Method of producing pyridinyl derivatives

专利摘要:
The invention relates to heterocyclic compounds, in particular to the production of pyridine derivatives FMR-ly 1: CR 1 = CR 2 -CR 3 = CR 4 - CR 5 = C-OCR 6 R 7 R 8 where R 1 -R 5 independently of one FROM A FRIEND -H, HALOGEN, C 1 -C 6 - ALKIL, TRIFTOROMETHYL, METHOXY, CF 3 -O- OR PHENYL R 6 and R 7 - INDEPENDENTLY FRIEND FROM A FRIEND -H, C 1 -C 4 - ALKYL OR PHENYL THAT CAN BE REPLACED BY HALOGEN R 8 - GROUP FOR-Ly A) - ( O ) C = N = CH-CH = CH-CH = CH, B) -C H ( ° R9) N ... = CH-CH = CH-CH = CH with the proviso that when R 3 is methoxy, R 6 is methyl, and R 1 , R 2 , R 4 , R 5 and R 7 mean H at the same time, the R 8 group is in the third or fourth position of the pyridine cycle R 9 -H, methyl or a group of R 10 -C (O) -, where R 10 -C 1 -C 4 is alkyl, methoxymethyl, trifluoromethyl, cyclopropyl or phenyl, which may be substituted with halogen, methyl, trifluoromethyl or methoxy, having fungicidal activity. The goal is to develop a method of obtaining new compounds with the indicated activity. The preparation of the target compounds is carried out from the compound Formula CR 1 = CR 2 -CR 3 = CR 4 -CR 5 = C-OCR 6 -R 7 = C (O) -OR 1 , where R 1 -C 1 -C 2 = alkyl, and R 1 -R 7 is as indicated above, and halopyridine formulas nAL N = CH-CH = CH-CH = CH in the presence of BULI. The resulting product, where R 8 - a), is isolated or reduced to form compounds 1, where c) R 8 - -C ( ° H) - N .. = CH-CH = CH-CH = CH, which in turn is isolated, or is reacted with the compound of the formula CH 3 J to form Compounds 1, where R 9 is methyl, or Compound 1, where R 8 is c), are acylated with an anhydride or acid anhydride of the general formula R 10 -COOH, where R 10 is listed o above, and get compound 1, where R 9 is a group of the formula -C (O) -R 10 . 5 tab.
公开号:SU1500157A3
申请号:SU864028298
申请日:1986-09-30
公开日:1989-08-07
发明作者:Тоблер Ханс；Акерманн Петер；Нифелер Роберт
申请人:Циба-Гейги, Аг (Фирма)；
IPC主号:

专利说明:

3 1500
This invention relates to the preparation of new heterocyclic compounds, in particular, pyridinyl derivatives of the total Lormula.
 Nb (I),
 Ryde independently of one another are hydrogen, halogen, alkyl, trifluoromethyl, methoxy, CFj-0 or phenyl; R and R are independently of each other hydrogen, C-C-alkyl or phenyl, which may be substituted by halogen 5 RJ is a group of the general formula
OR
-sn- @
Until „N
(Ii)
Oyae
provided that when Rj is methoxy,
RC and
and R ,, R,
R
R, Rg is methyl, and. ix, rvj, l.,
simultaneously hydrogen, group R. is in the third or fourth position of the pyridine cycle i
methyl or group
R
about
Rg is hydrogen,
with
II o
where R is C-C-alkyl, methoxymethyl, trifluoromethyl, hclclopropyl or phenyl, which can be substituted by halogen, methyl, trifluoromethyl or methoxy, having fungicidal activity.
The purpose of the invention is to create, on the basis of known methods, a method of obtaining new compounds, which have a high fungicidal activity.
Example 1. Preparation of 1- (3-β-pyridinyl) -2-methyl-2- (4-chlorophenox) -propanone (3)
12 ml of butyl lithium in 1.6 MP of hexane is dissolved in 50 ml of ether (argon atmosphere). 2.6 g of 3-bromopyridine are quickly added. After 30 minutes of stirring, 3.8 g of ethyl 2-methyl-2- (4-chloro-phenoxy) -propionic acid ethyl ester are instilled into the suspension. After 30 minutes of stirring at -7G ° C and 1 hour at 20 ° C, the reaction mixture is mixed with 20 ml of a saturated solution of ammonium sulfate and 5 ml of saturated soda solution, dried
0
50
five
0
five
0
five
about 5
(), are embedded and chromatographed (silica gel) with ethyl acetate / hexane (1: 2) as a solvent.
Compound 3 is obtained with a yield of 67.9% of theory and with so pl. 44-47 C (Table 1),
Example 2. Getting 1- (3- -pyridinyl) -2- (2,4-dichlorophenoxy) - -buten-1-ol (4).
11.16 g of 2- (2,4-dichlorophenoxy) -butyryl-3-pyridine in 105 ml of methanol is mixed in parts with 1.8 g of NaBH. After 1.5 hours of stirring, the solution is boiled, taken up in ethyl acetate, washed with water and brine, dried and bathed. The crude product is crystallized from ethyl acetate / hexane 1: 1.5. Get connection with so pl. 118-120 ° C (and a yield of 66%, mostly as pure geometrically isomeric in the ethylene series).
Example 3. Preparation of 1- (3- -pyridinyl) -1-methoxy-2- (2,4-dichlorophenoxy) -butane (5).
4.53 g of 1- (3-pyridinyl) -2- (2,4- -dichlorophenoxy) -buten-1-ol, mostly pure geometrically isomeric in an ethylene range of 15 ml of tetrahydrofuran, instilled into suspension 0.8 g NaH (50% oil on dispersion, washed in toluene) in 14 ml of tetrahydrofuran. After the termination of the hydrogen release, 10 ml of methyl iodide are added and allowed to react for two hours at. The reaction mixture is evaporated, mixed with water, extracted with ether. The organic phase is separated, washed with water and brine, dried (Na SO), the curing is given (active carbon) and evaporated. After distillation of the crude product at 145-150 C / 10 mbar, compound 5 of the formula is obtained with refraction.
JO.
D
1.5586 and a yield of 73%, mostly as pure geometrically isomeric in the ethylene range.
Example 4. Preparation of 1-acetoxy-1- (3-pyridinyl) -2- (2,4-dichlorophenoxy) -butane of formula (31).
5.2 g of 1- (3-pyridinyl) -2- (2,4-dichlorophenoxy) -butan-1-ol (example 3) in 25 ml of pyridine is mixed with 1.8 ml of acetic anhydride and stirred at room temperature in over night Vypa solution
515
Drain, absorb with ethyl acetate, wash with water and dry with NaCb () and dry. 5.0 g of product are obtained, yield 98.6% 1.5521.
Instead of the acetic anceride, 1.2 ml of acetyl chloride or acetyl bromide can also be used, which, dissolved in 5 ml of glacial acetic acid, are dropped into a solution of an equivalent amount of the starting product in 25 ml of glacial acetic acid at approximately. Then the reaction mixture is stirred for another 1 h and recycled.
Similarly, according to examples 1-3, compounds of the formula are also prepared. (tab. 1).
In this way, also compounds (Table 2) of the formula
Rn b
QHO-C-CO "7
where n is an index of 1, 2 or 3.
According to the method of one of the indicated examples 2 and 3, it is also possible to obtain a compound (Table 3) of the formula
Rn Fig ORg
 fy-O-C-CH-f / I Ic :. Ij
RV V
where n is index 1, 2 or 3.
According to the procedure of Example 4, compounds are also obtained (Table 4).
O-C-RIO
sg
N
w-d /
R.
and also compounds (Table 5)
ABOUT
SG
N
SNCHN-0
Rfi
Biological testing.
Action against Puccinia graminis on wheat.
Residual-protective action.
Wheat is sown 6 days after sowing with a compound made of a wettable powder.
0
five
five
0
five
0
five
0
five
0
five
formula I with a spray solution (0.02% of the test compound). After 24 hours, the treated plants are infected with a suspension of uredospore fungus. After incubation for 48 hours at a relative humidity of 95-100% and at approximately 20 ° C, the infected plants are placed in a greenhouse at about 22 ° C. Rust effects are assessed 12 days after infection.
