Method of preparing thiazolylideneoxopropionitriles

专利摘要:
A thiazolylidene-oxo-propionitriles of the formula <IMAGE> in which R1, R2 and R3 have the meaning defined in the specification. The compounds are valuable as insecticides of a superior activity against specific groups of insects.
公开号:SU902665A3
申请号:SU802912755
申请日:1980-04-23
公开日:1982-01-30
发明作者:Путтнер Райнхольд；Бюманн Ульрих；Йоппиен Хармут
申请人:Шеринг Аг (Фирма)；
IPC主号:

专利说明:

I
This invention relates to a process for the preparation of novel thiazolilide oxopropionitriles of general form.
A known method of producing 2-CHLOR-2-OXI-2- (4-fench-1-2-tnazolyl cinnamic acid)
about p
Xg-gzcf
where R is lower alkyl, phenyl, phenyl, substituted lower alkyl or halogen, 2-thienyl or 2-pyridyl; R, is a hydrogen atom, lower alkyl
or halogen;
R - - trifluoromethylphenyl, phenyl or phenyl, monosubstituted with halogen, lower alkyl or lower apkoxyl, or disubstituted with halogen. The compounds of general formula 1 possess insecticidal activity and can be used in agriculture.
which is that the 2-tsnanmethyl-A-fe1-Chl-thiazole is reacted with 2-chlorobenzonyllhlond at the boiling point of the reaction mixture. The compound of this formula has an insecticidal action ll.
The purpose of the invention is to obtain new 20 compounds of general formula 1, expanding the range of substances that have insecticidal properties.
This goal is achieved by the fact that 25 in the process for preparing compounds 39 of general formula T, thiazolylacetonitrile of general formula AND jPlI - x PTT. - CHO-CTT g where R and Rj have the above values, are reacted with acid halide of general formula 111 RJ -CO- X, where R is as defined above; X is halogen, in an organic solvent medium in the presence of an organic base 4 The process is preferably carried out in xylene medium and in the presence of pyridine or 4-dimethylaminopyridine. Example 1..3- (2-Chloro-6-fluorophenyl -2- (4-tert.butyl-2,3-dihydro-azol-2-ylidene) -3-ok copropioni-tril.} 55 g (1.55 molj cyanthioacetamide, dissolved in 1.7 l of ethanol, is continuously mixed with 280 g (1.55 mol) of brompinacoline and refluxed for 1 hour with reflux. After concentration in vacuum, the residue is treated with aqueous soda solution and extracted with methylene chloride. The organic phase is dried on magnesium sulfate, concentrated and subjected to distillation under high vacuum. 178 g (b3% of theory) of 4 tert. butyl-2-cyanmethyl-thiazole are obtained (bp. (2 mm Hg) 101-H8 p. 9, 0 g (0.05 mol) 4-tert.butyl-2cyanmet ilthiazole and 0.5 g of 4-dimethylaminopyridine are suspended in 20 NBI of xylene. After the addition of 9.7 g (0.05 mol) of 2-chloro-6-fluorobenzoyl chloride, the mixture is refluxed under reflux. The solvent is distilled off in vacuo and the residue is heated with 20 ml of ethanol for 5 min. After re-concentration in vacuo, it is crystallized from ethanol to yield 3- {2-gloro-6-fluorophenyl} -2- (4-tert.butyl-2, 3-dihydrothiazol-2-ylidene) 3-Oxoprop6 nitrile is 5.1 g (30% of theory); mp 198-199 C. Example 2. 3- (2-Chlorophenyl) -2 (2-methylphenyl -2,3-dihydrothiazole -2-ylidei} -3-oxopropionitrile. Solution of 94 g (0.94 mol) cyanthioacetamide b.1 l of ethanol at 40 s is slowly mixed while stirring with 50.6 g (0.94 mol) of sodium methylate 5 After 10 min, 200 g (0.94 mol) of 2-methyl-i) -bromoacetophenol and then boil for 20 minutes with reflux. The solution is concentrated in vacuo and mixed with 4 liters of water. The aqueous phase is extracted several times with methylene chloride. The combined organic phases are dried over magnesium sulfate and concentrated in vacuo. Oily residue, distilled under high vacuum. 