Method of producing derivatives of 1-azolyl-2-aryl-3-fluoralkan-2-ol

专利摘要:
Es werden 1-Azolyl-2-aryl-3-fluor-alkan-2-ole der allgemeinen Formel I beschrieben, worin Az für 1H-1,2,4-Triazol, 4H-1,2,4-Triazot oder 1H-Imidazol steht; Ar einen unsubstituierten oder substituierten aromatischen Rest aus der Reihe Phenyl, Biphenyl, Phenoxyphenyl und Naphthyl bedeutet; R, für Wasserstoff, C,-C4-Alkyl, C3-C5-Alkenyl oder Benzyl steht; R2 Wasserstoff, Fluor oder C1-C6-Alkyl bedeutet; und R3 Wasserstoff, Fluor, C1-C6-Alkyl, C1-C6-Haloalkyl, C1-C6-Alkoxy, C,-C6-Alkylthio, Phenyl, Phenoxy, Phenylthio oder C3-C7-Cycloalkyl steht, wobei jeder aromatische Substituent oder aromatische Anteil eines Substituenten unsubstituiert oder ein- oder mehrfach durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C,-C4-Haloalkyl, Nitro und/oder Cyanosubstituiert ist; unter Einschluss der Säureadditionssalze, quaternären Azoliumsalze und Metallkomplexe. Es werden ferner Methoden zur Herstellung dieser Produkte offenbart sowie agrochemische Mittel, die als Wirkstoff eine dieser Verbindungen enthalten. Ferner wird ein Verfahren zur Bekämpfung phytopathogener Mikroorganismen mit Hilfe dieser Substanzen beschrieben.
公开号:SU1326194A3
申请号:SU833675009
申请日:1983-12-12
公开日:1987-07-23
发明作者:Штурм Эльмар；Майер Альфред
申请人:Циба-Гейги Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to a process for the preparation of new substituted 1-azolyl-2-aryl-3-fluoroalkan-2-ols, which can be used to combat harmful microorganisms, preferably fungi damaging plants.
Example 1, A, 1- (., 4-Dichlorophenyl) -2-fluorobutanone.
To a mixture of 77 g of 1- (2, 4-dichlorophenyl) -2-bromobutanone and 500 mg of 18-cut-6 in 750 ml of absolute acetonitrile, 31 g of dry potassium fluoride are added and the mixture is slowly heated to 100-110 ° C with stirring. After 48 hours, the reaction is terminated (chromatographic control or NMR control).
The reaction solution is now poured into 2 liters of ice water and extracted several times with diethyl ether. The combined extracts are washed with water, dried over sodium sulfate and evaporated. 57 g yield of oily product. (H - F binding constant 50 Hz). Bp 77-78 ° C (0.008 mbar).
B. 2- (2,4-Dichlorophenyl) -2- (1-fluoropropyl) -oxirane.
8 g of 80% sodium hydride are suspended in 300 ml of absolute DMSO. Then, in the atmosphere, 68 g of trimethyloxosulfonium iodide are introduced in portions with stirring in portions. After termination of hydrogen evolution and after termination of the exothermic reaction, the mixture is stirred for another 2 h at RT. Then, a solution of 57 g of 1- (2,4-dichlorophenyl) -2-fluorobutanone in 100 ml of THF is added dropwise for 30 minutes, the mixture is stirred for 3 h and then diluted with ice water to five times the volume and extracted several times with diethyl ether. The combined extracts are washed with water, dried over sodium sulfate and freed from solvent in vacuo. Yield 55 g in the form of brown oil.
B. Obtaining the target product
A mixture of 55 g of 2- (2,4-dichlorophenyl) -2- (1-fluoropropyl) -oxirane, 30 g of 1,2,4-triazole and 3.5 g of potassium t-butylate in 500 ml of DMF is stirred for 80 hours at 80 ° s Then the reaction solution is cooled to room temperature, poured onto 2 l of ice water, extracted several times with diethyl ether. The combined extracts are washed with water, dried over sodium sulfate and concentrated. Output 1- (1H
five
0
five
0
five
0
five
0
five
1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-pentan-2-ol 26 g in the form of colorless crystals. M.p. 204 - 206 S.
D. The same target product is obtained by stirring for 29 hours a mixture of 20 g of 2- (2,4-dichlorophenyl) -2- (, Ftorprop 1) oxirane, 12 g of 1,2, 4-triaol and 3 g of tert-butyllate sodium in 200 ml of dimethyl sulfoxide and by treatment. Yield 1 g. T.sh1. 203-206 ° C.
D. The same target product is also obtained due to the fact that a mixture of 25 g of 2- (2,4-dich; jurfensh1) -2- (1-fluoro-propyl) -oxirane with В g of the potassium salt of 1,2,4-triazole , obtained from 1,2,4-triazole and potassium methylate, in 500 ml of triamide hexamethylphosphoric acid. You are stirred for 3 days. at 20-23 ° C and the reaction mixture is treated. Yield 9 g, T.PL. 204-207 S.
