Method of producing alcanoylanilide or its ammonium salts

专利摘要:
The present invention is an alkanoyl anilides exhibiting insecticidal and arachnicidal activity, wherein the alkanoyl is both branched and substantially or totally fluorinated.
公开号:SU1528343A3
申请号:SU864027304
申请日:1986-04-04
公开日:1989-12-07
发明作者:Питер Гаджевски Роберт
申请人:Эли Лилли Энд Компани (Фирма)；
IPC主号:

专利说明:

 s
The invention relates to organic chemistry, namely to a method for producing alkanoyl anilide or its ammonium salts of the general formula
I, o RO-C-C-N-R
where K ,, - fluorine, R, - SG-,
n, - ST, 1 ф interfluoro- (lower) alkoxy-C, -C, or perfluormorpholi io;
R, is polorod;
P, -5-nitro-2-pyridyl, A-nitro-1.-naphthyl polyphenyl, substituted 1-p1 nitro, two to five independently selected RJ, where R is bromine, chlorine or fluorine, or two independently selected groups R where H is iodine, nitro, cyano, trifluoromethyl, or by two groups, including one Rg group and one R group, or by two tons of rups, including one methyl and one nitro group, or by three groups, including two independently selected Rg groups and one R, group, or three gr groups, including two independently selected H groups and one Rj group, or its ammonium salts, in which ammonium has the following form
®l
 Ive
9
where R. - independently of C, -C, in the evil -
benzyl;
 is hydrogen or Rg, with the number of carbon atoms in all: q and R; is (o, which have insecticidal and arachicidal activity and can be used in agriculture,
The purpose of the invention is to develop an accessible method for the preparation of compounds of the general formula that possess high insecticidal and arachiicidal activity.
Example 1. 2-Bromo-4-nitro 2,3,3,3-tetrafluoro-2- (trifluoromethyl) -propionanilide (olefin method).
Potassium fluoride (23 g, 0.4 mol), KOTopbivi is thoroughly dried on a bunsen burner in a porcelain crucible and then ground to powder, added to 200 ml of a solution of 2-bromo-4-nitrophenyl isocyanate (b g, 0.025 mol in dimethylformamide (DIF). The resulting mixture is placed in an autoclave, rinsed with a weak stream of hexafluoropropene and heated until supplying hexafluoropropene

g 5 0
five
0
35
40
45
CQ
55
When a gas enters the reaction, a pressure drop occurs and the remaining hexafluoropropene is poured in portions until the cylinder is completely empty, heating is continued at 65 -70 ° C for 2.5 hours at a stable pressure of 5 psi (0.35 kg / cm, 1. Then the reactor is cooled and the solution is poured and extracted with hexane. The DMF solution is poured into water and filtered. The solids are transferred to chloroform, dried over sodium sulfate, filtered, evaporated and chromatographed on silica gel with ethyl acetate-hexane (1: 5). The product leaving at the beginning is collected;
H NMR of this product indicates the presence of the desired product. The material is then chromatographed on silica gel with gradient elution from 100% hexane to 100% ethyl acetate.
As a result of this procedure, a waxy solid product is obtained with a melting point of 57-59 ° C, yield 1.65 g (16%). The structure of the product was confirmed by mass spectrometry, H-NMR and F-NMR,
Calculated,%: C, 29.08; and 0.98; N 6.78.
Found,%: C 29.31; H 0.83; S 6.58.
Example 2 2-Bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide (method through alkanoyl fluoride with isomer separation).
2-Bromo-4-nitroaniline (141 g, 0.65 mol) is dissolved in 3.5 liters of diethyl ether, dried over sodium sulfate and filtered. Triethylamine (71 g, 0.070 mol) was added with stirring. A mixture of 2,2,3, 4,4-heptafluorobutyryl fluoride, 2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionyl fluoride, HF and inert gases is used. The resulting mixture should contain 70% of chemically active acyl fluorides, 100 g of this mixture is added under dry ice / acetone cooling conditions. The reaction mixture is allowed to stand overnight (about 17 hours) and an additional amount of the mixture is added, to a total of 210 g (0 , 70 mole).
Water is added to the reaction mixture, then diluted with an ice / HCl mixture until the pH of the aqueous layer becomes acidic. Water layer de 515283436
A layer of sodium hydroxide diethyl ether, and the resulting solution
distilled until the head temperature rises above the boiling point of tetrahydrofuran.
capturing
shat over anhydrous magnesium sulphate,
and the solvent is evaporated in vacuo.
The solid residue is placed in 800 ml of ethanol and treated with potassium carbonate at room temperature with stirring using a magnetic stirrer. J First add 68 g of K, CO, then 23 g after another 24 hours and another 12 g after 48 hours and stirring is continued for a total of 64 h. Ethanol is evaporated in vacuo, and the solid part is triturated three times with aqueous potassium carbonate. The resulting solution is filtered, and the resulting filtrate is acidified below 25 ° C HCl. The resulting product is filtered, washed with water, dissolved in methylene chloride, dried and ground. The gas chromatogram of the product gives less than 1% of the unbranched isomer, mp. 66 C yield 178 g (66%).