Systematic action.
5 days after sowing, wheat is sprinkled with a spraying solution made of a wettable powder of the test compound (0.006% of the test compound, calculated on the volume of the soil). After 48 hours, the treated plants are infected with a suspension of uredospore fungus. After incubation for 48 hours at a relative humidity of 95-100% and approximately when infected plants are placed in a greenhouse at a temperature of about. Rust scores are made 12 days after infection.
Compounds 1 (Table 1) show a very good action against Puccinia fungi. Untreated but infected control plants show a 100% defeat from Puccinia fungi. Compounds 2, 7, 19, 29, 30. 2.5-2.8, 2.11, 2.34, 3.1, 3.2, 3.14, 4.1, 4.2, 4.4, 4.22 inhibit the damage from Puccinia fungi to 10% or less.
Action against Cercospora arachi- dicola on peanut plants.
Residual-protective action.
Hazelnut plants with a height of 10–15 cm are sprayed with a spraying solution made from a wettable powder of the test compound (0.006% of the test compound) and contaminated with a conidia suspension of the fungus after 48 hours. Infected plants are incubated for approximately 72 hours at approximately high humidity and then placed in a greenhouse until typical spots appear on the leaves. Evaluation of the fungicidal action is made 12 days after infection for the number and magnitude of the spots.
Compared to untreated but infected control plants (the number and size of spots
 100%), the plants of the ground nut, which are treated with compounds 1 (Table 1), show a greatly reduced lesion from Cercospora fungi. Compounds 2, 19, 29, 2.5, 2.6, 2.7, 2.8, 2.11, 3.1, 3.2, 4.1, 4.2, 4.4, and others almost completely prevent the occurrence of the spot (0-10%).
Action against Erysiphae graminius on barley.
Residual-protective action. 8 cm high barley plants are sprayed with a spray solution made from a wettable powder of the test compound (0.002% of the test compound). After 3-4 hours, the treated plants are pollinated with conidia of the fungus. Infected barley plants are placed approximately in the greenhouse and fungal damage is assessed after 10 days
Systematic action 1e. Barley plants, about 8 cm high, are sprayed with a spraying solution made from a wettable powder of the test compound (0.006% of the test compound based on the final volume). In so doing, care is taken to ensure that the spray solution does not come into contact with the elevated parts of the plants. After 48 hours, the treated plants are pollinated with conidia of the fungus. Infected barley plants are placed in a greenhouse at approximately 22 ° C and fungal damage is assessed after 10 days.
The compounds of the formula I show a good action against Erysiphae fungi. Untreated but infected control plants show defeat from the fungus Erysiphae 100% Compound 2, 3, 5, 8, 19, 20, 23, 27, 29, 30, 97, 96, 2.5-2.11, 2.30- 2.35, 3.1-3.3, 3.11, 3.13-3.15, 3.1 4.1, 4.2, 4.4, 4.22 and other inhibit fungal infection in barley to 0-5%.
Residual-protective action against Venturia inaegualis on block shoots.
Apple plugs with fresh shoots 10–20 cm long are sprayed with a spraying solution (0.006% of the test compound) made from the wetting powder of the test compound. 24 hours later
five
0
five
0
five
0
five
0
five
cultivated plants are infected with a conidium suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90-100% and placed in a greenhouse at 20-24 s for the next 10 days. Scab damage is assessed 15 days after infection. Compounds of the formula I inhibit disease damage by up to 10% or less, for example, compounds 29, 30, 3.1, 3.2, etc. Untreated but infected control shoots, on the contrary, have a lesion of 100%.
Action against Botrytis cinerea on beans.
Residual-protective action.
Legumes about 10 cm tall are sprayed with a spray solution (0.02% of the test compound) made with a wettable powder of the test compound. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubation of infected plants for 3 days at a relative humidity of 95-100% and when the lesion is evaluated by fungi. The compounds in many cases are very inhibited by infection with fungi. At a concentration of 0.02%, the compounds of the formula I are completely effective. The lesion is 10% or less, for example, after treatment with compounds 3, 5, 11, 29, 30, 2.5.-2.8, 3.1, 3.2, 4.1, 4.4.
The damage from unprocessed but infected legume plants from Botrytis fungi is 100%.
Action against Firicularia oryzae on rice plants.
Residual-protective action.
After two weeks of refining, rice plants are sprayed with a spray solution made from a wettable powder of the test compound (0.002% of the test compound). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After 5 days of incubation at a relative humidity of 95-100%, fungal infection is assessed.
Rice plants treated with a spraying solution that contains one of the compounds of Formula I as an active substance show less than 20% fungal damage compared to non-working control plants (100% damage), partially without any fungal infection.