E. The same target product is obtained by the fact that 12 g of 1,2,4-triazole, 3.2 g of sodium isopropoxide and 25 g of 2- (2,4-dichlorophenyl) 2- (1-fluoropropyl) - oxirane in a mixture of 200 ml of N, N-diethyl acetamide with 300 ml of xylene is heated for 8 hours at 100 ° C. Output 9.8 g, T.PL. 202-205 ° C.
Example 2. Preparation of 1- (1H-- 1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3-fTorpropan-2-ol.
A. - (2,4-Dichlorophenyl) 2-bromo-2-fluoroethanone.
To a solution of 20.7 g of o-fluoro-2,4-dichloroacetophenone in 100 ml of carbon tetrachloride at 40-45 seconds a solution of 16 g of bromine in 100 ml of carbon tetrachloride is added. After I h, the brown solution becomes colorless. Stir for another 1 h and then shake with an aqueous solution of sodium bicarbonate and evaporate in vacuo. The oily residue is then distilled under high vacuum. Yield 17 g, bk. 89-92 ° C (0.02 mbar).
B. I- (2,4-Dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoroethanone.
12.8 g of chlorophenol and 13.8 g of potassium carbonate in 200 ml of acetone are stirred for 1 hour. To this suspension 28 g of N (2,4-dichlorophenyl) -2-bromo-2-fluoroethanone in 50 ml of acetone are added dropwise and the mixture is boiled t with reflux for 3 hours. After cooling to room temperature
3J326
Colorless precipitates are filtered off, the acetone is removed in vacuo and diethyl ether is added. The ether solution is washed with water, dried over sodium sulfate, filtered and concentrated. The particulate product crystallizes after insisting with n-hexane. Output 21.5 g in the form of
yellowish crystals. M.p. 85-87 C,
B. 2 - (. 2, -Dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) -oxirane.
1 g of 80% sodium hydrate under nitrogen is stirred in 80 ml of DM 60 and 10.3 g of trimethyloxosulfonium iodide are mixed in portions. After the termination of the exothermic reaction, the mixture is stirred at room temperature for another hour, then a solution of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoranthanone in 30 ml of THF is added dropwise, the mixture is further stirred for 5 h at 25-30 C and then poured into 1 liter of water. The product is extracted with diethyl ether, the margins are washed with water, dried over sodium sulfate, filtered and concentrated. Yield 5 g as a yellowish oil.
G. Obtaining the target product. A solution of 13 g of 2- (2,4-dichlorophenyl) 2g (4-chlorophenoxyfluoromethyl) -oxirane, 4 g of 1,2,4-triazole and 0.5 g of tert-buty potassium in 100 ml of DMF is stirred for 15 hours at 80 - 100 ° C. After cooling to room temperature, the reaction solution is poured into 500 ml of water, the crude product being isolated as an oil. It is extracted with diethyl ether, the combined extracts are washed with water, dried over sodium sulfate, filtered and concentrated. The yield is 1 I g of an oily crude product, which crystallizes on addition to n-hexane. The yield of the valuable product 7 g. 155 - 157 ° C.
D. The same target product is obtained by the fact that a mixture of 25 g of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) oxirane, 7.5 g of 1,2,4-triazole and 10 g of sodium carbonate in 600 ml of sulfanol (tetramethylene sulfone) is stirred for 3 days. at 90 - 100 ° C, cooled to room temperature, the re- {; the ionic mixture is poured onto 3000 cm of crushed ice, extracted with dimethyl ether, the combined extracts are washed with water, dried over
0
five
n 5
about q d
d
five
94 sodium sulfate, the solvent is distilled off and the remaining acl is stirred in r-hexane. Exit 12.3 g. Tp.153-.
E, 1A, 3 g T tKoro the same target product is obtained by the method; ke 1E, when 8 g of potassium hydroxide is used instead of sodium carbonate and npir are working. " 80-100 ° C in 1000 ml of dimethyl sulfoxide. M.p. 155- 56 p.
Froze 1- (1H-1,2,4-Tpiazol-l-yl) -2-p- (4-chlorophenoxy) -2-methylphenyl-3-fluoropropan-2-ol.
30 g of 2- (4-chlorophenoxy) -2-methylphenyl 2-fluoromethyloxyran, 15 g of triazole and 10 g of sodium hydroxide in 650 ml of sulfolane are stirred for 12 hours at 95-100 ° C. After cooling to room temperature, the solution is poured onto 3000 cm of crushed ice, extracted several times with diethyl ether, the combined extracts are washed with water, dried over sodium sulfate, filtered and concentrated. The oily crude product is dissolved in 100 MP of methylene chloride, filtered through silica gel and the solvent is removed in vacuo.
Output 1 3.2 g of resin with p, 1.5131. The same result comes due to the use of P, P-diethyl acetamide as a solvent and sodium methyl acetate as a base, if it is operated at 60 - 70 ° C.