Calculated,%: C, 29.08; H 0.98; N 6.78.
C, oH4BrF7N., 03
Found,%: C 29.30; H 0.92; N 6.99.,,
Example 2 -Brom-4-nitro-2,3,3,3, -tetrafluoro-2 "- (trifluoromethyl) propionanilide (alkanoyl fluoride method, with the separation of isomers).
2-Bromo-4-nitroaniline (35.84 rj 0.16 mol), triethylamine (21.15 g; 0.21 mol), and 250 ml of tetrahydrofuran- are added to a 500 ml round-bottom flask equipped with a reflux condenser ( dry ice-acetone) and gas feed. The reactor is flushed with nitrogen. Use the same mixture of acyl fluorides as in Example 2 as reagents of the considered example (54.60 g; O, 18 mol). The resulting mixture is added at the rate of 10.
66 C. The temperature in the reactor is kept constant until, according to thin layer chromatography, the hydrolysis of the unbranched product by the basic solution is confirmed. The resulting aniline precipitates at this time and is filtered off.
The obtained filtrate is cooled, then washed twice with 150 ml and 100 ml.
15 methylene chloride. The aqueous layer is separated and vacuum is created to remove the residual organic solvent. The resulting solution is then placed in an ice bath and the pH is lowered to 7 with concentrated hydrochloric acid. The target 2-bromo-4-nitro-2,3,3,3-tetrahyd ro-2- (trifluoromethyl) propionanilide precipitates and is filtered off, washed with distilled water and su
25 shat overnight in vacuum at room temperature. Obtain 42.95 g (86%) with a purity of 99.5% according to high performance liquid chromatography
30 Other proposed compounds are obtained through alkanoyl fluoride, unless specifically indicated. Products obtained through alkanoyl fluoride are made in the form of isomeric
35 mixtures except for examples 8 and 13.
These other compounds of the present invention are listed in the following 40 examples. In each of the examples, the structure of the product was confirmed according to H-NMR. The percentage of the branched isomer in the product, determined by
baking slow boil with reverse 45 d F NMR
Example4. 2-Cyano-4-nitro 2,3,3, 3-tetrafluoro-2- (trifluoromethyl) - propionanilide, so pl. lOO-lOl C, yield 50% (72% of the branched isomer),
50
fridge This addition takes approximately 90 minutes, and the resulting brown solution is stirred for about 1 hour after completion of the addition. The reaction mixture is then washed with 60 ml of a 50/50 water / saturated sodium chloride solution and a saturated solution of sodium chloride. Water layers are drained.
Then 150 ml of 1N is added. hydro-sodium oxide to the organic layer and 90 ml of volatile product are distilled off at atmospheric pressure. Then another 100 ml of 1N hydrocalcified is added to the solution,%: C, 36.79; H 1.12; N 11.70.
C, N4G, ISO
Found,%: C 37.05; H 1.22; N 11.89
Example 5 about 2-Methyl-4-nitro-2,3,3,3, -tetrafluoro-2- (trifluoromethyl) propionanilide, mp. 120-122 ° C, yield 22% (93% of the branched isomer).
66 C. The temperature in the reactor is kept constant until, according to thin layer chromatography, the hydrolysis of the unbranched product by the basic solution is confirmed. The resulting aniline precipitates at this time and is filtered off.
The obtained filtrate is cooled, then washed twice with 150 ml and 100 ml.
methylene chloride. The aqueous layer is separated and vacuum is created to remove the residual organic solvent. The resulting solution was then placed in an ice bath and the pH was lowered to 7 with concentrated hydrochloric acid. The desired 2-bromo-4-nitro-2,3,3,3-tetrahydro-2- (trifluoromethyl) propionanilide precipitates and is filtered off, washed with distilled water and dried overnight in vacuo at room temperature. Obtain 42.95 g (86%) with a purity of 99.5% according to high performance liquid chromatography
Other proposed compounds are obtained through alkanoyl fluoride, unless specifically indicated. Products obtained through alkanoyl fluoride are made in the form of isomeric
mixtures except in examples 8 and 13.
These other compounds of the present invention are listed in the following examples. In each of the examples, the structure of the product was confirmed according to H-NMR. The percentage of the branched isomer in the product, determined by
F-NMR data
Calculated,%: C, 36.79; H 1.12; N 11.70.
C, N4G, ISO
Found,%: C 37.05; H 1.22; N 11.89
Example 5 about 2-Methyl-4-nitro-2,3,3,3, -tetrafluoro-2- (trifluoromethyl) propionanilide, mp. 120-122 ° C, yield 22% (93% of the branched isomer).
propionanilide, mp, 104-108 ° С, code 31% (78% of the branched isomer)
Calculated,%: C, 33.26; H 0.56; N 3.88.
