 4 aCOH (A) ca 101 2,4-C12 4 acoa (B) N
102 2,4-C12 4 acoa (B) ca 103 2,4-C12 5 C-O N
104 2,4-C12 5 C-O ca 105 2,4-C12 5 acoa (A) N
106 2,4-C12 ' 5 acoa (A) ca 107 2,4-C12 5 aCOH (B) N
108 2,4-C12 5 acoa (B) ca 109 2,4-C12 5 acoa (B) N
110 2,4-C12 6 C-O ca 111 2,4-C12 6 acoa (A) N
112 2,4-C12 6 acoa (A) ca 113 2,4-C12 6 acoa (B) N
114 2,4-C12 6 acoa (B) ca 115 2,4-C12 7 C-O N
116 2,4-C12 7 C~O ca 117 2,4-C12 7 acoa (A) N
: ~ 118 2,4-C12 7 acoH (A) ca 119 2,4-C12 7 acoa (B) N
i20 2,4-C12 7 acoa (B) ca 121 2,4-C12 8 C-O ' N
122 2,4-C12 8 C-O C~
:~ ~ : 123: 2,4-C12 B acoa (A) N
: 124 2,4-C12 8 acoa (A) ca 125 2,4-C12 8 acoa ( B) N

; ~
: ' :, ' ~' lZ'7~21 o. z . oo50/37398 Nt~. Rn m Y Z Physical data IR bands -126 2,4-C12 8 ~CO~ (B) CH
127 4-C1 2 C-O N 1717, 1502, 1492, 1090, 1015 05 128 4-C1 2 C-O C~
129 4-C1 2 ~COH (A) N 1134, 1123, 1097, 1087, 1014 130 4-C1 2 HCO~ (A) C6 131 4-C1 2 ~COH (B) N
132 4-C1 2 ~CO~ (B) C~

10 133 4-C1 3 C~O N 1717, 1492, 1097, 1089, 1015 134 4-C1 3 C-O ca 1714, 1492, 1108, 1096, 1087 135 4-C1 3 aCOH (A) N 2956, 1275, 1136, 1093, 1015 136 4-C1 3 acoa (A) C~ .
137 4-C1 3 aC~H (B) N 3320, 2963, 1510, 1146, 809 15 138 4-C1 3 aCOE (B) ca 140 4-Cl. 4 C'O CH
141 4-C1 4 acoa (A) N
142 4-C1 4 aco~ (A) C~
20 143 4-C1 4 aCOH (B) - N
144 4-C1 4 aco~ (B) ca 145 4-C1 5 C~O N 2936, 2863, 1716, 1492, 1090 146 4-Cl 5 C-O C~
147 4-C1 5 HCOa (A) N 2939, 2863, 1492, 1090, 1015 25 148 4-C1 5 HCOH (A) ca 149 4-Cl 5 ~coa .(B) N 2952, 2935, 2867, 2852, 813 150 4-C1 5 HCOH (B) ca 152 4-C1 6 C~O ca 30 153 4-C1 6- HCOa (A) N
154 4-C1 6 HCOH (A) C~
155 4-C1 6 aco~ (B) N
156 4-C1 6 ~COH (B) C~

35 158 4-C1 7 C'O CH
159 4-C1 7 ~COH (A) N
160 4-C1 7 acoa (A) ca 161 4-C1 7 aco~ (B) N
162 4-C1 7 HCO~ (B) CH

164 4-C1 8 C~O CH
165 4-C1 8 HCOa (A) N
166 4-C1 8 aCOH (A) . ca .

.

.~s lZ7~5Z~
- 1 2 o. z . 0050/37398 Nt1. Rn m Y ~ Physical data IR bands _ _ 167 4--C1 8 ~C0~ (B) N
168 4--C1 8 ~coa (B) CE

170 4-OCE3 2 C~0 C~
171 4-oca3 2 ~coa (A) N
172 4--OCE3 2 ~COH (A ) C~
173 4-OCH3 2 aco~ (B) N
174 4--OCE3 2 ~COH (B ) CE
175 4-oca3 3 c~o N

177 40C~3 3 ~COH (A) N
178 4-oca3 3 ~COH (A) CEl 15 179 4-oca3 3 ~co~ (B ) N
180 4-oca3 3 HCO~ (B) C~
181 4--OCE3 4 c~o N

133 4-oca3 4 ~COH (A) N
20 184 40CE3 4 aCOE (A) CE
185 4-OCH3 4 ~coa (B) N
186 4--oca3 4 acoH (B ) CE
187 4-oca3 5 c~o N