Example 4. 1- (1H-1,2,4-Triazol-1-yl) (4-chlorophenoxy) -phenyl 2-methoxy-3-fluoropropane.
To O, 7 g of sodium hydride dispersion (55% in mineral oil) in 20 ml of dimethylformamide in an atmosphere of nitrogen and with stirring a solution of 5 g of 1- (1H-, 2,4-tripiazol-I-yl) -2- f is added dropwise p-l4-chlorophenoxy) phenyl-3-fluoropropan-2-ol., 25 ml of dimethylformamide and 3 ml of absolute tetrahydrofuran. The mixture is stirred at up to the termination of hydrogen separation. Then it is cooled to room temperature and then 1 ml of methyl iodide is added dropwise. The reaction mixture is stirred for approximately 12 hours at room temperature, then poured into a saturated solution of sodium chloride and the mixture is extracted three times with ethyl acetate. The combined extracts are washed 2 more times with semi-saturated solution of yatri chloride, dried over sodium sulfate, filtered and dried.
center. The crude product is obtained by column chromatography (silica-gel-dichloromethane / methanol 9: 1). The title compound is obtained in the form of a high viscous oil. Yield 5 g 96% of theory 1,5998.
Froze 1- (1H-1,2,4-Tri-ZOL-yl) -2- (2,4-dichlorophenyl) -3-fluoro-butan-2-ol ..
A mixture of 22 g of 2- (2.4 dichlorophenyl) -2- (1-fluoroethyl) -oxirane, 9.6 g of 1,2,4-triazole and 1.0 g of potassium tert-butylate in 250 ml of dimethylfirmamide is stirred for 5 days at 20 ° C. After that, the reaction solution is poured onto 800 ml of ice-cold water and extracted three times with diethyl ether. The combined extracts are washed with water; dried with 1% sodium sulfate and concentrated. The residue is recrystallized from ethyl acetate and the title compound is obtained in the form of white crystals. M.p. 202-204 ° C
IT e rm 6. G - (1H-1, 2, | -Tri-azole 1 -yl) (4-chlorophenoxy 11) -phenyl-3 fluorobutane 2ol.
A mixture of 38.4 g of (4-chlorophenoxy) -phenyl-2 (1-fluorostil) -oxirane, 18.g of sodium salt of triazole in 250 ml of dimethylformamide is stirred for 25 hours at 150 ° C. After that, the reaction-ion solution is cooled to room temperature, and extracted into 800 ml of ice-water, extracted several times with ethyl acetate of acetic acid. The combined extracts are washed with water, dried over sodium sulfate and concentrated. The residue is recrystallized from ethyl acetate and the title compound is obtained in the form of yellow crystals.
T.gsh. 146-147 C.
Example 7. 1- (1H-1,2, azol-1-yl) -2 - (, 2,4-dichlorfesch) -2-benzyloxy-3-fluoropropane.
In 0.7 g of sodium hydride dispersion (55% in mineral oil) in 20 ml of dimethylformamide, a solution of 4.5-g - (1H-, 2,4-triazol-1-yl) is instilled under nitrogen and with stirring -2- (2,4-dichlorophenyl) -3-fluoropropan-2-ol 25 ml of dimethylformamide and 3 ml of absolute tetrahydrofuran. The mixture is then stirred until the end of hydrogen separation at 40 ° C, then allowed to cool to room temperature, and after this, 2.8 g of benzyl bromide are instilled. The reaction mixture .mixed with o korio for 14 h at rooms
o
five
0
five
40
45
50 55
0
35
NOI teureture, then poured onto a saturated solution of sodium chloride and extracted the mixture three times with ethyl acetate. The combined extracts are washed twice with a half-saturated solution of sodium chloride, dried over sodium sulfate, filtered and concentrated. The crude product is purified by chromatography on a column (silica gel-dichloromethane / methanol 10: 1). The title compound is obtained as a gum.
 1.5762.
EXAMPLE 8 1- (1H-1,2,4-Tpi-azol-l-yl) -2- (2-chloro-4-fluoro-phenyl) -2-allyl oxy-3-ft6-pentane -2-ol.
In 0.7 g of sodium hydride dispersion (55% in mineral oil) in 20 ml of dimethylformamide, a solution of 4.5 g of I- (IH-1,2,4-trizolol-1-yl) - 2- (2 chlorop-4-fluorophenyl) -3-fluoropentan-2-ol ,, 25 ml of dimethylformamide and 3 ml of absolute tetrahydrofuran. The mixture is stirred until the evolution of hydrogen is complete at 40 ° C, set to cool to room temperature, and 0.5 ml of allyl bromide is instilled in this. The reaction mixture is stirred for about 10 h at room temperature, then poured onto a saturated solution of sodium chloride and the mixture is extracted 3 times with ethyl acetate acetic acid.
The combined extracts are washed twice with a half-saturated solution of sodium chloride, dried over sodium sulfate, filtered and concentrated. Get the title compound in the form of resin
The elemental composition data are presented in Table 2.
