CN1127293C - 2-pyrimioxybenzyl substituted phenyl amine derivatives - Google Patents
2-pyrimioxybenzyl substituted phenyl amine derivatives Download PDFInfo
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- CN1127293C CN1127293C CN 00130735 CN00130735A CN1127293C CN 1127293 C CN1127293 C CN 1127293C CN 00130735 CN00130735 CN 00130735 CN 00130735 A CN00130735 A CN 00130735A CN 1127293 C CN1127293 C CN 1127293C
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Abstract
The present invention relates to 2-pyrimioxybenzyl substituted phenyl amine derivatives which are shown in a structural formula (I). Substituted phenylamine and salicylaldehyde react to generate an intermediate, and the obtained intermediate reacts with 2-methylsulfonyl-4, 6-substituted pyrimidine after reduced; thereby, a (R1 =H) compound shown in the structural formula (I) is obtained. The compound reacts with acyl chloride to obtain a (R1, H) compound shown in the structural formula (I), wherein R1 is unequal to H. The amine derivates shown in the structural formula (I) has high weed removal activity and is suitable for compounding a weed removal agent for cotton fields, rape fields and wheat fields. The derivatives have good control efficiency, low dosage, wide weed removal range, low toxicity and no damage on crops and are friendly to the environment.
Description
The present invention relates to pyrimidines, 2-pyrimioxybenzyl substituted phenyl amine derivatives particularly, their preparation method and as the prescription and the application of agricultural chemicals weed killer herbicide.
Now, the development of agricultural modernization need constantly provide effective, and consumption is low, to crop and environmentally friendly new herbicides, to reduce the agricultural workforce, promotes the raising of agricultural mechanization, modernization development and crop yield.
Known various 2-phenoxy pyrimidine derivates is effective as weed killer herbicide, as United States Patent (USP) 4,906,285 have set forth the Sulfadiazine Compound salicylic acid compounds has the weeding scope of wide spectrum, and United States Patent (USP) 4,932,999 have been disclosed the pyrimidine phosphorothioate salicyclic acid derivatives perennial and annual careless class have been demonstrated excellent herbicidal effect.But they are only applicable to the weeding of cotton field and paddy field, and they have in various degree infringement to rape.
Based on demands of social development, and for enlarging the scope of application, exploitation is applicable to the weed killer herbicide in rape field simultaneously, and the inventor is on the basis of existing invention, carry out guide's expansion, developed a class 2-pyrimioxybenzyl substituted phenyl amine derivatives shown in structural formula (I).
In the formula (I):
D can be identical or different groups with E, is respectively hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl or
C
1-C
4Haloalkyl, wherein preferable D of being and E are methoxyl group, or one of them is methoxyl group, another
Be chlorine or methyl, especially preferably D and E are methoxyl group;
R
1Be hydrogen, C
1-C
4Alkanoyl, C
1-C
4Alkyl halide acyl group, benzoyl group or C
1-C
4The alcoxyl acetyl group, wherein
Be preferably hydrogen, acetyl group, chloracetyl, dichloro-acetyl, benzoyl group or methoxy acetyl group, more desirable
Be hydrogen, chloracetyl or methoxy acetyl group, especially preferably hydrogen.
R
2Be hydrogen, halogen, C
1-C
4Alkyl or trifluoromethyl, wherein preferable be hydrogen, fluorine, chlorine, bromine, iodine, methyl,
Ethyl or trifluoromethyl;
R
3Be hydrogen, halogen, C
1-C
4Alkyl, trifluoromethyl, nitro or cyano group, wherein more preferably hydrogen, fluorine, chlorine,
Methyl, trifluoromethyl, nitro or cyano group;
R
4Be hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl, C
1-C
4Carbalkoxy, trifluoromethyl, cyano group, carboxyl
Or its alkali metal salt, alkali salt, transition metal salt or organic ammonium salt, wherein more preferably hydrogen, fluorine, chlorine,
Bromine, iodine, methyl, trifluoromethyl, methoxyl group, C
1-C
4Carbalkoxy, carboxyl or its sodium salt, sylvite or ammonium salt.