,, NO
Found,%: C 33.54; H 0.78;
Calculated,%: C 37.95; H 2.03; N 8.05.
C ,, H, F,
Found,%: C 38.10; H 1.95; S 8.26.
Example 2- (Trifluoromethyl) -4-nitro-2,3,3,3-tetrafluoro-2- (trifluoro-N 3.94. Methyl) propionanilide, mp. 53-54 ° C, Example 10
yield 15% (95% of branched isotloro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, mp 69-72 ° C; yield 55% (87% of the branched isomer).
Calculated,%: C 30.60; H 0.77, 15 N 3.57 "
2,4, 5 -Trimer).
Calculated,%: C 32.85; H 1.00; N 6.97.
C ,, H4F ,,
Found,%: C 32.79; H 1.15; N 7.01.
Example7. 2, з, 4,5, б, 2,3,3,3-Nonafluoro-2- (trifluoromethyl) - propionanilide, so pl. 137-142 ° C, yield 85% (60% of the branched isomer). 20
Calculated,%: C, 31.68; H 0.27; N 3.69
C, oHF, iNO
Found,%: C 31.42; BUT, 23; 25 N 3.89.
ExampleB 2-Chloro-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilde, so pl. 52-53 s, yield 94% (86% of the branched isomer).
Calculated,%: C 32.59; H 1.09; N 7.60.
WITH,.
Found,%: C 32.82; H 0.97; N 7.63.
This product is purified by treating a solution of potassium carbonate in ethanol as follows. The product (4 g; 0,0108 mol-) is dissolved in 20 ml of 95% ethanol and carboxy-Q sodium potassium (1.1 g; 0,008 mol) is added. . The resulting mixture was incubated for 5 days at room temperature. Then ethanol is evaporated at room temperature. KADSLIA carbonate (1.1 g) in 50 ml of water at 40 ° C is added with vigorous stirring. The resulting mixture is filtered and washed with water (40 s). The resulting filtrate
C, oH5Cl, 4NO
Found,%: C 30.69; H 1.01; N 3.62.
As a result of another preparation, the same compound is obtained with a yield of 67% (91% of the branched isomer) with mp. 80-81 ° C
Found,%: C 30.47; H 1.04; S 3.43.
Example 11. Z, B, 2,3,3, Z-Octaftor-2- (trifluoromethyl) - propionanilide, so pl. 94-99 ° C, yield 69% (82% of the branched isomer).
Calculated,%: C, 33.26; H 0.56; N 3.88.
Found,%: C 33.06; H 0.34; N 4.00.,,,
35
Example 12. 2, 3, 4
I
Tetrachloro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) -propionanilide, so pl. 82-83 ° C, yield 18% (95% branched isomer).
Calculated,%: C 28.13; H 0.47; N 3.28.
Found,%: C 28.35; H 0.52; N 3.30.
Example 13 2, 5-Dichloro-4-nitro-2,3,3,3-tetrafluoro-2- (tri-fluoro-tyl) -prop-ion-anilide is obtained by a process through an olefin, t „pl. 80-82 s, yield 12% (99% branched nso cooled, acidified with HC1, filtered CQ measure).
and dried in air, resulting in a gain of 2.8 g (70% yield) of the purified product with so pl. 67 C. Gas chromatogram and F-NMR spectrum
confirm that the product is
branched isomer with a purity of 99% „
Example9. 2,3,4, b, 2,3,3,3, -Octafluoro-2- (trifluoromethyl)

Propionanilide, mp, 104-108 ° С, code 31% (78% of the branched isomer).
Calculated,%: C, 33.26; H 0.56; N 3.88.
,, NO
Found,%: C 33.54; H 0.78;
94 Example 10
torus-2- (triftorm
2,4, 5 -Tri0
five
about
Q З
C, oH5Cl, 4NO
Found,%: C 30.69; H 1.01; N 3.62.
As a result of another preparation, the same compound is obtained with a yield of 67% (91% of the branched isomer) with mp. 80-81 ° C
Found,%: C 30.47; H 1.04; S 3.43.
Example 11. Z, B, 2,3,3, Z-Octaftor-2- (trifluoromethyl) - propionanilide, so pl. 94-99 ° C, yield 69% (82% of the branched isomer).
Calculated,%: C, 33.26; H 0.56; N 3.88.
Found,%: C 33.06; H 0.34; N 4.00.,,,
five
Example 12. 2, 3, 4
I
Tetrachloro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) -propionanilide, so pl. 82-83 ° C, yield 18% (95% branched isomer).
Calculated,%: C 28.13; H 0.47; N 3.28.
Found,%: C 28.35; H 0.52; N 3.30.
Example 13 2, 5-Dichloro-4-nitro-2,3,3,3-tetrafluoro-2- (tri-fluoro-tyl) -prop-ion-anilide is obtained by a process through an olefin, t „pl. 80-82 s, 12% yield (99% of branched NZO calculated,% C 29.80; H 0.75; N 6.95.