2s 189 4-OCE3 5 EECOH (A) N
4-OCH3 5 HCOE (A) C~
-oca3 5 acoa (B) N
192 4--OCE3 5 aco~ (B) CE
193 4-OC~3 6 C~0 N
30 194 4-OCX3 6 C~0 C~
195 4-OCE3 6 ECOEI (A) N
196 4--oca3 6 acoE (A) CE
197 4--oca3 6 ~COE (B) N
198 4--oca3 6 ~COE (B) ca 199 4-OC~3 7 c~o N O
200 4--OCE3 7 c~o CE
201 4--OCE2 7 ECOE (A) N
202 4-OC~3 7 ~COEi (A) CE
20 3 4--OCE3 7 ~COE (B ) N
204 4--oca3 7 ~COE (B ) ca 20 5 4-oca3 8 c~o N
20 6 4-oca3 8 c~o CE
20 7 40C~3 8 ~COE (A ) N

1;~'7'15~
- 13 - O,Z. oo50/37398 N~ m Y Z Physi ca l data IR bands .
208 4-OC~3 8 HCOH (A) CH
209 4-oCH3 8 ~CO~ (B) 05 210 4-oca3 8 HCOE (B) C~
211 4-CF3 2 C'O N 1718, 1327, 1164, 1124, 1067 212 4-CF3 2 C~O ca 213 4-CF3 2 aco~ (A) N 1326, 1164, 1128, 1125, 1067 214 4-CF3 2 Hcoa (A) . ca 10 215 4-CF3 2 ~CO~ (B) N 1327, 1164, 1124, 1067, 1018 216 4-CF3 2 HCOH (B) C~
217 4-CF3 3 C~O N 1717, 1327, 1164, 1124, 1108 218 4-CF3 3 C-O C~
219 4-CF3 3 HCOH ~A) N 1327, 1164, 1125, 1106, 1067 15 220 4-CF3 3 ~COH (A) C~
221 4-CF3 3 ~CO~ (B) N 1327, 1168, 1129, 1126, 1104 2Z2 4-CF3 3 ~COH (B) ca 223 4-CF3 4 C~O N 1326, 1124, 1607, 1105, 1164 224 4-CF3 4 C-O C~ .
20 225 4-CF3 4 ~CO~ (A) N 1326, 1164, 1125, 1105, 1067 226 4-CF3 4 ~coa (A) CH
227 4-CF3 4 ~CO~ (B) N 1328, 11~8, 1123, 1099, 1067 228 4-CF3 4 ~COH ~B) ca 229 4-CF3 5 C-O N 1327, 1164, 1124, 1105, 1067 231 4-CF3 5 ~CO~ (A) N 1236, 1164, 1125, 1106, 1067 232 4-CF3 5 ~coa (A) ca 233 4-CF3 5 ~CO~ (B) N 1327, 1164, 1125, 1105, 1067 234 4-CF3 5 HCOH (B) CH
30 235 4-CF3 6 C=O N

237 4-CF3 6 HCOH ~A) N 1327, 1164, 1125, 1104, 1067 238 4-CF3 6 ~COH (A) C~
239 4-CF3 6 ~CO~ (B) N
35 240 4-CF3 6 ~coa (B) C~