R
5Be hydrogen or halogen, preferable is hydrogen or chlorine;
R
6Be hydrogen, halogen or C
1-C
4Alkyl, preferable is hydrogen, methyl or ethyl.
The inventor by MOLECULE DESIGN, changes middle D of structural formula (I) and E and reaches from R
1To R
6Each substituting group and different combinations thereof have synthesized a series of compounds, and by giving birth to the survey expert it are carried out the evaluation of measuring of activity of weeding and toxicity, have wherein filtered out a collection of compound that higher activity of weeding is arranged, and these compounds are summed up and tabulated in 1.Table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
1 | OCH 3 | OCH 3 | H | H | H | Br | H | H | 54.68 | 4.30 | 10.20 | 415 |
2 | OCH 3 | OCH 3 | H | H | H | I | H | H | 49.11 | 3.86 | 9.00 | 463 |
3 | OCH 3 | OCH 3 | H | H | H | CO 2(CH 2) 2CH 3 | H | H | 65.10 | 5.88 | 9.99 | 423 |
4 | OCH 3 | OCH 3 | H | H | H | OCH 3 | H | H | 65.33 | 5.75 | 11.25 | 367 |
5 | OCH 3 | OCH 3 | COCH 2Cl | H | H | CO 2(CH 2) 2CH 3 | H | H | 60.21 | 5.28 | 8.30 | 499 |
6 | OCH 3 | OCH 3 | COCH 2Cl | H | H | OCH 3 | H | H | 59.25 | 4.99 | 9.40 | 443 |
7 | OCH 3 | OCH 3 | COCH 2CH 3 | H | H | I | H | H | 50.70 | 4.28 | 8.21 | 519 |
8 | OCH 3 | OCH 3 | COCH 3 | H | H | I | H | H | 49.88 | 4.00 | 8.11 | 505 |
9 | OCH 3 | OCH 3 | CO(CH 2) 3Cl | H | H | Br | H | H | 53.11 | 4.50 | 8.10 | 519 |
10 | OCH 3 | OCH 3 | COPh | H | H | Br | H | H | 60.01 | 4.28 | 8.09 | 519 |
11 | OCH 3 | OCH 3 | COCHCl 2 | H | H | Br | H | H | 47.77 | 3.47 | 7.97 | 527 |
12 | OCH 3 | OCH 3 | COCH 2CH 3 | H | H | Br | H | H | 55.81 | 4.65 | 8.72 | 471 |
13 | OCH 3 | OCH 3 | COCH 2Cl | H | H | Br | H | H | 51.22 | 3.89 | 8.44 | 491 |
Continuous table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
14 | OCH 3 | OCH 3 | COCHCl 2 | H | H | OCH 3 | H | H | 55.00 | 4.40 | 8.66 | 477 |
15 | OCH 3 | OCH 3 | CO(CH 2) 3Cl | H | H | OCH 3 | H | H | 61.12 | 5.60 | 8.78 | 471 |
16 | OCH 3 | OCH 3 | H | Cl | H | H | Cl | H | 56.30 | 4.22 | 10.33 | 405 |
17 | OCH 3 | OCH 3 | H | CH 3 | H | H | Cl | H | 62.07 | 5.25 | 10.88 | 385 |
18 | OCH 3 | OCH 3 | COCH 2Cl | Cl | H | H | Cl | H | 52.11 | 3.71 | 8.56 | 481 |
19 | OCH 3 | OCH 3 | COCH 2Cl | CH 3 | H | Cl | H | H | 57.25 | 4.59 | 9.20 | 461 |
20 | OCH 3 | OCH 3 | H | F | H | H | H | H | 64.09 | 5.10 | 11.88 | 355 |
21 | OCH 3 | OCH 3 | H | Cl | H | H | H | H | 61.21 | 4.86 | 11.54 | 371 |
22 | OCH 3 | OCH 3 | H | H | H | Cl | H | H | 61.29 | 4.89 | 11.33 | 371 |
23 | OCH 3 | OCH 3 | H | Cl | Cl | H | H | H | 56.30 | 4.21 | 10.50 | 405 |
24 | OCH 3 | OCH 3 | H | H | H | CH 3 | H | H | 68.25 | 5.99 | 11.88 | 351 |
25 | OCH 3 | OCH 3 | H | H | Cl | Cl | H | H | 56.06 | 4.14 | 10.44 | 405 |
26 | OCH 3 | OCH 3 | H | H | Cl | H | H | H | 61.50 | 4.86 | 11.50 | 371 |