CeHjCljFTN Os
Found,%: C 29.90; H 0.53;
N 6.98,
2, 5-dichloro-A-nitro-2,3,3,3-tetrapheptop-2- (triphthromophenyl) -propion-anilide is also prepared via alkanoyl fluoride, m.p. 81-83 s,
yield 47% (94% of the branched isomer).
The microanalysis gave the following results //: C 30.07; And 0.53; N 6.92.
This product is purified by treating with potassium carbonate according to Example 8, mp 83-85 ° C, yield 82% of the branched isomer with a purity level greater than 99%.
Example 14. 2, 3-Dichloro-2, 3,3,3-tetrafluoro-2- (trifluoromethyl) about pionanilide, so pl. 71-73 ° C, yield 32% (99.4% of the branched isomer).
Calculated,%: C, 33.55; H, 1.13; N 3.91.
C oH Cl F-fNO
Found,%: C 33.59 H H 1.25; N 3.95.
PRI me R 15. N- (5-Nitro-2-pyr dil) -2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionamide, m.p. 75-77 C, yield 42% (97% of the branched isomer).
Calculated,%: C 32.26; H 1.20; N 12.54o
C ,, N, 03
Found,%: C 31.19; H 1.00; N 2.45 „
Example 16. 2, 6-Dichloro-4-nitro-2, 3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 128-134 ° C, yield 13% (59% of the branched isomer),
Calculated,%: C, 29.80; H 0.75; N 6.95.
, P, MgOz.
Found,%: C 29.84; And 0.97; N 7.09.
Example17. 2-Methyl-4-nitro-5-chloro-2, 3,3,3-tetrafluoro-2- (trifluoro metip) propionanilide, so pl. 114-116 With the yield of 53% (91% of the branched isomer).
Calculated,%: C 34.53; H 1.58; N 7.32 „
C ,, HgClF7N203
Found,%: C 34.40; H 1.61; N 7, ZK
Example 18. 2,3,3,3-tetrafluoro- (trifluoromethyl) propionanilide, m.p. , yield 33% (87% of the branched isomer).
Calculated,%: C 30.60; H 0.77; N 3.57.
C “) NzS1,7NO
Found,%: C 30.47; H 0.92; N 3.47,
2.4, b-Trichlor0
five
0
Example 19 3, 4, 5-tri-chloro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 145-146 C, 38% yield (95% of the branched isomer).
Calculated,%: C 30.60; H 0.77; N 3.57o
Found,%: C 30.82; H 1.06; N 3,50. Example 20. 2-Chloro-5-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 68-70 0, yield 35% (84% of the branched isomer).
Calculated,%; C 32.59; H 1.09; N 7.60.
Found,%: C 32.64; H 1.33; N 7.49 „
Example 2 K 2, 4-Dinitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, 50-51 ° C, yield 5–21% (85% of the branched isomer).
Calculated,%: C, 31.68; H 1.06; N 11.08.
C, OH, F, N, Os
Found,%: C 31.42; H 1.15; 0 N 10.84.
Example 22. 2-Iod-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, ToPL „107-1, yield 8% (39% of the branched isomer).
Calculated,%: C 26.11; H 0.88; N 6.09.
,
Found,%: C 26.28; H 1.11, N 5.90.
Example 23 2-Cyano-4-chloro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide, ToPL 90-91 ° C, yield 5% (91% of the branched isomer).
Calculated,%: C 37.90; H 1.16; N 8.04.
WITH,
Found,%: C 38.08; H 1.10; N 7.84.
five
0
EXAMPLE 24 Tetra-n-propyl-ammonium salt of 2-bromo-4-nitro2, 3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide.
2-Bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide (20 g of the material not containing the unbranched isomer, 0.048 mol) is dissolved in 200 ml of acetone. The solution is kept at room temperature, and at this time 2 N. hydroxide
sodium i25 ml; 0.05 mol) and tetra-n-propyl mmonium bromide (13.5 g; OjObi mol) are added. The reaction mixture is stirred for 45 minutes, filtered; Л1Бпют at room temperature and 1-.а: -1 department 1ot between methylene chloride and, odn, o1k Orgapic phase, twofold- (ai washed with water, dried over sodium sulfate and D.mapnnaioT to dryness, resulting in 23.7 g The target salt (99% yield) of the structure of the product was confirmed by H-NMR. The product on standing cures Jt 57-65 ° C.
Calculated,%: C, 44.16; H 5.22; N 7.02.
With ,, nz,
Found ,,: C 44.14; H 5.05, N 6.80.
The second synthesis was carried out in the same way, and the structure of the product was also confirmed by H-NMR. The yield was 9.2 g (91%), m.p. 72-75 ° C.