76 g (38% of theory) of 2 cyanomethyl-4- {2-methylphenyl} -thiazole are obtained; bp (0.1 mm Hg) 159-162 ° C. 10.7 g (0.05 mol of 2-cyanmethyl-4- (2-methylphenyl) -thiazole) are suspended in 20 ml of xylene and mixed with 0.5 g of 4-dimethylaminopyridine. After the addition of 8.8 g (0.05 mol) 2-Chlorobenzoyl chloride is boiled under reflux for 20 minutes, the solvent is removed in a vacuum, boiled with 20 ml of methanol and concentrated again. The residue is recrystallized from acetonitrile. The yield is 3- (2-chlorophenyl) (2-methylphenylJ-2, Zgdihydrothiazol-2-ylidene-3-6 xopropionitrile is 9.5 g 54% of theorif, mp .. In a similar way, the compounds shown in Table 1 are obtained in the same way. vorimy in water and gasoline, moderately soluble in methanol, apetone and ethyl acetate and well soluble in dimethylformamide. Insecticidal activity test. Example 3. The compounds of formula 1 are used in the form of aqueous suspensions with a specified concentration. With the help of ready-made formulations biologically active the substances are sprayed by pouring cauliflower in Petri dishes from polystyrene (at a dose of 4 mg of the solution for spraying 1 After the applied coating dries, 10 young caterpillars of cabbage cockroach are counted into each Petri dish {Plutella maculipcnnis) and kept for 2 days in closed Petri dishes on the treated feed. The criterion for assessing the effect is the death of the larvae after 2 days. Table 2 shows the test results of compounds of general formula 1 for insecticidal activity.
Example 4. Compounds of formula I are used as sub-suspensions of the desired concentration. Comparative agents are also diluted with water and used as suspensions or emulsions of the desired concentrations.
Using these formulations, the sprays and bases of Petri dishes made of polystyrene are sprayed {at a dose A mg of spray solution I cm L. On these applied coatings, 48 adult Mediterranean flies (Cevatitis capitata) in closed Petri dishes are sprayed for 48 hours Long day conditions in the laboratory.
The criterion for evaluating the effect is the mortality of flies after 48 hours.
In Table 3, certain percentages of mortality are compared.
required concentrations. Similarly, the comparative agents are diluted with water and receive suspensions or emulsions of the desired concentrations.
With these active ingredients, cauliflower leaves are sprayed in Petti polystyrene cups (at a dose of 4 mg of the spray solution I cm). After drying of the applied coatings, 10 young cabbage cockroach caterpillars (Plutella maculipennis) are counted in each Petri dish and kept in closed Petri dishes on the processed feed for 2 days.
The criterion for evaluating the effect is the death of the larvae after two days.
3- (2-Methylphenyl) -2- (5-methyl-4-phenyl-2,3-dihydrothiazol-2-ylidene) -3-oxopropionitrile
3- (2-Fluorophenyl) -3-oxo- (4-tert.butyl-2,3-dihydrothiazol-2-ylidene) propionitrile
3- (2-Chlorophenyl) -3-oxo-2- (4-tert.butyl2, 3-dihydrothiazol-2-ylidene) propionitrile
2- (4ttret. Butyl-2, 3-dihydrothiazol-2-ylidene) -3- (2-trifluoromethylphenyl) -3-oxopropionitrile