27 | OCH 3 | OCH 3 | COCH 2Cl | F | H | H | H | H | 58.28 | 4.35 | 9.66 | 431 |
28 | OCH 3 | OCH 3 | COCH 2Cl | Cl | H | H | H | H | 56.21 | 4.30 | 9.50 | 447 |
29 | OCH 3 | OCH 3 | COCH 2Cl | H | H | Cl | H | H | 56.20 | 4.21 | 9.52 | 447 |
30 | OCH 3 | OCH 3 | COCH 2Cl | Cl | Cl | H | H | H | 52.17 | 3.75 | 8.56 | 481 |
31 | OCH 3 | OCH 3 | COCH 2Cl | H | H | CH 3 | H | H | 61.68 | 5.20 | 9.87 | 427 |
Continuous table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
32 | OCH 3 | OCH 3 | COCH 2Cl | H | Cl | Cl | H | H | 52.15 | 3.80 | 8.55 | 481 |
33 | OCH 3 | OCH 3 | COCH 2Cl | H | Cl | H | H | H | 56.18 | 4.30 | 9.39 | 447 |
34 | OCH 3 | OCH 3 | H | CH 3 | Cl | H | H | H | 62.22 | 5.25 | 10.79 | 385 |
35 | OCH 3 | OCH 3 | H | CH 3 | H | H | H | H | 68.25 | 5.89 | 11.88 | 351 |
36 | OCH 3 | OCH 3 | H | H | Cl | H | Cl | H | 56.22 | 4.14 | 10.45 | 405 |
37 | OCH 3 | OCH 3 | H | Cl | H | Cl | H | H | 56.09 | 4.17 | 10.33 | 405 |
38 | OCH 3 | OCH 3 | H | CH 3 | H | CH 3 | H | H | 69.01 | 6.35 | 11.64 | 365 |
39 | OCH 3 | OCH 3 | COCH 2Cl | CH 3 | H | H | H | H | 61.76 | 5.21 | 9.78 | 427 |
40 | OCH 3 | OCH 3 | COCH 2Cl | H | Cl | H | Cl | H | 52.33 | 3.69 | 8.79 | 481 |
41 | OCH 3 | OCH 3 | COCH 2Cl | Cl | H | Cl | H | H | 52.40 | 3.77 | 8.55 | 481 |
42 | OCH 3 | OCH 3 | COCH 2Cl | CH 3 | H | CH 3 | H | H | 62.45 | 5.49 | 9.70 | 441 |
43 | OCH 3 | OCH 3 | COCH 2Cl | CH 3 | H | H | H | CH 3 | 62.60 | 5.41 | 9.66 | 441 |
44 | OCH 3 | OCH 3 | H | CF 3 | H | H | H | H | 59.33 | 4.48 | 10.45 | 405 |
45 | OCH 3 | OCH 3 | COCH 2Cl | CF 3 | H | H | H | H | 54.90 | 4.01 | 8.88 | 481 |
46 | OCH 3 | OCH 3 | H | H | H | CF 3 | H | H | 59.27 | 4.40 | 10.30 | 405 |
47 | OCH 3 | OCH 3 | COCH 2Cl | H | H | CF 3 | H | H | 54.79 | 3.99 | 8.56 | 481 |
48 | OCH 3 | OCH 3 | COCH 2Cl | H | H | I | H | H | 46.80 | 3.54 | 7.88 | 539 |
49 | OCH 3 | OCH 3 | H | H | F | H | H | H | 64.33 | 5.11 | 11.77 | 355 |
Continuous table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
50 | OCH 3 | OCH 3 | COCH 2Cl | H | F | H | H | H | 58.29 | 4.35 | 9.90 | 431 |
51 | OCH 3 | OCH 3 | H | H | I | H | H | H | 49.25 | 3.85 | 9.11 | 463 |
52 | OCH 3 | OCH 3 | COCH 2Cl | H | I | H | H | H | 46.66 | 3.59 | 7.79 | 539 |
53 | OCH 3 | OCH 3 | H | H | CH 3 | CH 3 | H | H | 69.20 | 6.35 | 11.56 | 365 |
54 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | H | Cl | H | H | 59.36 | 4.90 | 9.40 | 443 |
55 | OCH 3 | OCH 3 | H | H | CF 3 | H | H | Cl | 54.53 | 3.81 | 9.66 | 439 |
56 | OCH 3 | OCH 3 | H | C 2H 5 | H | H | H | C 2H 5 | 70.15 | 6.82 | 10.78 | 393 |
57 | OCH 3 | OCH 3 | H | I | H | H | H | H | 49.19 | 3.80 | 9.14 | 463 |
58 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | F | H | H | H | 61.68 | 5.10 | 9.69 | 427 |