N%; C: 43.88; H 4.50; N 6.83 „
The third synthesis is carried out in the same way, except that the final anilide makes up only 86% of the desired 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionapilide, and the remaining 14 % is the corresponding unbranched isomer. The product of this reaction is oil. Its structure is confirmed by danngi N NM.
Found,%: C 44.02; H 5.07; N 7.02.
Other salts are prepared in the same way. In each of the subsequent examples, the structure of the product is confirmed by H NMR data. In these examples, the result is nv1 anilide and the corresponding salt. or npaKTtmecKH pure 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, which is called the pure isomer, or a mixture, 86% of this compound and 14% of the corresponding unbranched isomer (which is called 86 % isomer).
EXAMPLE 25 Tetraethylammonium salt monohydrate of 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanipide, m.p. 112 ° C, yield 60% ± 60% (pure isomer).
Calculated,%: C 38.59; H 4.50, S 7.50 ,,
C, eH, .BrF, N, 04
five
0
five
0
five
0
Naidio,%: C 38.85; H 4.25, N 7.48.
Example 26, Tetra-n-butyl ammonium monohydrate salt of 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 78-80 ° C, yield 66% (pure isomer).
Calculated,%: C, 46.44; H 6.14; N 6.25.
.BrFTl O
Found,%: C 46.66; H 6.29; K 6.12.
EXAMPLE 27 Tetra-n-pentylammonium salt monohydrate of 2-bromo-4 - nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide.
Getting 1, so pl. 55-57 ° C, yield 80% (pure isomer).
Calculated,%: C 49.45; H 6.73; N 5.77.
,
Found,%: C 50.80; H 6.93; N 5.69 „
r84-lN9-277,
Getting 2, so pl. 54-56 ° C, yield 76% (86% isomer).
EXAMPLE 28 Tetra-n-heptylammonium salt monohydrate of 2-bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide as an oil, 50% yield (pure isomer ).
Calculated,%: C 54.28; H 7.79; N 5.00
Calculated%: C 54.7; H 7.66; N 5, P „
C gHgjBi-FtNjO. I
Found,%: C 56.27; H 8.68, N 4.59 „
 - not a hydrate.
EXAMPLE 29 Methyl tri-n-octylammonium salt 2-bromo-4 monohydrate - nitro-2,3,3, 3 tetrafluoro-2- (trifluoromethyl) propio anilide a in the form of an oil, 70% yield (86 % isomer).
Calculated,%: C 52.11; H 7.20; N 5.36.
C, 5H5, BrFTN, 0
Found,%: C 52.63; H 7.39; N 5.26.
EXAMPLE 30 Methyl tris monohydrate (Cg-C) ammonium salt of 2-bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide as an oil, 60% yield (86% isomer).
EXAMPLE 31 Monohydrate Hexadecyltrimethylammonium salt 2 - bromo-4-nitro-2 J3,3,3-tetras1) Tor-2- (trifluoromethyl) propionanilide.
13
Preparation 1, in the form of an oil, yield 48% (pure isomer).
Calculated,%: C, 48.74; And 6.63; N 5.88.
,
Found ,,: C 49.03; F 6.39; N 5.78.
Preparation 2, as an oil, yield 6% (86% isomer).
Found,%: C 47.54; And 6.09; N 5.90 „
EXAMPLE 32 Octadecyltrimethyl ammonium salt of 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 45-48 ° C, 52% yield (86% isomer).
Calculated,%: C, 51.38; And 6.76; N 5.80.
C E c BrF-il - O ,,
Found,%: C 52.03; H 6.67; N 5.67.
PRI me R 33. Benzo-tri-n-butylammonium salt 2-bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide monohydrate as an oil, yield 14% (86 % isomer) o
Calculated,%: C 49.30; H 5.56; N 5.95o
, N „VgK7I Oh ,.
Found,%: C 50.21; H 5.96; N 5.64 „
EXAMPLE 34. Dimethylbis (C ,.) monohydrate monohydrate 2-bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide, TaPL. 65-70 ° С, yield 48% (86% isomer) „
Example 35. Dimethylbis (C, o-) ammonium salt of 2-bromo-4-nitro-2, 3,3, 3-tetrafluoro-2- (trifluoromethyl propionanilide as an oil, yield 42% (pure isomer).
EXAMPLE 36. Dimethylbis monohydrate (18) from monium salt of 2 — bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide as an oil, 45% yield ( 86% isomer).
EXAMPLE 37. Tributylammonium salt of 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2 (trifluoromethyl) propionane lead, mp 58-60 ° C, yield 87% (pure isomer).
Calculated,%: C 44.15; H 5.18; N 7.02.
CjjHj, Found,%: C 43.27; H 3.47; N 6.96.
152834314
Unless otherwise indicated, the following additional examples are obtained as previously described.
Example 38. 4 -Nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionyl- 112-115 C, yield 60% (85%
LEAD, m.p.
branched isomer,
0
five
0
five
0
five
0
0
five
H 1.51;
1.50;
Calculated,%: C 35.95; N 8.38,
C oHjFrN O, Found,%: C, 36.21; H N 8.39.