242 4-CF3 7 C'O C~
243 4-CF3 7 ~COH (A) N
244 4-CF3 7 ~CO~ (A) C~
~0 245 4-CF3 7 ~COH (B) N
246 4-CF3 7 ~CO~ (B) CH
247 4-CF3 8 C~O N
248 4-CF3 8 C~O ca 1274SZl - 1 4 -o . z . oo50/37398 Ntl. ~ m Y ZPhys;cal data IR bands _ 249 4-CF3 8 ~CO~ (A) N
2s0 4-CF3 8 ~COH (A) ca 05 251 4-CF3 8 ~CO~ ~B ) N
252 4-CF3 8 8CO~ (B) C8 253 4-C~3 2 c-o N 1718, 1502, 1276, 1139, 1096 254 4-ca3 2 c~o c~
255 4-C~3 2 ~co~ (A) N 1134, 1123, llll, 1~98, 809 256 4--ca3 2 ~CO~ (A) C~
257 4-CH3 2 ~co~ (B) N
258 4-C~3 2 ~co~ (B) ca 259 4-CH3 3 c~o N 2965, 2933, 2867, 1717, llOO
260 4-CH3 3 c~o ca 15 261 4CH3 3 aCOH (A) N
262 4-ca3 3 acoH (A) ca 263 4-ca3 3 acoa (B) N 2956, 2868, 1504, 1138, lO99 264 4-CH3 3 acoH (B ) ca 265 4-C~3 4 c~o N
20 266 4-ca3 4 267 4-ca3 4 acoa (A) N
268 4-ca3 4 Hcoa (A) ca 269 4-ca3 4 Hcoa (B) N
2-70 4-ca3 4 acoa (B) ca 25 271 4-ca3 5 c~o N
272 4-ca3 5 c~o ca ~73 4-CX3 5 ~coa (A) N
274 4-C~3 5 ~COH (A) C~
275 4-ca3 5 ~co~ (B) N
30 276 4-ca3 5 acoa (B) ca 277 4-ca3 6 c~o N
278 4-C~3 6 c~o ca 279 4-CH3 6 acoa (A) N
Z80 4-C~3 6 acoa (A) ca 3S 281 4-ca3 6 aCOH (B) N
282 4-ca3 6 acoa (B) ca 283 4-C~3 7 C-O N
284 4-ca3 7 C-O ca 285 4-ca3 7 ~coa (A) N
40 286 4-ca3 7 BCOa (A) ca 287 ~-ca3 7 aCoa (8) 288 4-ca3 7 acoa (B) C~
289 4-ca3 8 c~o N
,~ .

74S2~l - 1 s - o . z . ooso/~73g8 N~ . m Y 2 Physi ca l data IR bands 290 4-CH3 8 C~O CH
291 4-CH3 8 HCOE (A) N
06 292 4-CX3 8 HCOH (A) C~
293 4-ca3 8 ~CO~ (B) N
294 4-CH3 8 HCOH (B) . CH
295 4-F 2 C-O N 1717, 1510, 1223, 1111, 1094 296 4-F 2 C~O CH
10 297 4-F 2 HCOH (A) N m.p. ~ 75-80-C
298 4-F 2 HCOH (A) CH
299 4-F 2 HCO~ (B) N
300 4-F 2 ~CO~ ts) ca 301 4-F 3 C-~O N
15 302 4-F 3 C-O ca 303 4-F 3 HCO~ (A) N
304 4-F 3 HCO~ (A) C~
305 4-F 3 HCO~ ( B) N
306 4-F 3 ~CO~ (B) C~
20 307 4-F 4 C~O N
308 4-F 4 C-O C~
309 4-F 4 HCOH (A) N
310 4-F 4 ~COH (A) CH
311 4-F 4 ~COH (B) N
25 312 4-F 4 acoa (B) C~
313 4-F 5 C=O N
314 4-F 5 C-O C~
315 4-F 5 HCOH (A) N
316 4-F 5 HCOH (A) ca 30 317 4-F 5 HCOH (B) N
318 4-F 5 HCOH (B) ca 320 4-F 6 CAO C~
321 4-F 6 ~CO~ (A) N
35 322 4-F 6 ~COH (A) CH
323 4-F 6 ~COH (B) N
324 4-F 6 HCOH (B) CH

40 327 4-~ 7 HCOH (A) N
328 4-F 7 HCOH (A) CH
329 4-F 7 HCOH (B) N
330 4-F 7 HCOH (B) CH
.. ~ .