59 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | H | I | H | H | 49.20 | 4.14 | 7.72 | 535 |
60 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | Cl | Cl | H | H | 55.26 | 4.35 | 8.88 | 477 |
61 | OCH 3 | OCH 3 | COCH 2Cl | H | CH 3 | CH 3 | H | H | 62.55 | 5.40 | 9.60 | 441 |
62 | OCH 3 | OCH 3 | COCH 2Cl | C 2H 5 | H | H | H | C 2H 5 | 63.89 | 5.97 | 8.99 | 469 |
63 | OCH 3 | OCH 3 | COCH 2Cl | H | CF 3 | H | H | Cl | 51.30 | 3.43 | 8.15 | 515 |
64 | OCH 3 | OCH 3 | COCH 2Cl | I | H | H | H | H | 46.88 | 3.53 | 7.78 | 539 |
65 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | Cl | H | H | H | 59.45 | 4.91 | 9.50 | 443 |
66 | OCH 3 | OCH 3 | COCH 2OCH 3 | H | I | H | H | H | 49.50 | 4.17 | 7.85 | 535 |
67 | OCH 3 | OCH 3 | H | H | H | H | H | H | 67.70 | 5.63 | 12.55 | 337 |
Continuous table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
68 | OCH 3 | OCH 3 | H | CH 3 | H | Br | H | H | 55.68 | 4.70 | 9.92 | 429 |
69 | OCH 3 | OCH 3 | H | Br | H | H | H | H | 54.77 | 4.41 | 10.20 | 415 |
70 | OCH 3 | OCH 3 | H | H | H | F | H | H | 64.40 | 5.10 | 11.89 | 355 |
71 | OCH 3 | OCH 3 | H | H | CF 3 | H | H | H | 59.29 | 4.50 | 10.34 | 405 |
72 | OCH 3 | OCH 3 | H | H | Cl | F | H | H | 58.44 | 4.31 | 10.77 | 389 |
73 | OCH 3 | OCH 3 | H | CH 3 | NO 2 | H | H | H | 60.49 | 5.10 | 14.30 | 395 |
74 | OCH 3 | OCH 3 | H | H | NO 2 | CH 3 | H | H | 60.56 | 5.08 | 14.20 | 395 |
75 | OCH 3 | OCH 3 | COCH 2Cl | H | H | H | H | H | 60.88 | 4.80 | 10.16 | 413 |
76 | OCH 3 | OCH 3 | H | H | H | CN | H | H | 66.21 | 4.94 | 15.44 | 362 |
77 | OCH 3 | OCH 3 | H | H | CN | H | H | H | 66.29 | 4.99 | 15.56 | 362 |
78 | OCH 3 | OCH 3 | H | H | H | CO 2CH 3 | H | H | 63.77 | 5.25 | 10.70 | 395 |
79 | OCH 3 | OCH 3 | H | H | H | CO 2C 2H 5 | H | H | 64.45 | 5.60 | 10.41 | 409 |
80 | OCH 3 | OCH 3 | H | H | H | CO 2C 4H 9-n | H | H | 65.88 | 6.21 | 9.56 | 437 |
81 | OCH 3 | OCH 3 | H | H | H | CO 2CHCH 3) 2 | H | H | 65.33 | 5.88 | 9.78 | 423 |
82 | OCH 3 | OCH 3 | H | H | H | CO 2Na | H | H | 59.65 | 4.52 | 10.45 | 403 |
83 | OCH 3 | OCH 3 | H | H | H | CO 2K | H | H | 57.41 | 4.26 | 10.11 | 419 |
84 | OCH 3 | OCH 3 | H | H | H | CO 2H | H | H | 62.79 | 4.89 | 11.20 | 381 |
85 | Cl | OCH 3 | H | H | H | CO 2C 2H 5 | H | H | 60.88 | 4.80 | 10.31 | 413 |
Continuous table 1
Numbering | D | E | R 1 | R 2 | R 3 | R 4 | R 5 | R 6 | Elementary analysis (%) | Mass spectrum M + | ||
C | H | N | ||||||||||
86 | CH3 | OCH 3 | H | H | H | CO 2C 2H 5 | H | H | 67.30 | 5.81 | 10.59 | 393 |
87 | OCH 3 | OCH 3 | H | H | H | CO 2H·NH(CH 3) 2 | H | H | 61.99 | 6.19 | 13.25 | 381 |
Give birth to survey and show that the 2-pyrimioxybenzyl substituted phenyl amine derivatives has good weeding activity shown in the structural formula (I), and herbicidal spectrum is wide, low toxicity is environmentally friendly, does not injure crop.Therefore, they are effective active things of preparation agricultural herbicide.