Example 39 2-Chloro-5 - (fluorosulfonyl) -2,3,3,3-tetrafluoro-2 (trifluoromethyl) propionanilide, mp. 63-65 ° C, yield 33% (87% of the branched isomer).
Calculated,%: C 29.6); H 0.99; N 3.45.
C oH ClFgNO 3
Found,%: C 29.88; H 0.98; H 3.27.
EXAMPLE 40. N- (4-Nitro-1-naphthyl) -2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionamide, 127-128 ° C, 5% yield (80 % branched isomer).
Calculated by / ;: C 43.77; H 1.84; N 7.29.
Ci4H7F7Nz03
Found,%: C 43.96; H 1.82; N 7.52.
Example 41. 2 -Brom-4-chloro-6-cyano-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propianilide as an oil, yield 45% (53% of the branched isomer).
Calculated,%: C 30.91; H 0.71; N 6.55.
WITH
Found,%: C 31.15; H 0.99; N 6.30.,
Example 42. 3-Chloro-4-nitro 5 2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilde, m.p. 55-57 s, yield 9% (73% of the branched isomer).
Calculated,%: C 32.59; H 1.09; N 7.60. ,
Found,%: C 32.55; H 1.34; N 7.30.
EXAMPLE 43e 2 -Brom-4-nitro-2,3,3,3-tetraphor-2- (trifluoromethyl) propionanilide is reacted with methyl iodide in acetone in the presence of potassium carbonate, to give N-methyl -2 - bromo-4 -nitro-2,3,3, 3-tetrafluoro-215
(trift p -1ygil) propionic acid in the form of oil, yield 70% (-99% of the branched isomer)
Calculated,%: C, 30.94; H 1.42; N 6.56,
C, HgBrF7N2.03
Found,%: C 31.01; H 1, 28; N 6.77.
PRI me R 44. 2 -Brom-4 -nitro b -cyano-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propnonanilide, mp. 109-PGS, 10% yield (30% branched isomer).
Calculated,%; C 30.16; H 0.69; N 9.59.
C ,, H, BrF7N, 03
Found,%: C 30.41; H 0.62;
N 9.8U,
Example 45. 2-Methyl-3-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionannlide, mp. 100-102 C, yield 53% (82% of the branched isomer).
Calculated,%: C 37.95; H2.03; N 8.05.
With „Н7Р Н.Г.Оэ
Found,%: C 37.68; H 2.01; N 8.01.,,
Example 46 24-Dinitro-5-ethoxy-2,3,3, H-tetrafluoro-2- (methyl trifluoro) pr) pionanilide, m.p. 117-119 is obtained in 10% yield after an attempt to purify the crude 2 4-dinitro-5-fluoro-2,3,3, 3-tetrafluoro-2- (trifto methyl) propionan in ethanol (99% of the branched isomer).
Calculated,%: C 34.04; H 1.89; N 9.93.
C, 06
Found,%: C 34.19; H 1.80;
N 10.15.,
Example 47 about 2 -Brom-4-nitro 2,3,3, 3-tetrafluoro-2- (pentafluoroethoxy) propionanilide, yield 51% mixed with 2-bromo-4-nitro-2,2,3,3 , tetrafluoro- (pentafluoroethoxy) propion nanilide and unidentified third component.
Calculated,%: C 27.56; H 0.84; N 5.85 „
With „H4BrF, Ni04
Found,%: C 27.46; H 0.91; N 5.75. .
EXAMPLE 48. The mixture of products from the previous example is purified by treatment in ethanol to give 2-bromo-4-nitro-2,3,3,3-tetrafluoro-2- (pentafluoroethoxy) propionanilide,
528343
sixteen
m.p. 49 C, yield 50% (14% unidentified third component).
Calculated.: C 27.58; H 0.84; N 5.85.
C ,,,
Found,%: C, 27.80; H 1.04; S 6.08.
Example 49. 2-Bromo-4-nitro-2,3,3, 3-tetrafluoro-2- (octafluormorphlino) propionanilide, TopPLo 50-52 ° C, yield 74% (99% of the branched isomer)
5 Calculated,%: C, 27.20; H 0.70; N 7.32.
C ,, N.
Found,%: C 27.42; H 0.75;
  32.
Example 50. 2 -Brom-4-nitro 2,3,3, 3-tetrafluoro-2- (heptafluoro-n-proxy) propionanilide, Topl. 49-51 ° C, yield 35%. A small admixture of 2-bromo-5 4 -nitro-2,3,3, 3-tetrafluoro-2- (nonafluoro-n-butoxy) propionanlnide is determined by F-NMR.
Calculated,%: C, 27.22; H 0.76; N 5.29.
Found,%: C 26.99; H 0.72; N 5.55.