about
3- (2-Chlorophenyl) -3-oxo-2- 4- (2-thienyl) 2, 3-dihydrothiazol-2-ylidene-3 propionitrile
3- (2-Bromophenyl) -3-oxo-2- 4- (2-thienyl) 2, 3-dihydrothiazol-2-ylidene propionitrile
3- (2-Fluorophenyl) (2-methylphenyl) -2,3 dihydrothiazol-2-ylidene-3-oxopropionitrile
3- (2-Chloro-6-fluorophenyl) -2-4- (2-methylphenyl) 2, 3-dihydrothiazol-2-ylidene-3-oxopropionyryl
3- (2-Bromophenyl) (2-methylphenyl) -2,3 dihydrothiazol-2-ylidene-3-oxopropionitrile
108-110
176-177
217-219
195-196
162-163
147-148
163-164
191-192
167-168
3- (2-Methylphenyl} -2- (5-methyl-A-phenyl-2,3-dihydrothiazol-2-ylidei) -3-oxopropionitri
3- (2-Fluorophenyl-3-oxo-2- (D-tert.butyl2, Z-digdrothiazol-2-ylidene) propionitrnl
3- (.2-Chlorophenyl) -3-oxo-2- (4-tert. Butyl2, 3-dihydrothiazol-2-ylidene propionitrile,
3- (2-Chloro-6-fluorophenyl-2- (4-tert.butyl2, 3-dngidrs tiaz) l-2-ylidene) -3-oxopropionitrnl
2 - (, 4-tert. Butyl-2,3-dihydrothiazol-2-ylidene-3- (2-trnfluoromethylphenyl) -3-oxopronio nitrile
3-j2-Chl6pfenil) -3-oxo-2-C4- (2-thienyl -2, 3-dihydrothiazole-2-nliden1 propionitrile
3- (2-Bromophenyl) .- 3.-pkso-2- A- {2-thienyl) -2, d11hydrothiazol-2-nldep propionitrml
Continued table. I
100
100
100
100.
100
100
100 3- (2-Chlorophenyl) -2-C4- (2-methylphenyl) -2.3 dihydrothiazol-2-ylidene-3-oxopropionitrip 3- (2-Fluorophenyl -2-Li 2-methylphenyl) -2.3 dihydrothiazole-2 -ylidene -Z-oxopropionitrile E-C2-Chloro-6-fluorophenyl) (2-methylphenyl) -2,3-dihydrothiazol-2-ylidene-3 oxopropionitrile 3- (2-Bromophenyl) (2-methylphenyl 2, 3-dihydrothiazole- 2-ylidene-3-oxopropionitrile 3- (2-Methoxyphenyl) (2-methylfennl -2, 3-dihydrothiazol-2-ylidene-3-oxopropionitrile 3- (2-Iodophenyl) -2-14-C2-methylphenyl) -2 , 3-dihydrothiazol-2-ylidene-3-oxopropionitrile 3- (2-Chlorophenyl) (3-methylphensh1) -2,3 diridrothiazole 2-ylidene T.-3-oxopropirnitrile (2-chlorophenyl) -2,3-dig Dothiazol-2-yliden-3-oko-3-phenylpropionitrile - (2-Chlorophenyl) (. 2-chlorophenyl) -2,3 dihydrothiazol-2-ylidene-3-oxopropionitrile 3- (, 2-Chlorophenyl) -2- 4-C2- fluorophenyl) -2,3 dihydrothiazol-2-ylidene-3-oxopropionitrile 2-C5-Bromo-4-phenyl-2,3-dihydrothiazol-2-yliden) -3- (2-chlorophenyl) -3-oxopropionitrile 3-C2-Chlorophenyl) -Z-oxo-2- 4- (2-pyridyl) 2, 3-dihydrothiazol-2-ylideene propionitrile
Continued. Tab.2
riiiii: 0.1 100 0.1 100 0.1 100 0.1 100 0.1 100 0.1 100 0.1 100 0.1 100 0.1100 O, 1100 0.1100 0.1100
2- / 4-tert. Butyl-2,3-dihydr6thiazol-2ylidene) -3- (2-trifluoromethylphenyl) -E-oxopropionitrile
3- (2-Chloro-6-fluorophenyl) -2-C4- (2-methylphenyl) -2,3-dihydrothiazol-2-ylidene-3 oxopropionitrile
3- (2-Iodophenyl) -2-14-C2-methylphenyl) -2.3 dihydrothiazol-2- .ylidene | -3-oxopropionitrile
3- (2-Chlorophenyl) -2- 4- (2-chlorophenyl) -2,3 dihydrothiazol-2-ylidene-3-oxopropionitrile
Comparative means
Nitrile 2-chloro-3-oxy-2 - (. 4-phenyl-2thiazolyl) cinnamic acid
(cyan-3-phenoxybenzyl ester of 2- (4-chlorophenyl) isovaperianic acid
6,7,8,9,10,1 o-Hexachloro-1,5,5, 6,9,9in1-hexahydro-6,9-methano-2,4,3benzodioxatiepin-3-oxide
2 3- (2-Chloro-6-fluorophenyl) -2 - /. 4- (2-methylphenyl -2,3-dngidrotiazol-2-ylidene / -3 oxocapropionitropyl
Table a j
0,0025
90
98
0,0025
0,0025
95
93
0,0025
73
65
68
Table 4
90 90
0.01 0.005
Comparative means
3Nitrile Z-bromo-3-oxy-2- (4-phenyl-2-thiazolyl) basic acid
41-Na4) tilmethylcarbamate