.g lZ745Zl - 16 - o. z. 0050/37398 No. R~ m Y Z Phys;cal data IR bands 331 4-F 8 C~O N
332 4-F 8 C-O ca OS 333 4-F 8 HCOH (A) 334 4-F 8 aCOH (A) C~
335 4-F 8 HCOH (B) N
336 4-F 8 HCOH (B) CH
337 4-C(CH3)3 2 C'O N . 2963, 2907, 2869, 1718, 1274, 1110 10338 4-C(C~3)3 2 C-O C~
339 4-C(Ca3)3 2 HCOH (A) N 2960, 2869, 1186, 1109, lOgO
340 4-C(Ca3)3 2 ~COH (A) C~
341 4-C(C~3)3 2 ~COH (B) N
342 4-c(Ca3)3 2 ~COH (B) CH
lS343 4-C(Ca3)3 3 C-O N 2963, 2868, 1717, 1275, 1109 344 4-C(Ca3)3 3 C~O CH
345 4-C(Ca3)3 3 HCOH (A) N 2959, 2908, 2868, 1108, 1100 346 4-C(CH3)3 3 HCOH (A) CH
347 4-C(Ca3)3 3 HCOH (B) N 2961, 2907, 2868, 1363, 1109 20348 4-C(Ca3)3 3 HCOH (B) CE
349 4-c(Ca3)3 4 C~O N 2963, 2868, 1717, 1276, 1109 350 4-C(CH3)3 4 C-O CE -351 4-C(CH3)3 4 HCOH (A) N 2958, 2907, 2867, 1368, 1108 352 4-C(Ca3)3 4 HCOH (A) CX
25353 4-C(CH3)3 4 ~COH (B) . N
354 4-C(CH3)3 4 aCOH (B) CH
355 4-C(Ca3)3 5 C'O N 2963, 2865, 1717, 1501, 1109 356 4-C(Ca3)3 5 C-O ca 357 4-C(Ca3)3 5 HCOH (A) N 2959, 2908, 2865, 1363, 1109 30358 4-C(CH3)3 5 HCOH (A) CE
359 4-C(Ca3)3 5 HCOH (B) N 2959, 1363, 1274, 1109 360 4-C(Ca3)3 5 ~COH (B) CH
361 4-C(Ca3)3 6 C~O . N 2953, 2935, 2861, 1717, 1326 362 4-C(CH3)3 6 C~O CH
3S363 4-C(CH3)3 6 HCOH (A) N
364 4-C(Ca3)3 6 HCOH (A) CH
365 4-C(CH3)3 6 ~COH ~B) N 2958, 2907, 2867, 1363, 1108 366 4-C(CH3)3 6 aCOH (B) CH
367 4-C~Ca3)3 7 C'O N
40368 4C(Ca3)3 7 C~O CH
369 4-C(C~3)3 7 HCOH (A) N
370 4-C(CH3)3 7 HCOH (A) CH
371 4-C(CH3)3 7 HCOH (B) N

1Z74S~;~
- 17 - o. z. oo50/37398 N~. Rn m Y Z Physica~ data IR bands 372 4 - C(CE3)3 7 . HCOa (B) ca 373 4 - C(C~3)3 8 C~O N
05 374 4-C(Ca3)3 8 C~O ca 375 4 - C(CH3)3 8 ~COE (A) N
376 4-C(CH3)3 8 acoa (A) C~
377 4 - C(C~3)3 8 HCO~ (B) 378 4-C(C~3)3 8 ~COH (B) . CE
10 379 2-CF3 2 CO N 1718, 1315, 1165, 1122, 1060 380 2-CF3 2 aCOH (A) N 1315, 1165, 1123, 1060, 1040 381 2-CF3 2 HCOH (B) N 1317, 1178, 1135, 1123, 1090 382 2-Br 2 CO N 1717, 1502, 1276, 1138, 1107 383 2-Br 2 aCOH (A) N
15 384 2-Br 2 HCOH (B) N 2957, 2924, 1138, 1103, 751 385 3-F 2 CO N 2968, 1717, 1276, 1256, 1139 ~i274521 - l& - O.Z. 0050/37398 The novel compounds have an excellent action on a broad spectrum of plant-pathogenic fungi, especially from the Ascomycetes and sasidiomycetes classes. Some of them have a systemic action and may be used as soil and foliar 05 fungicides.
The fungicidal compounds are of particular interest for combatting a large number of fungi in various crops or their seed, especially wheat, rye, barley, oats, rice, Indian corn, cotton, soybeans, coffee, sugarcane, fruit, ornamentals in horticulture, and vegetables, such as cucum-bers, beans and Cucurbitaceae.
The novel compounds are particularly suitable for comba~ing the following diseases: Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in grapes, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugarcane, Venturia inaequalis (apple scab), Septoria nodorum in wheat, Botrytis cinerea in grapes and strawberries, Cercospora musae in bananas, Pseudocercosporella herpo-trichoides in wheat and barley, Hemileia vastatrix in coffee, Piricularia oryzae in rice, Alternaria solani in potatoes and tomatoes, Plasmopara viticola in grapes, and Fusarium and Verticillium species in various plants.
The compounds are applied by spraying or dusting the plants, or treating the seed with the active ingredients.
Application may be effected before or after infection of the plants or seed by the fungi.
The novel active ingredients can be converted into the conventional formulations, e.g. solutions, emulsions,suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agent is to be used; at all events, it should ensure a fine and uniform distribution of the active ingredients.
3S The formulations are prepared in the conventional manner, for example by diluting the active ingredient with sol-.: ' . , ' .
.
-1;Z745Zl - 19 - o.z. 0050/37398 vents and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without an organic auxiliary solvent.
Suitable auxiliaries are, essentially, solvents, for 05 example aromatics, e.g. xylene and benzene, chloro-aromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g. ethanolamine, and dimethylformamide and water;
carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g.
highly disperse silica and silicates; emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxy-ethylene fatty alcohol ethers, alkylsulfonates and aryl-sulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.
The fungicidal agents generally contain from 0.1 to 95, preferably from 0.5 to 90, wt% of active ingredient.
The application rates depend on the effect desired, and range from 0.02 to 3 kg of active ingredient per hec-tare, or more.
The novel compounds may also be used for protectingmaterials, inter alia for combatting wood-destroying fungi such as Coniophora puteana and Polystictus versicolor. The novel active ingredients may also be used as fungicidally effective components of oily wood preservatives for protecting wood against wood-discoloring fungi. The agents are applied by treating, e.g., impregnating or painting, the wood with them.
The agents and the ready-to-use formulations made therefrom, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in known manner, for example by spraying, atomizing, dusting, scattering, seed-disinfecting, or watering.