Example 51.2,4 -Dinitro-2,3,3, 3-tetrafluoro-2- (heptafluoro-n-propoxy) propionans, in the form of an oil, yield 50%. A small admixture of 2,4-dinitro-2,3,3, 3-tetrafluoro-2- (nonafluoro-n-butoxy) propionanilide
0
ib
determined by dan F-NMR.
Calculated,%: C 29.11; H 0.81; N 8.49.
Found,%: C 29.31; H 1.05;
five , /
Example 52, 2 -Brom-4-nitro2- (trifluoromethyl) -2.3,3, 4,5,5,5g octafluoro-valeranlide, Topl. 39--40 С, yield 44% (pure isomer).
Calculated,%: C, 28.07; H 0.78; ° N 5.46.
C ,,,,
Found,%: C 28.42; H 0.96; N 5.67.
Example 53. 2- (Trnfluoromethyl) -4-bromo-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide, mp, 37-40 s, yield 49% (81% of the branched isomer) .
Calculated,%: C 30.30; H 0.92; N 3.21.
With „H4BrF, oNO.
Found,%: C 30.07; H 1.02; N 3.20.
PRI me R 54. Monohydrate octade of Cyltrimethylammonium salt 2, dichloro-4-nitro-2,3,3, 3-tetrafluoro-2- (trifluoromethyl) propionanilide, mp 80-82 ° С, yield 99% ( 96% branched isomer).
Calculated,%: C, 51.81; H 7.01; N 5.74.
C ,, H5oCl F, N, 04
Found,%: C 49.75; H 5.56; N 5.42.
Example 55o Hexa-decyltrimethylammonium salt monohydrate of 2,5-dichloro-4-nitro-2,3,3,3-tetrafluoro-2- (trifluoromethyl) propionanilide, m.p. 79-81 ° C, yield 99% (94% of the branched isomer).
Calculated,%: C 49.43; H 6.53; N 5.96.
C, H4eCl F, N, 0
Found,%: C 47.65; H 6.11; N 7.16.,
Example 56. 2-Cyano-4-nitro 2,3,3,3-tetrafluoro-2- (heptafluoro-n-propoxy) propionanilide, m.p. 96 C, yield 17%. A small admixture of 2-cyano-4-nitro-253,3,3-tetrafluoro-2- (nano-fluoro-n-butoxy) propionanilide is determined according to F-NMR.
Calculated,%: C 32.86; H 0.85; N 8,84
, M, 04
Found,%: C 33.06; H 1.14; N 8,69 „,
Example 57 about 2-4-dinitro-5 - fluoro-2,3,3,3-tetrafluoro-2 (pentafluoro-n-propoxy) propionanilide as an oil, yield 62%, a small amount of 2, 4-dinitro-5 - Fluoro-2,3,3,3-tetrafluoro-2- (nonafluoro-n-butoxy) propion-anilide is determined according to F-NMR
Calculated,%: C 28.09; H 0.59; N 8.19.
C, iH, F ,, iN ,, 06
Found,%: C 27.99; H 0.75; N 8.27.
Example 58. 2, 4-dinitro-2- (trifluoromethyl) -2,3,3,4,4,5,5-octafluoro-veranilide as an oil, yield 13%.
Calculated,%: 36.08; H 0.84; N 8.77.
Found,%: C 30.36; H 0.88; G 8.98
ten
Example59. 2 and -Dnnitro-5-fluoro-2- (trifluoromethyl) -2,3,3,4,4,5,5, 5-octafluoro-veranilide in B1 than oil, yield 58%.
Calculated,%: C, 28.99; H 0.61; N 8.45.
.
Found,%: C 29.20; H 0.8A; N 8.71.
PRI me R 60j 2 -Brom-4-chloro-6-cyano-2,3,3,3-tetrafluoro-2- (hepta-j fluoro-and-propoxy) proinonanilide as an oil, yield 51%. A small amount of 2-bromo-4-chloro-6 -iuiaHo-2, 3, 3, 3-tetrafluoro-2- (yunafts) p-and-butoxy) propionanilide is determined by the number dai:
20
F-NMR.
Calculated,%: C, 29.21; And 0.61; N 5.68.
C HjBrClF,.
Found,%: C 29,; H 0.87;