Biological examples. Action against Puceina graminis on wheat.
Residual-protective action.
 Wheat: 6 days after sowing, after sowing, spray broth (0.02% of the active substance) prepared from a wettable powder of a biologically active substance is sown. After 24 hours, the treated plants are infected with ribad uredodore suspension. After incubation for 48 hours at a relative humidity of 95-100% and at about 20 ° C, the infected plants are placed in a greenhouse at about. Rating
713
Rust, pustules are developed after 12 days. after infection.
System action
Fluffy plants after 5 days. after sowing, sprinkle the broth for spraying prepared from the wettable powder of the biologically active substance (0.06% of the active substance per soil volume) after 48 hours. After 48 hours, the treated plants are infused with a suspension of fungi uredospores. After incubation for 48 hours at a relative humidity of 95 100% and at about 20 s infected plants are kept in a greenhouse at about. An assessment of the development of rust pustules is carried out after 12 days. after infection.
The compounds of Table 3 show a good anti-rust activity. Untreated, but infected control plants show a rust fungus of 100%. Compounds 28 and 30-30 suppress the rust fungus to 0-5%.
Action against Cercosfora arachi- dicola on peanut plants.
Residual-protective action.
 Peanut plants 10–15 cm high are sprayed with spraying broth prepared from a wettable powder of the biologically active substance (0.006% of the active substance). and 48 hours later, they are infected with a conidia suspension of the fungus. Infected plants are incubated for about 72 hours at about 21 C of high relative air humidity and then kept in a greenhouse until typical spots appear on the leaves. The evaluation of the fungicidal action is carried out after 12 days. after infection, the assessment is based on counting and determining the size of the occurrence of spots.
Compared to untreated but infected control plants (the number and size of the penta is 100%), the peanut plants that have been treated with biologically active substances show a greatly reduced lesion. So, connections 1–9, F3, 16, 17, 18, 19, 2 2–28, as well as 31 pre-. the occurrence of the spot is almost completely eliminated (0-10%).
Action against Erysiphae graminis on barley.
948
Residual-protective action.
At about 3 cm high, the plants are sprayed with a spraying broth prepared from a wettable powder of the biologically active substance (0.002% of the active substance). After 3-4 hours, the treated plants are dusted with fungus conidia. Infected barley plants are placed in a greenhouse at about 22 ° C and the fungal damage is assessed after 10 days.
System action
Barley plants about 8 cm tall are poured with a spraying broth prepared from a wettable powder of a biologically active substance (0.006% of the active substance per soil volume). At the same time, it is important that the spraying broth does not come into contact with the above-ground parts of the plants. After 48 hours, the treated plants were dusted with conidia of the fungus. Infected barley plants are placed in a greenhouse at about 22 ° C and fungal damage is assessed after 10 days.
The compounds of formula (I) have a good action against the fungus Erysiphe. Untreated but infected control plants show a defeat to Erysiphe YuO. Compounds 1-10, 13-19, 21-29, and 30- 33 suppress the fungal infection in the case of barley to 0-5%, in particular, compound 2 causes a complete reduction of the damage.
Residual-protective action against Venturia-inaegualis on the blond shoots.
Blon cuttings with fresh shoots 10–20 cm long are sprayed with broth prepared from a wettable powder of a biologically active substance (.0.006% of the active substance) After 24 hours, treated plants are infected with a suspension of conidia of the fungus. The plants are then for 5 days. incubated at a relative humidity of 90-100% and kept in a greenhouse at 20-24 ° C for the next 10 days. A scabby lesion is assessed after infection. Compounds 1-6, 8, 9, .13, 15, 16, 17, 19, 24, 26-28, and 30 and 34 suppress disease damage to less than 10%. Untreated but infectious
913
In the control shoots, on the contrary, they are 100% affected.
Action protin Botrytis cinerea on the beans. Residual safety action
Bean plants of about 10 cm high are sprayed with spraying broth prepared from a wettable powder of the biologically active substance (0.02% of the active substance). After 48 hours, the treated plants are infected with a copy of the fungus copy. After incubation of infected plants for 3 days. at a relative humidity of 95-100% and at 21 s, the assessment of fungal damage is carried out. The compounds in many instances very strongly suppress the fungal infection. At a concentration of 0.02%, compounds 1-6, 8, 9, 13, 14, 17, 18, 19, 21, 24, 26, 27, 28 and 30, 34 were completely active. The disease was 0- eight%. Botrytis damage to untreated but infected bean plants is 100%.
The action against Piricularia is ogusal on rice plants.
Residual-protective action.
After two weeks of cultivation, rice plants are sprayed with a broth for spraying prepared from a wettable powder of a biologically active substance (0.002% of the active substance). After 48 hours, treated plants are infected with a suspension of conidia of the fungus. After incubation for 5 days. at relative air humidity of 95-100% and 24 ° C, the fungal damage is assessed.
Rice plants that have been treated with spraying broth containing one of the compounds as an active substance, for example 13 or 19, compared with untreated control plants (100% damage) show less than 10% fungal damage.