12t~4521 - 20 - O.Z. 0050/37398 Examples of formulations are given below.

I. 90 parts by weight of compound no. 11 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A
05 mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 2 is dis-solved 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-monoethanol-amide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic 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. 15 is dis-solved 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 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 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 finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 87 is dis-solved 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 and 280C, and 10 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.
V. 80 parts by weight of compound no. 99 is well mixed with 3 parts by weight of the sodium salt of di-isobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid 1274S~l - 21 - O.Z. 0050/37398 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.
05 VI. 3 parts by weight of compound no. 129 is intimately mixed with 97 parts by weight of parti~ulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 147 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. 213 is intimately mixed with lO parts 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 dis-persion.
IX. 20 parts of compound no. 215 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate and 68 parts of a paraffinic mineraloil. A stable oily dispersion is obtained.
In these application forms, the agents according to the invention may also be mixed and applied with other active ingredients, e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers. When mixed with other fungicides, the spectrum of fungicidal action is in many cases increased.
The following list of fungicides with which the compounds according to the invention can be combined is intended to illustrate , and not restrict, the combination 12~7~5~1 - 2- - O.Z. 0050/37398 possibilities.
Examples of fungicides which may be combined with the active ingredients according to the invention are as follows:
05 sulfur dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate zinc dimethyldithiocarbamate manganese ethylenebisdithiocarbamate 1~ zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate zinc-(N,N'-propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and N,N'-polyethylene-bis-(thiocarbamoyl)-disulfide ammonia complex of zinc-(N,N'-propylene-bisdithio-carbamate) and N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide nitro derivatives, such as dinitro-(l-methylheptyl)-phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate diisopropyl 5-nitroisophthalate heterocyclic structures, such as 2-heptadecyl-2-imidazoline acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethylphthalimidophosphorothionate 5-amino-1-~bis-(dimethylamino)-phosphynyl]-3-phenyl-1,2,4--triazole 2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio-(4,5-b)-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate 2-methoxycarbonylaminobenzimidazole 2-[furyl-(2)]-benzimidazole 127~5~1 - 2~ - O.Z. 0050/37398 2-~thiazolyl-(4)]-benzimidazole N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide N-trichloromethylthiotetrahydrophthalimide N-trichloromethylphthalimide 05 N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl--sulfuric acid diamide 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole 2-thiocyanomethylthiobenzthiazole 1,4-dichloro-2,5-dimethoxybenzole 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone pyridine-2-thio-1-oxide 8-hydroxyquinoline and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-di-lS oxide2-methyl-5,6-dihydro-4-H-pyran-3-carboxanilide 2-methyl-furan-3-carboxanilide 2,5-dimethyl-furan-3-carboxanilide 2,4,5-trimethyl-furan-3-carboxanilide 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide 2-methyl-benzoic acid anilide 2-iodobenzoic anilide N-formyl-N-morpholine-2,2,2-trichloroethylacetal piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-di-methylmorpholineN-~3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine 1-~2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]--l-H-1,2,4-triazole 1-~2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl--ethyl]-1-H-1,2,4-triazole lZ7~5Zl - 24 - O.Z. OOS0/37398 N-(n-propyl)-N-(2,4,6-trishlorophenoxyethyl)-NI-imidazol--ylurea 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)--2-butanone 05 1-(4-chlorophenoxy)-3,3-dimethyl-1-~lH-1,2,4-triazol-1-yl)--2-butanol alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimidine-methanol 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene and various substances, such as dodecylguanidine acetate 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutar-imide hexachlorobenzene D,L-methyl-N-(2,6-dimethylphenyl)-N-(2-furoyl)-alanate methyl D,L-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)--alanate N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyro-lactone methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxa-zolidine3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxa-zolidin-2,4-dione 3-(3,5-dichlorophenyl)-1-isopropyl-carbamoylhydantoin N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-di-carboximide2-cyano-N-(ethylaminocarbonyl-2-methoximino)-acetamide 1-(2-(2,4-dichlorophenyl)-pentyl)-lH-1,2,4-triazole 2,4-difluoro-alpha-(lH-1,2,4-triazol-1-yl-methyl)-benz-hydryl alcohol.