25 N 5.48.
Example 2 -Brom-4-nitro-2,3,3,4,4,5,5,6,6-decafluoro-2- (penta-fluoroethyl) hexananyl
This compound is derived from 2,3,3,
30, 5,6,6, 6-decafluoro-2- (pen t af tortil ethyl) hexanoic acid by conversion into electrofluoride fluoride by electrofluorization using the following method, ohm, B te (} 1 liter vessel equipped with
 A stainless steel cooler, in which the temperature is maintained from -40 to -50 ° C, is placed approximately 80 cm of commercial anhydrous HF before conducting electrolyte 40 to remove the last traces of moisture. An electrode block of about 2 inches 3 (33 cm) is used, consisting of alternating nickel plates and carbon steel in an atmosphere of nitrogen at a maximum III current density of about 20 mA / cm with a cell voltage of 5.2 V or not; relation to the copper electrode. 4.1 g of acid are added and about 0.5 Ah are passed. The reaction mixture is extracted with four portions of 20 CM CFClj, and the extracts are added to 1.6 g of 2-bromo-4-nitroaniline and 1.5 g of triethylamine in 25 cm
its methylene chloride. The organic layer is washed with dilute HC1, and the residue is chromatographed on scapicagel with toluene to obtain a crude mixture, F-NMR. the range of which corresponds to the target product. The crude mixture is again chromatographed with ethyl acetate / hexane (1: 5) to obtain 100 mg of the desired anilide as an oil in a yield of 1.6%.
Calculated,%: C, 27.43; H 0.66; N 4.57.
With „H4BrF, 5N2, Ob
Found,%: C 27.56; H 0.73; N 4.75.
The products of the proposed process are low toxic compounds, especially in comparison with other compounds used as soil insecticides, such as counter.
The compounds obtained by the proposed method are useful as insecticides, particularly for controlling the larvae of the long-beetle beetle. When dealing with these larvae, a very important factor is the residual effect or the effect of the compound "On pra0, 5 pounds / acre 0.56 kg / ha; 1.0 lb / acre 1.12 kg / ha
As can be seen from the presented data, the proposed compounds are superior in that they retain residual activity for many weeks longer.
The proposed compound of example 1 was also tested against four insect species: the southern migratory worm (SAW), spider bison mite mite (2SSM), gourd aphid (MA) and long-haired south flea (SCRW) compared to 4-chloro-2-hydr hydroxy-6-oxo-1-cyclohexene-1- (carboxaziline II).
In ticking, an active agent for the control of the beetle beetle with a long-haul should be used during planting of maize, while hatching of larvae occurs some time after planting.
Thus, it is necessary that the bugbug control agent
the longnose had a residual effect, otherwise the larvae would not be destroyed. This requirement for a residual effect is even more important in those infrequent
spring periods when weather conditions delay hatching or the appearance of larvae. The advantage of the invention is that the proposed compounds exhibit a good residual effect.
The residual efficacy of the compounds with respect to the beetle-flea beetle during field trials is presented in Table 1.
Table 1
The composition containing the corresponding compound was applied to each of said insects on the plants or, in the case of the last insect, to his personal substances in the soil. For the first three insects, the test compound concentration was in the composition 1.56-200 gm. For SCRW, the concentration of the test compound in the composition during trimenenia and on the soil was 0.09-12.0 gm.
55
The results of destruction,%, are given in table 2.
Table 2
Continuation of table 3
Thus, the proposed compounds generally exhibit excellent properties as insecticides in comparison with known compounds.

权利要求:
Claims (1)
[1]
Invention Formula
The method of producing alkanoyl anilide of the general formula
RO-C-C-N-R :,
RT RO
where Rp is fluorine;
K - CFj, SzRt
 CFj, perfluoro- (lower) alkok-, perfluormorpholi- 45
no-hydrogen;
Compiled by V. M Kusheva Editor A. Kozoriz Tehred I. Veres
Order 1009
Circulation 344
VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
K-5-nitro-2-pyridyl, 4-nitro-1-naphthyl or phenyl substituted by p-nitro, two to five independently selected Rj, where Rj is bromine, chlorine or fluorine, or two independently selected groups Rg, where Rg - iodine, nitro, cyano, trifluoromethyl, or two groups, including one group Rj and one group Rg or two groups, including one methyl and one nitro group, or three groups, including two independently selected R groups and one Rg a group, or three groups comprising two independently selected Rg groups and one Rg. group, or its ammonium salts, in which ammonium has the following form.
L
RD
where Rg is independently C -Cg-alkyl, benzyl;
Rq is hydrogen or Rg, and the number of carbon atoms in all Rg and R is different from that amine of the general formula
HNR.jR4 J
where R and R have the indicated meanings are reacted with an alkanoyl halide of the formula
l
40
(SKDK, K;) COX
0 "
R have the indicated values R (cheni;
X is halogen
with the subsequent selection of the target product or transfer it to the corresponding ammonium salt.
Proofreader T.Paly
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US3113967A|1960-10-25|1963-12-10|Du Pont|Addition of carbonyl fluoride to polyfluoro-olefins|

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DE2042300A1|1970-08-26|1972-03-23|Farbwerke Hoechst AG, vormals Meister Lucius & Brüning, 6000 Frankfurt|Halocarboxylic acid anilides, their production and use as herbicides|

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US3839446A|1970-11-18|1974-10-01|Stauffer Chemical Co|Ether and sulfide meta-substituted anilides|US4962284A|1985-04-05|1990-10-09|Eli Lilly And Company|Alkanoyl anilides|

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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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US72023685A| true| 1985-04-05|1985-04-05|

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