In the following studies, for comparison, the following structurally closest substances were tested:
Known compound
J VH „
(X1 Cl-fJV-C-CHj-X P
 -1 --TsJ
CH
H Clrl2, CH j
9410
Offered compounds
Cl
OH
(C1-Q C-CH2.- CH
/
F CH2-CH

Cl OH
(S). - N (1
N.
year
B1

CH-CHj
I-j

CO ci-Oc-CH-i n
CH /
F CH2,
Water solubility test
Water solubility at, ppm
X40.00
A0.05
B0,01
0.50
Treatment; data and evaluation.
The introduction of a fluorine atom at the coordination site of a molecule of a known compound entails a significant change in the physicochemical properties. Thus, the water solubility of the proposed compounds varies significantly. The solubility in water decreases, in contrast to the known compound, by a factor of 4000 - 80. This means simultaneously the correspondingly increased lipid solubility of these compounds. These properties of biologically active substances play a significant role in the application to the plant. At high water solubility, the biologically active substance is easily washed off by rain from the leaves, while the limited solubility in water, which is equal to the correspondingly high lipid solubility, increases the penetration ability
biologically active substance through the fat-soluble wax layer of the leaf surface and as a result of this leads to a better absorption of the biologically active substance by the plant and to a more rapid manifestation of the fungicidal activity. This results in a generally lengthening of the spraying intervals over the entire treatment period, and thus a reduction in the overall rate of rust, and the appearance of rust blisters we are consuming during the sowing season.
A long-term test against Puceinia hordei and against Puccinia triticina.
In the following experiments, under real 5 conditions of use (open ground), prolonged activity of substances A, B, C and X was tested. Both important species of pest fungi 20 Puccinia hordei on barley and Puccinia triticina on wheat were selected as indicator fungi.
Test 1. Action against Puccinia hordei on barley.
Two separated by space small areas of open ground from open ground with a northern area of each 4 m are sown with barley and, after planting, with bushes, sprayed with a spraying solution made by spraying (30.5 g of biologically active substance per 1 ha), 24 hours after application of biologically active
on the surface of plant leaves and compared with untreated, but also contaminated open ground plants.
i The experiments are repeated three times. Assessment produced after 5 weeks. after applying an appropriate biologically active distribution. Table 3 shows the fungal infection after the application of the biologically active substance.
In experiments I and 2, compounds of the invention A, B, and C after another 5 weeks. after applying biologically active substances to cultivated plants, they still cause practically complete protection (11–13% or 7–10%; control plants of 100% fungal damage) against the occurrence of harmful fungi, while compound X very close in structure the prior art does not have acceptable for practical use in open ground
In experiments I and 2, compounds of the invention A, B, and C after another 5 weeks. after applying biologically active substances to cultivated plants, they still cause practically complete protection (11–13% or 7–10%; control plants of 100% fungal damage) against the occurrence of harmful fungi, while compound X very close in structure the prior art does not have acceptable for practical use in open ground
the plant substances are inoculated with a standard suspension of uredospores 35 fungicidal activity (71% or 52% of the fungus Puccinia hordei. 14, the site of the fungal lesion). Consequently, the ki of the earth are somewhat exposed to natural environmental conditions, like day-night-rhythm.
Compounds A, B and C in open ground are significantly superior to Comparative X.
solar radiation, precipitation, etc. and continuously check for the appearance of rust blisters on the surface of the leaves of the plants and compare them with untreated, but also infected, open ground plants. The test is repeated three times. The evaluation was made 5 weeks after the application of the corresponding biologically active substance.
Test 2: Action against Puccinia triticina on the sack.
Two separated shallow areas of open ground with a cultivated area of t M. are sown with syenitz and, after planting, with bushes, sprayed with wetting powder made with spraying solution (62.5 g of biologically active substance per 1 ha). 24 hours after the application of the corresponding biologically active substance, the plants are inoculated with a standard suspension of uredospores of the fungus Puccinia triticina. Small plots of the earth are exposed to natural conditions of the environment for several weeks, such as day-night-rhythm, solar radiation, atmospheric precipitation, etc. and continuously
rust bubbles are repeated
on the surface of plant leaves and compared with untreated, but also contaminated open ground plants.
i The experiments are repeated three times. Assessment produced after 5 weeks. after applying an appropriate biologically active distribution. Table 3 shows the fungal infection after the application of the biologically active substance.
In experiments I and 2, compounds of the invention A, B, and C after another 5 weeks. after applying biologically active substances to cultivated plants, they still cause practically complete protection (11–13% or 7–10%; control plants of 100% fungal damage) against the occurrence of harmful fungi, while compound X very close in structure the prior art does not have acceptable for practical use in open ground
fungicidal activity (71% or 52% fungal infection). Consequently,
fungicidal activity (71% or 52% fungal infection). Consequently,
Compounds A, B and C in open ground are significantly superior to Comparative X.
The lethal dose of Dena in table 4.