,~ . .

~Z~7 ~S21 - 2~ - O.Z. 0050/37398 For the following experiments, the prior art active ingredient 2,2-dimethyl-4-(1,2,4-triazol-1-yl)-5-phenyl-pen-tan-3-one (A) was used for comparison purposes.

05 Use Example 1 Action on cucumber mildew The leaves of pot-grown cucumber seedlings of the "Chinesische Schlange" variety were sprayed at the 2-leaf stage with a spore suspension of cucumber mildew (Erysiphe cichoracearum). After about 20 hours, the plants were sprayed to runoff of aqueous emulsions consisting (dry basis) of 80~ of active ingredient and 20% of emulsifier.
After the sprayed-on layer had dried, the plants were set up in the greenhouse at from 20 to 22C and a relative humidity of 70 to 80%. To assess the action of the novel compounds, the extents of fungus spread was determined after 21 days.
The results of this experiment show that for instance compounds nos. 2, 11, 15, 87, 99, 129, 147, 213, 215, 231, 233, 255, 339, 351, 365, 379, 380, 381~ 383 and 384, applied as 0.025% spray liquors, had a better fungicidal action (e.g., 100%) than prior art active ingredient A
(60%).

Use Example 2 Action on BotrY is cinerea in Pimientos Pimiento seedlings of the "Neusiedler Ideal Elite"
variety were sprayed, after 4 to 5 leaves were well developed, to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsi-fier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus Botrytis cinerea, and placed at 22 to 24C in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses covered the major portion of the leaves.

lZ74521 - 2G - 0. z . 0050/37398 The results of this experiment show that f or instance compounds nos. 17 t 147, 231, 233, 255 and 297, applied as 0.05~, spray liquors, had a better fungicidal action (e.g., 97~) than active ingredient A (60~,).

,:

. . . .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A benzyloxyalkylazole of the formula:

(I) where R is halogen, alkyl of 1 to 4 carbon atoms, alkoxy where alkyl is of 1 or 2 carbon atoms, haloalkyl in which alkyl is of 1 or 2 carbon atoms, unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted pyridyl, benzyl, alkylthio of 1 to 4 carbon atoms or hydrogen, n is an integer from 1 to 5, m is an integer from 1 to 8, Y is a C = O or HCOH group and Z is a CH group or an N atom.

2. A benzyloxyalkylazole of the formula (I) as set forth in claim 1, where R is hydrogen, halogen, lower alkyl of 1 to 4 carbon atoms, or haloalkyl of 1 to 2 carbon atoms and 1 to 3 halogen atoms.

3. A benzyloxyalkylazote of the formula (I) as set forth in claim 2, where Rn is 4-CF3, m is 2 or 5, Y is CHOH, Z is N.

4. A process for combatting fungi, wherein a benzyloxyalkylazole of the formula:

(I) where R is halogen, alkyl of 1 to 4 carbon atoms, alkoxy where alkyl is of 1 or 2 carbon atoms, haloalkyl in which alkyl is of 1 or 2 carbon atoms, unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted pyridyl, benzyl, alkylthio of 1 to 4 carbon atoms or hydrogen, n is an integer from 1 to 5, m is an integer from 1 to 8, Y is a C = O or HCOH group and Z is a CH group or an N atom, is allowed to act on fungi, their habitat, seeds, plants, soil or materials.

5. A process for combatting fungi as set forth in claim 4, wherein a benzyloxyalkylazote of the formula (I), where Rn is 4-CF3, m is 2 or 5, Y is CHOH, Z is N, is allowed to act on fungi, their habitat, seeds, plants, soil or materials.

6. A fungicidal composition comprising fungicidally effective amount of a compound as claimed in claim 1, 2 or 3, in admixture with at least one acceptable carrier.