权利要求:
Claims (1)
[1]
Invention Formula
The method of producing pyridyl derivatives of the general formula
Kg R
i
(I)
RB
RJ-O-C-RB Rt RS Ry. . .
where is independently from each other hydrogen, halogen, alkyl, trifluoromethyl, methoxy, CFj-O- or phenyl;
R and R are. Independently of each other hydrogen, C-C4-alksh1 or phenyl, which may be substituted by halogen; Re group of general formula
About N
 have the indicated values interact with gal
genpyridine general formula
Hal (IV
15
N
or
OR9
(Ii)
in the presence of BuLi and the resulting howl product, where
   "
About N
they either replace or restore to call the compound of the general formula
II 4V, which is outside
HE
or interact with the dinenem of the formula CH -J, with
20
25 wherein Rn is the compound of general formula I,
with the proviso that when Kz methoxy, zo f - q is methyl, or the compound Rg is methyl, and R, R ,, R, R5 and R are hydrogen at the same time, the group Rg is in the third or fourth position of the pyridine cycle, Rg - hydrogen, methyl or group R-C-,
ABOUT
Where
35
General formula I, where Rg
-9
OH N
acylated with anhydride or an acid halogen hydride of the general formula R-COOH, where R. has the indicated

1500157 About
characterized in that the compound of general formula
 Nb Rj- O-C-C-ORi
I / t RS RV Oh
where R, -,
alkyl,
 have the indicated meanings, are reacted with halopyridine of the general formula
Hal (IV)
15
N
in the presence of BuLi and the resulting target product, where
   "
About N
either reduced or reduced to form a compound of general formula I,
II 4V, which are allocated
HE
either reacted with a compound of the formula CH —J, with education
25 where Rgзо f - q methyl, or a compound
35
General formula I, where Rg
-9
OH N
acylated with anhydride or acid halide of the general formula -COOH, where R. has the indicated
R
- C-C-alkyl, methoxymethyl, trifluoromethyl, cyclopropyl or phenyl.
and receive a compound of general formula I, where Rg is a group
which may be substituted by halogen, Q formula
methyl, trifluoromethyl or methoxy and
Group, Oh
Table T
Cl HCl HHHH.
RI "5
ABOUT
d
-about
p 1,5884
N
C1 HHH
n Q
he N )
N
f)
N
p 1,5705 (85.9)
15
1500157
16 Table 2
Note: Me is methyl; Et is ethyl, pGr is p-propyl; iPr - isoprogash,
Table 4
3.16
go
(n) nt 1.5702 (82.3)
) n 1.5739 (70.6) (n) n 1.5673 (66.2)
.JO
(n) n 1.5396 (83.5)
go
.JO
Table 5

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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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CH424585|1985-10-01|

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