50% () preferred inventions
The method of obtaining derivatives of I-azolyl-2-arsH1-3-fluoroalkan-2-ol of the general formula
OBi R2 Az-SNg-C- (j; -F
Ar RS
(I)
Az - lH-1,2,4-tripiazo-Jl or IHimidazole;
Ar is an unsubstituted or substituted A aromatic residue from the series enyl, phenoxyphenyl; 13 R is hydrogen, C is alkyl, C
alkenyl, or benzyl; RJ, is hydrogen; RJ is hydrogen, C is C alkyl,
phenyl or phenoxy, each aromatic substituent or aromatic part of the substituent is unsubstituted or substituted by one or multiple halo with the n / or methyl genome, characterized in that, at 20, in an aprotic solvent, oxirane of the formula
/ H
Af-SSNg ()
F
subject to interaction in the presence of an organic or inorganic base with an azole of the formula
1326194
14
i - AZ,
(Iii)
where M is hydrogen or with a compound of formula (III), where M is an alkali metal atom to form a compound of formula
CH2-Ag I Ñ With -F
Af R2,
(la)
where the radicals have the indicated meanings; if necessary, the alcohol of general formula (1a) is reacted with a compound of formula IV
 R, - W,.
where R., has the indicated meanings; W - HE or halogen, with the selection of the target product in free form,
Table I
15
1326I9A
16 Continued table. t
7111
ten
13
Untreated control plants 100
Table 3
100
47.8 7.4 6.4 9.2
92

权利要求:
Claims (1)
[1]
Claim
The method of obtaining derivatives of 1azolyl-2-aryl-3-fluoroalkan-2-ol of the General formula
Az-CHg-C - ^ - P ₍₁₎ ^Ar where Az is 1H-1,2,4-triazode or 1Nimidazole;
Ag - unsubstituted or substituted aromatic residue from the series phenyl, phenoxyphenyl;
R, is hydrogen, C is alkyl, C alkenyl, or benzyl;
R ₂ is hydrogen;
Rj is hydrogen, C ₄ = alkyl, phenyl or phenoxy, each aromatic substituent or aromatic part of the substituent being unsubstituted or substituted once or repeatedly by halogen and / or methyl, characterized in that at 20-100 ° C in an aprotic solvent, oxirane formulas
F
And _g- C --- CH _g (I)
F is reacted in the presence of an organic or inorganic base with an azole of the formula
And - Az, where M is hydrogen or with a compound of formula (III), where M is an alkali atom. "* A metal to form a compound of formula (1a) where the radicals have the indicated meanings! If necessary, the alcohol of general formula (1a) is reacted with a compound of formula IV'R, - W,
20 where R ^, - has the indicated meanings;
W - OH or halogen, with the release of the target product in free form.
Table 'I
Compound Ag~~ --A. — w ---- X Physical constants ^R '^R 3 1 2 3 4 5 · 6 7 1 1C, H, C1, (2.4) H H θ'Ό ^-01N Mp t55-157’C 2 C _t H, 01, (2,4) H H C, H H Mp 204-206®С 3 € ^, 01, (2,4) H H H N '' 142-143 * C 4 C, H ₄ C1 (4) H H H-CjH, H  149-151’s ; 5 C, H, C1 (2) F (4) H H H N  132-133 * S. 6 "Ό-ο-Ο ·. H H eleven N  118-12O * S 7 α-Ο-ο-Ο H II H CH  156-157’s IN Ο, Η, ΟΙ (2,4) H H^CH i N  202-204’s 9H H H H  87-YuO’S 10H H H CH  100-105 “C AND C _t H | Cl, (2,4) CH H C _t H H  176-179’s.· 1 12' C ₍ H, C1, (2,4) Benzyl H H N ί 1Resin; nj1,5762 thirteen C, H, Cl (2) F (4) a and C, H, I Mp 171-173 ⁱⁿ C
