Method of producing substituted semicarbazones or salts thereof

专利摘要:
The invention relates to novel compounds of formula (A) <CHEM> wherein R<2> is the group -C(=NR<1><0>)-SR<9> or -C(=X)-NHR<1><0>, and R, R<3>, R<4>, R<9> and R<1><0> are as stated in the specification, the synthesis thereof, the use of said compounds for the control of weeds and compositions for weed control comprising such compounds.
公开号:SU1450738A3
申请号:SU864028053
申请日:1986-08-19
公开日:1989-01-07
发明作者:Джеймс Андерсон Рихард；Марио Ляйппе Михаель
申请人:Сандос Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to organic chemistry, namely to a method for producing substituted semicarbazones of the general formula
R-cn-mh-CO-t H
Ri
(one)
R

COORi
COORj
ON
COOR,
RI - C, -S.-alkyl}
Z is halogen or CFj;
Zj - hydrogen or halogen
R is hydrogen, St-C.4-alkyl or
CH (RJ-0-CO-R4,
Rj is hydrogen or C -C-alkyl R4 - C, -C4 alkyl,
or their salts, which have herbicidal activity and can be used in agriculture.
The aim of the invention is to develop an accessible process for the production of substituted semicarbazones which have a high herbicidal activity.
Example 1. A solution of 4-phenylsemicarbazide (0.37 g, 2.4 mmol) in 5 ml of methanol was added to a 2-acetylene-THYNNY1THOTYNIC acid solution (0.40 g, 2.4 mmol) in 7 ml of methanol. The resulting mixture was stirred at room temperature overnight, after which the solid precipitate was filtered, washed with ethanol and dried to give 4-phenylsemicarbazone 2-acetyl-nicotinic acid (Table 1, compound 1), mp. 174 ° C (with decomposition),
Example 2. According to the method of Example 1, each of the semicarbazones or thiosemicarbazones 2-11 in Table 1 is obtained from the corresponding semicarbazides or thiosemicarbazides and acetyl compounds.
Example 3. To a solution of 4-phenylsemicarbazone 2-acetylnicotinic acid (0.32 g) in 5 ml of methanol was added 1 eq. sodium methylate. The resulting mixture was stirred at room temperature for 5 minutes, after which the solvent was distilled off in a rotary evaporator to obtain sodium hydroxide.
five
0
five
0
five
4-phenylsemicarbazone 2-acetylnicotinic acid sodium salt, m.p. 203 s (with decomposition).
According to the method of example 3, each of 1 islot in the table. 1-3 process 1 eq. methylene sodium to the corresponding sodium salt. Example 4. To 4-phenylsemiO-carbazone 2-acetylnicotinic acid (0.32 g) in. 5 ml of methanol was added with 1 eq. ammonium hydroxide aqueous solution. The resulting mixture was stirred at room temperature for 5 minutes, after which
the solvent is distilled off in a rotary evaporator to obtain the ammonium salt of 4-phenylsemicarbazone 2-acetylnicotinic acid, m.p. 1460-150 ° C (softened) and 198-200 ° C (gas).
In this way, each of the acids in Table 1-3 is prepared with 1 eq. ammonium hydroxide to give the corresponding ammonium salt.
Example 5. According to the method of Example 4, using isopropylamine, 2-oxyethylamine or diisopropylamine, the following salts are obtained: isopropylammonium salt of compounds 1, mp.
0
five
94 s (softening), 120 C (gas) -, isopropylammonium salt of compound 3, mp, 111-118 ° C, -2-hydroxyethylammonium salt of compound 1, mp. 131 ° C (gas) -, 2-hydroxyethylammonium salt of compound 5, m.p. 118 ° C (gas) -, the diisopropylammonium salt of compound 2, m.p. 208-210 С; the diisopropylammonium salt of compound 3, mp 210-102 C (the structures of the compounds are given in Table 1). I
Example 7. A mixture of sodium salt of 4- (3-fluorophenyl) semicarbazone 2-acetylnicotinic acid (compound 4) (1.0 g, 3.0 mmol) and chloromethyl acetate (0.4 g, 3.5 mmol) in 18 ml of DMF is stirred at room temperature for 3 days. The reaction mixture is poured onto ice. The solid precipitate is filtered off, washed with water and air dried. It is stirred in 40 ml of chloroform for 2 hours and then filtered. The resulting filtrate is evaporated to a glassy material, which is triturated with ether until the crude product is obtained. After purification by preparative thin layer chromatography, D- (3-fluorophenyl) semibarbazole 2-acetstrate nicotinate is obtained, m.p.
isg-ieo c.
Example 8 In the procedure of Example 7, chloromethylbutanoate, 1-chloroethylpropionate, methyl iodide, methyl bromide, 1-chloroethylpropionate, chloromethylbutanoate, and chloromethyloctanoate are reacted with the corresponding sodium salt to give compounds 12-15 in Table 2.
Example 11. To a stirred solution of 2-acetyl-3-thiophenecarboxylic acid (1.70 g, 10.0 mmol) in 15 ml of dry methanol was added 4-phenylsemicarbazide (1.51 g of 10.0 mmol) at a time. in 25 ml of dry methanol. Stirring is continued for 18 h, after which the precipitate is filtered off, washed with diethyl ether and dried to obtain 4-phenylsemicarbazone 2-acetyl-3-thiophencarboxylic acid, m.p. 238 ° C.
Compound 17 (Table 3) is prepared in a similar manner.
Example 12. A suspension of 4-phenylsemicarbazone 2-acetylnicotinic acid (0.50 g) in 20 ml of methanol is treated with diazomethane until the yellow color of the solution is maintained. The solvent is distilled off in vacuo to give 4-phenyl semicarbazone 2-acetyl nicotinate, m.p. 177-178 ° C (compound 16, table 2).
The herbicidal activities prior to germination of selected compounds of the invention are determined as follows. Seeds of selected weeds are planted in the soil and watered with a solution, with residual from water (17%), surfactant compound (0.17%) and test compound in an amount equivalent to 10 pounds / acre (approximately 11 kg / ha) The evaluation was carried out 2 weeks after treatment. The treatment of the following herbs is carried out: Setaria viridis, Echinoch-loa crus-galli. Sorghum bicolor and Avena fatua, Ipomea purpurea, Brassi ca juncea, Solanum nigrum and Abutilon theophrasti.
The average activity when introduced before germination is presented in Table 5.
Herbicidal activity when applied after germination for selected
five
The compounds of the present invention were tested as follows: the seedlings of the selected weeds were sprayed with a water / acetone solution (1: 1), a surface-active agent (0.5%) and evaluated 2 weeks after the spraying. The following herbs were processed: Setaria viridis, Echinochloa crus-galli. Sorghum bicolor and Avena fatua, Ipomea purpurea, Brassica juncea, Solonum nigrum and Abutilon theophrasti,
The average post-germination activities for a number of compounds are shown in Table 4.
Tables 5 and 6 show the herbicidal activity of the proposed compounds in comparison with the known ones (standards I and II).
In Table 5, the following notation is accepted: IW jimsonweed - Datura stramonium; SH sheperdspurse - Capsella bursa-pastoris; SP sicklepod - Cassia 5 obfusifolia; VL velvefleaf - Abutilon theophrasfi; PW pigweed - Amaranthus retroflixus; BG barrardgrass - Echinochloa crus-galli; FT giant foxtail - Setaria faberi; DB dovmy brome - Bro- 0 mus tectorum; WO wild oat - Avena fatua; NS nutsedge - Cyperus rotundus.
The resulting compounds have low toxicity: LDfo for P.O. rats. is 2500 mg / kg.
It is evident from Tables 1-6 that the new compounds have a high activity against herbs during pre-emergence treatment and against broadleaf grasses during post-emergence treatment.
0
five
40