权利要求:
Claims (1)
[1]
5 0,0-dimethyl-0 - (;; l-nitrophenyl) thionophosphoric acid ester The claims The method for producing the thiazolylidene propionitriles of the general formula I V-if is D.-s-c 2 3 where R. is lower alkyl, phenyl, substituted by lower alkyl or halogen, 2-thienyl or 2-pyridyl; Rj is a hydrogen atom, a lower alk or halogen; Rj - trifluoromethylphenyl, phenyl or phenyl, monosubstituted with halogen, lower alkyl or lower alkoxy, CL disubstituted with halogen.
Continued table. four
90 50
50 10
70
0.01 0.005 characterized in that the thiazolylacetonitrile of the general formula I .. CHo-CiJ, where R and R, are as defined above, is reacted with an acid halide of the general formula 1 and Rj is CO - X, where R has the above values; X is halogen, in the medium of an organic solvent in the presence of an organic base. Sources of information taken into account in the examination I. Published in the German Federal Republic K 2703542, cl. C 07 D 277/30, published “978.

类似技术:

---

公开号 | 公开日 | 专利标题

---

JP3250825B2|2002-01-28|Substituted nitroguanidine derivatives, their production and insecticides

---

SE442995B|1986-02-10|SUBSTITUTED PHENOXYBENZYLOXICARBONYL DERIVATIVES AND USE THEREOF TO FIGHT INSECTS AND / OR ACARIDS

---

CA1130308A|1982-08-24|Preparation of cyclopropane carboxylic acids andesters

---

SU902665A3|1982-01-30|Method of preparing thiazolylideneoxopropionitriles

---

IL30145A|1972-07-26|Pyrimidine derivatives and pesticidal compositions containing them

---

JP2704655B2|1998-01-26|Tri-substituted phenylpyrazole derivatives or their salts and herbicides

---

CN108341808B|2020-02-18|Oxadiazole pyrazole compound and application thereof

---

SK43597A3|1997-11-05|Oxime ethers, preparation method thereof and microbicidal agents containing the same

---

CZ169797A3|1998-04-15|Aromates substituted by benzyloxy group and their use as fungicidal and insecticidal agents

---

CS214681B2|1982-05-28|Fungicide means

---

LT3521B|1995-11-27|Methods for weeds control

---

GB1573668A|1980-08-28|N-trichloracetyl-n&#39;-chlorobenzoylhydrazine derivatives

---

GB2051060A|1981-01-14|Insecticidally active salts of thiazolylideneoxo-propionitriles and their manufacture and use

---

CA1059530A|1979-07-31|Combating fungi with n-chloroacetyl-n-|-alanine esters

---

JP2690816B2|1997-12-17|Quinolinyl oxadiazole herbicide

---

JPH0625095A|1994-02-01|New derivatives of 7-ethylyl-alpha-|-1- naphthaleneacetic acid, their production and their use as noxious living organism exterminating agents

---

CS224622B2|1984-01-16|Microbicide

---

CS202092B2|1980-12-31|Fungicide means and method of preparation of its active substance

---

US4187096A|1980-02-05|Biocidally-active 1,3-benzodithiole-2-thione compounds

---

JP3163545B2|2001-05-08|4-thienyl-oxa | azoline derivatives and insecticides and acaricides containing the same

---

JPH05194445A|1993-08-03|New derivatives of 1-naphthaleneacetic acid, their production and their use as pesticides

---

JP3877789B2|2007-02-07|2-Chloro-6-hydroxyisonicotinic acid derivative and plant disease control agent

---

JP3054977B2|2000-06-19|Fungicidal furanone derivative

---

US3949023A|1976-04-06|Novel oximino -phosphorothiolate derivatives

---

JPH06287171A|1994-10-11|Semicarbazide derivative, its production and its insecticidal composition

同族专利:

---

公开号 | 公开日

---

IL60080D0|1980-07-31|

---

CA1136143A|1982-11-23|

---

IE49802B1|1985-12-25|

---

LU82457A1|1980-10-08|

---

FR2456737B1|1983-05-27|

---

ES491527A0|1980-12-16|

---

MX6405E|1985-05-28|

---

MA18847A1|1980-12-31|

---

ZA802923B|1981-05-27|

---

CH644601A5|1984-08-15|

---

IT1140847B|1986-10-10|

---

DE2920183A1|1981-04-30|

---

JPS5925789B2|1984-06-21|

---

PT71243A|1980-06-01|

---

GB2051052A|1981-01-14|

---

RO80087A|1983-02-01|

---

DK211380A|1980-11-18|

---

ES8107204A1|1980-12-16|

---

IT8021877D0|1980-05-08|

---

PL121559B1|1982-05-31|

---

NZ193666A|1982-12-21|

---

FI70889B|1986-07-18|

---

HU187276B|1985-12-28|

---

EG14276A|1983-09-30|

---

IL60080A|1984-01-31|

---

ATA263680A|1981-10-15|

---

FR2456737A1|1980-12-12|

---

FI801379A|1980-11-18|

---

GB2051052B|1983-08-24|

---

TR20541A|1981-10-21|

---

BE883348A|1980-11-17|

---

RO80087B|1983-01-30|

---

BR8003059A|1980-12-23|

---

AU5833980A|1980-11-20|

---

DD150840A5|1981-09-23|

---

JPS55154963A|1980-12-02|

---

GR67663B|1981-09-02|

---

FI70889C|1986-10-27|

---

CS216221B2|1982-10-29|

---

US4297361A|1981-10-27|

---

AU531811B2|1983-09-08|

---

NL8001920A|1980-11-19|

---

AT366886B|1982-05-10|

---

SE8003465L|1980-11-18|

---

YU41208B|1986-12-31|

---

BG34443A3|1983-09-15|

---

PL224257A1|1981-02-13|

---

YU116380A|1983-02-28|

---

IE801018L|1980-11-17|

---

IN154174B|1984-09-29|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB1192701A|1968-03-22|1970-05-20|Ici Ltd|Novel Thiazole Derivatives, the preparation thereof and Compositions containing the same|

---

US3769040A|1970-11-09|1973-10-30|Int Flavors & Fragrances Inc|Substituted thiazoles in flavoring processes and products produced thereby|

---

US3637707A|1970-11-24|1972-01-25|Pfizer|2- 2-thiazolines for the control of rice blast|

---

DE2703542C2|1977-01-26|1985-09-26|Schering AG, 1000 Berlin und 4709 Bergkamen|Thiazolyl cinnamonitriles, insect control agents containing these compounds and processes for their preparation|

---

DE2801794A1|1978-01-17|1979-07-19|Basf Ag|PROCESS FOR MANUFACTURING THIAZOLE DERIVATIVES AND NEW THIAZOLES|JPH0317751B2|1983-10-14|1991-03-08|Tokyo Tatsuno Kk|

---

US4626543A|1985-02-01|1986-12-02|Shell Oil Company|Insecticidal 2,6-difluorobenzoyl derivatives of 4-substituted-1,3-thiazole-2-acetonitriles|

---

EP0842931A4|1995-04-27|1998-09-02|Nissan Chemical Ind Ltd|Oxopropionitrile derivatives and insect rest control agents|

---

PT913392E|1996-04-25|2003-11-28|Nissan Chemical Ind Ltd|ETHYLENE DERIVATIVES AND PESTICIDES|

---

DE19851986A1|1998-11-11|2000-05-18|Bayer Ag|Phenyl-substituted cyclic enaminones|

---

KR20020067577A|1999-12-27|2002-08-22|닛뽕소다 가부시키가이샤|Thiazolylcinnamonitrile compounds and insecticides and miticides|

---

AU4117001A|2000-03-17|2001-09-24|Nippon Soda Co|Acrylonitrile compounds and pest controllers|

---

JPWO2002088099A1|2001-04-27|2004-08-19|日本曹達株式会社|Thiazolyl cinnamate nitrile compounds and pesticides|

---

WO2003064401A1|2002-01-29|2003-08-07|Nippon Soda Co., Ltd.|Acrylonitrile compounds and pest controllers|

---

USD702103S1|2012-04-12|2014-04-08|Qaid Zohar Zakiuddin Shahpurwala|Padlock|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

DE19792920183|DE2920183A1|1979-05-17|1979-05-17|THIAZOLYLIDEN-OXO-PROPIONITRILE, INSECTICIDAL AGENT CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF|

---