Continuation of the table. I
1 ιξ „r_ ::. ξγ -... 3-. _T4 J ...... 5 ...... 1 ; 6 L 7 14^cl Oo-0 ^ fl - th I 5 Mp 160-163’s !5 C _< fl _J Cl (2) F (4) CHjCB’CHj n s, y. < I Resin 16 C ₄ H, Cl _t (2.4) in and sgsnd I Mp 175-176’s 17 C <H, F (4)^c h ₂ -Q-ci 'I at B I Resin, p * p1.7801 18 C ^ HjCl, (2,4) CH in CH I Resin, n ¹ '1.5332 19 'C _t H, Br (4) H inN 20 C _t H. “Br (4)n C _lHjI Mp 163-165’s 21 C ₄ H ₃ C1 (2) F (4) in in sn I Mp 163-165’s 22 I-O-0-O- fl n sn cn T.PL. 173-174 ^e C 23^C1 O- ° - € Y H in sn I Mp 146 ~ 147 ° C 24 C ₄ B ₄ C1 (2) F (4) in in sn cn Mp 186-198’s 25 ^ 11.0 ^ (2.4) in in s, n cn Mp 195-196 ^e C 26 C _t H, 0 ^ (2,4) Η in C, in the _7thI Mp 141-142 ° C 27 0 ^^ (2.4) . in in C, H I Mp 101-102’s 28 Br ^ Q-O-Q- Η in in I Mp 118-119 ° C 29th Br-oo-o a in in sv Mp 120-125 ° C thirty C _t H, F (4) . in . in^C A I Mp 141-143’s 31 ^ 11 ^ (2,4) CH ₃in in s, n _gI Mp 154-15b “C 32^cl O-0 - <> ch3 ^ci ~ O “° O“ CH3 in in I I Viscous oil 33 Chj in CH I Resin,1,5903 34 Cl <> 0-O- a in "A I Resin, p "1,513! ³⁵ I in Cjh I Mp 1О7-! О8 * С 36 ci-O-o-O- ^ha ₅ in in I Naela1,5998 37 about I in in I Resin, η1,5757
table 2
Compound
Calculated / found,%
II
49.0
49.2 '
49.1
49.0
45.6
45.6
56 _f 2
56.4
48.3
Ζδ74
58.7
58.7
----- J ... L______ Cl F Br 3,1 10.1 125.53.0 10.1 25.2. - 4.4 13,2 22.2 - 4,5 13,2 22.2 ' - - 3,5 14.5 25.5 - 3.4 14.5 24.4 - - 5.8 14.2 11.9 - 5.7 14.2 12.0 -. - 3,7 15.3 12.9 13.9 3,7 15.1 12.8 13.7 - LL. 12.1 10,2 - -
4.4
12.0
8.1
62,4
10,2
5.5
4 ^ 6
62,2 4,5 8.2 10,2 5,4 47.4 4.0 13.8 23.3 47., 6 3.9 13.9 23.1 - 61, 7 4,5 12.7 - 11.5 61.9 4.6 12.8 - H, 3 65.5 4.9 8.5 - H, 5 65.8 5 ° 8.4 • - 11.3 50.6 4.9 12.7 21, 3 5.7
ί
50,4
4.8
56.9
56.8 '
51.8
51.7
..53,5
56.2
56.0
4.1
4.7
4.8
3,7
3.9
5.3
5.2
12.9 21, 0 5.7 - IJ., 1 18.7 5,0 11.1 18.3 4.9 - 13.9  - 12.6 13.9 - 12.5’- - 11.0 18.5 - 10.8 18.2 - - I12.3 10,4 11.1 12.3 10.1 1 1, 0 -
Continuation of Table 2
Calculated / found,%
ıiedppspns[ΞΖΙL _____ γξζ: Br 16 50.6 4.8 12.6 21, 3 - - 50,5 4.9 12.8 21,4 - - 17 62.7 4.7 12,2 10.3 5.5 - 62.8 4.7 12.0¹ ° < ² ^ 5,4 ' - 18 47.1 4.6 13.7 23-, 2 6.247.0 4.6 13.8 23.0 6.0 - 19 50.1 4.2 14.613,2 - 50,0 4.4 14.5 - 13.0 20 63,4 5,0 7.8 - 5.3 - 63.3 5.1 7.6 - 5.2 - 21 59.9 4.7 11, 6 - 5.2 - 60.1 4.8 11,4 - 5,0 - 22 54.5 4.6 9.8 12,4 13.3 __ X = CH 54.6 4.6 9.7 12.1 13.3 “· 23 53.0 4.7 8.8 22.3 - - 52.8 4,5 9.0 22.1- 24 50.7 4.8 12.6 21,4 50.9 4.8 12.7 21.1- 25 52.1 5.2 12.1 20.5 - - 52.0 5.2 11.9 20,2- 26 52.1 3 _t 8 10.7 - - 20,4 52,2 3.9 10.6 20.3 27 55.3 4.1 7.2 - 4.9 20,4 ί · 55,2 4.1 7.04.9 20,0 28 58.5 5,6 15.7 - 14.258.6 5.7 15.614.0 - 29th 54.8 4.9 IhZ14.820,055.0 ' 4.820.1 - thirty 59.8 4.7 11.6 - 5.2 __ 59.9 4.9 11.5 - 5.2. -
Continuation of the table. 2
CompoundCalculated / found 7 FROM N N C1 F Vg
31 62.161, 9 4.6 32 60,4 5,6 60,2 5,4
10.9
10.9
9.2
9.0
And, 1
11, 3
9,4
10.0
5,0
5.1
33 55.6 4.4 .. 10,2 17.3 4.6 - 55.5 4.4 10.0 17,2 4.4 - '34 59.8 4.7 1 1, 6 9.8 5.359.5 4.7 1 1.3 9.9 5.5 1 49.0 3.0 10.1 25.5 4972 10.1 25,2- 2 49.1 4.4 13,2 22.222.2 49.0 4,5 13,2 - - „S 45.6 3,5 •! 4,5 24.5 35 ”6 3.4 14.5 24.4 - -