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining substituted semicarbazones of the general formula
45
.K-S -Y-1H-CO-1 НRI.
where R COOR2
(G
N
COOR,
55
g
COOR
c, -C4-alkyl; halogen or
hydrogen, or halogen,
Rj is hydrogen, Cf-C4-alkyl or hCH (Ee) -0-CO-K4;
Rj is hydrogen or C, -C-alkyl;
Rjj - C "S-alkyl,
or a salt thereof, differing from the fact that a compound of the formula R — C (0) —R, where R and RI have the indicated meanings, is reacted with a compound of the formula
 7.1
HiN-NH-CO-NH- @ r
Zo
507386
where Z and ZJP have the indicated meanings, followed by isolation of the desired product, where RJ is hydrogen, or by esterifying it with diazomethane or a compound of the formula
C1-CH (R3) -0-CO-R
Q, where RJ and R, have the indicated meanings, followed by allocation of the target product, in free form or as vice salt.
T a b l and c 5 1
17
CH
SNN
HH252222
Table 4
Pre-emergence treatment
Table 5
13
1450738
14 Continued table. five
Compound
Medium herbicidal activity, Z at a dose of 11 kg / ha
before germination
12 13 14 15 16
Herbs
80 85 85 82 88
Continued table. 6
after vshod
Trvgvy
76 63 71 67
Wide sheet
82 85 78 81

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法律状态:
2007-09-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20040820 |

优先权:

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申请号 | 申请日 | 专利标题

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US76746585A| true| 1985-08-20|1985-08-20|

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