The The compounds of this invention kind is a lot, but structural formula is similar, belong to the homologous series compound, thereby its synthetic method is also similar substantially.The synthetic method that the inventor adopted is as follows:
(R shown in A, the structural formula (I)
1=H) the synthetic method of compound divided for three steps, can reaction equation be expressed as follows:
R in the above-mentioned reaction equation in each compound
2, R
3, R
4, R
5, R
6Reach the substituting group of D, E representative, as previously mentioned, X is halogen or methylsulfonyl.
That is to say (R shown in the structural formula of the present invention (I)
1=H) compound (2) synthetic, at first by substituted aniline (3) and salicylide (4) with 1: the mol ratio of 1.0-1.2 is dissolved in methyl alcohol, ethanol or the propyl alcohol class alcoholic solvent, to the temperature range internal reaction of solvent boiling point 20-60 minute, obtain intermediate (5) in room temperature.Reaction can be carried out under the situation of catalyst-free, and adds catalyzer and under the situation of azeotropic dehydration, can add fast response, improves reaction yield.Used catalyzer can be p-methyl benzenesulfonic acid, methanesulfonic acid, sulfuric acid or hydrochloric acid in the reaction.
Solvent for use is except that alcohols solvent in the reaction, and also available aromatic hydrocarbons is as benzene, toluene or dimethylbenzene; Halogenated hydrocarbons is as carrene, dichloroethane or chloroform; Ether solvents is as oxolane or dioxane; Ketone solvent is as acetone or methyl iso-butyl ketone (MIBK); Or dimethyl formamide or dimethyl sulfoxide (DMSO); Or acetonitrile and their mixture.
Then, the intermediate (5) of first step gained in methyl alcohol, ethanol or propyl alcohol kind solvent, is got intermediate (6) in the room temperature reduction reaction in the presence of sodium borohydride or potassium borohydride reduction agent.
The 3rd step made intermediate (6) and 2-halo-4,6-substituted pyrimidines or 2-methylsulfonyl-4, and 6-substituted pyrimidines (7) is with 1: the 1.0-1.2 mol ratio is reacted in solvent and under the condition that alkali exists, and promptly gets product of the present invention (R shown in structural formula (I)
1=H) compound (2).In this step reaction, used alkali can be sodium metal or potassium and so on alkali metal, or sodium hydride, hydrofining and so on alkali metal hydride, or calcium hydride and so on alkaline earth metal compound, or sodium alkoxide, potassium alcoholate and so on alcoxyl metallic compound, or sodium carbonate, potash and so on alkali carbonate, or organic amines such as triethylamine, pyridine.