56.2.5.814.2
56.4 5.714.2
48.3 3,715,3
48.4 3.7 15.1
And 9
12.0
12.9 13.9
THAT 13.7
58.7
58.7
62,4
62,2
4.6
4,5
47.4
3776
AND
4.9
5,0
50.6
fifty"
12.1 10,2 - - 12.0 10.1 - - 8.1 10,2 5.5 - 8.2 10,2 5,4 13.8 23.3 - 13.9 23.1 - - 12.7 - 11.5 - 12.8 - I., 3 8.5 - 11.5 8.4 - 1 1.3 - 12.7 21, 3 5.7 12.9 21, 0 5.7 -
Continuation of Table 2
Calculated / findDayo,%
ΖΞΣΗΞΞΖΞ
Compound
F
FROM
12 56.9 4.2 And, 1 18.7 5,0 - 56.8 ' 4.1 ’ 11.1 18.3 4.9. - thirteen 51, 8 4.7 13.9 - 12.6 '51.7. 4.8 13.912.5 - 14 53,4 3,7 Ji o '18, 5 53.5 3.9 10.8 18.2 - - fifteen 56.2 5.3 12.3 10,4 11.156.0 5.2 12.3 10.1 1 1, 0 - 16 50.6 4.8 12.6 21.3 50.5 ’ 4.9 12.8 21.4 - 17 62.7 4.7 12,2 10.3 5.5 - 62.8 4.7 12.0 10,2 5,4 - 18 47.1 4.6 ... 13.7 23,2 6.2 - 47.0 4.6 13.8 23.0 6.0 19 50.1 4.2 14.6 - 13,2 - 50,0 . ⁴ ' ⁴14.5 · " 13.0. 20 63,4 5,0 7.8 - 5.3 - 63.3 5.1 7.6 - 5.2 21 59.9 4.7 11.6 - 5.2 - 60.1 4.8 11.4 · 5,0 22 54.5 4.6 9.8 12,4 13.3 - X = CH 5T ~ 6 4.6 9.7 12.1 13.3 23 53.0 4.7 8.89.0 22.3 - • - 52.8.22, G - - 24 50.7 4.8 12.6 21,4 - - 50.9 4.8 12.7 21.1 - 25 52.1 5.2 12.1 20.5 - - '52, 0 , 5.2 11.9 20,226 52.1 3.8 10.7 - λ 20,4 52,2 3.9 10.6 • 20.3
Continuation of table 2 '
Calculated / found,%
Compound
eleveneleveneleveneleven1 I"Υ ι ρ-η----- Br ] Cl 27 55.3 4.1 7.2 - 4.9 20 55,2 4.1 7.0 - 4.9 - 20 28 58.5 5,6 15.714.258.6 5.7 15.6 - 14.0 - 29th 54.8 4.9 14.7 - 20,055.0 4.8 14.8 - 20.1 thirty 59.8 4.7 11.6 '5.2 - 59.9 4.9m 11.5 - 5.2 31 62.1 4.7 10.9 9.2 4.961.9 4.6 10.9 9.0 4.8 - 32 60,4 5,6 11.1 9,4 5,060,2 5,4 11.3 10.0 5.1 * - 33 55.6 4.4 10,2 17.3 4.655.5- 4.4 .10.0 17,2 4.4 - 34 59.8 4.7 1 1, 6 9.8 5.3 - 59.5 4.7 11, 3 9.9. 5.5 -
0
Table 3
Compound Experience 1P.hordei on barley Experience 2R. triticinaon wheat relative to control in% absolute in% relative to control in% absolute in% X 71- 68,2 52 47.8 A eleven 10.6 8 7.4 IN 10 9.6 7 6.4 FROM thirteen 12.5 10 9.2 Untreated control plants 100 96 100 92
Table 4
Soi LDyo, Microorganism experience dine hours per million nie
1 6 Venturia inoegualis 2 6 Botrgtis cinerea 3 20 Puccinia graminis 4 20 Venturia inaeguali9 5 20 Cercospora drachidicola 6 2 Erysiphae graminis 7 60 Erysiphae graminis 8 2 Cercospora arachidicola 9 2 Venturia inaegualis 10 60 Venturia inaegualis 14 2 Cercospora arachidicola fifteen 20 Erysiphal graminis 19 0.06 Cercospora arachidicola 33 20 Cercospora arachidicola 34 thirty PuccirflLa graminis 35 6 Puccinia graminis 45 0.6 Cercospora arachidicola 46 6 Puccinia graminis 47 0.2 Cercospora arachidicola 48 0.6 Cercospora arachidicola 49 0.20 Puccinia graminis 51 thirty Cercospora arachidicola 53 20 Botrytis cinerea Π p and me h a h and e. The type of experience is protective.
VNIIIPI Order 3129/58 ________ Circulation 371 _____ Subscription
Production-polygraph, before, Uzhhorod, st. Project, 4

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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CH726982|1982-12-14|

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