Used solvent in three-step reaction, can be aromatic solvents such as benzene, toluene or dimethylbenzene, alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, ether solvent such as oxolane, dioxane, ketones solvent such as acetone, methylisobutylketone, dimethyl formamide, dimethyl sulfoxide (DMSO) equal solvent, or acetonitrile and their mixture.(B) (R shown in the structural formula (I)
1≠ H) the synthetic method of compound:
As previously mentioned, through three-step reaction gained (R shown in structural formula (I)
1=H) compound (2) promptly is one of our needed active matter with weeding function, and if itself and acyl chlorides (8) are further reacted in solvent and under the condition of alkali existence, also can be had (the R shown in structural formula (I) of activity of weeding equally
1≠ H) compound, reaction can be represented with following reaction equation;
D and E, R in the reaction equation
1-R
6Equal (R as previously mentioned
1≠ H).
The temperature of this reaction in room temperature to the solvent boiling point temperature range, reaction solvent for use and alkali and aforementioned shown in structural formula (I) (R
1=H) synthetic the 3rd step of compound (2) is identical.
2-pyrimioxybenzyl substituted phenyl amine derivatives of the present invention, synthetic method is uncomplicated, and product all has good weeding activity, is the effective active matter of preparation agricultural herbicide.
Formula provided by the invention (I) compound and preparation thereof can be prevented and treated most of farmland weeds effectively, (g ai/ha is gram active matter/hectare to 45-75g ai/ha, as follows) the following effectively control grassy weed of low dosage, 150-300g ai/ha high dose is is effectively prevented and treated broad leaved weed and nutgrass flatsedge down, as barnyard grass grass (Echinochloa crusgalli), lady's-grass (Digitaria sanguinalis), eleusine indica (Eleusine indica), green foxtail (Setaria viridis), annual bluegrass (Poa annua), wild oat (Avena fatua), amur foxtail (Alopecurus aequalis), Japan amur foxtail (Alopecurus japonicus), Amaranthus retroflexus (Amaranthusretroflexus), thorn amaranth (Amaranthus spinosus), lamb's-quarters (Chenopodium album), leaf mustard (Brassica juncea), kitchen garden (Portulaca oleracea), acalypha copperleaf (Acalypha australis), difformed galingale herb (Cyperus difformis), moleplant seed (Leptochloa chinensis), the rhizome of nutgrass flatsedge (Cyperus rotundus), grass (Fimbristylismiliacea) floats sunshine, Veronica (Veronica diayma), chickweed (Stallaria media), common vetch (Vicia sativa), Stellaria alsine Grim. (Stellaria alsine), annual fleabane herb (Erigeron annuus), short arrowhead (Sagittaria sagittifolia), field bindweed (Convolvulus arvensis) etc.As weed killer herbicide, they have the following advantage and characteristics:
1, activity of weeding height, the low dosage consumption is also effective;
2, have efficiently herbicidal effect behind the bud under the low dosage, also have herbicidal effect before the bud under the higher dosage;
3, broad weed-killing spectrum can not only effectively be prevented and kill off grassy weed in the farmland, and can prevent and kill off broad leaved weed and nutgrass flatsedge;
4, safe to crop, thing is other as safe as a house to cotton, rape, paddy rice;
5, adopt the undergraduate course weeds and also have highly effective activity of weeding the 3-7 leaf is above the average age for marriage;
6, residual life, is short in soil, and the growth of crop rotation succession crop is had no adverse effects;
7, mammal or fish are not had overt toxicity, the environmental safety height belongs to the environmentally friendly agricultural chemicals of low toxicity;
Use for reality, reactive compound of the present invention can be processed as various granulas, pulvis, finish, emulsion, aqueous suspension or capsule etc. by common prescription technology in the pesticide industry.
By the following examples, synthetic method of the present invention is done further to specifically describe, but should declare, the present invention never is limited to this concrete example.
Synthesis example 1: (R shown in the structural formula (I)
1=H) the preparation of compound (2)
Example: 9.3 gram (0.1 mole) aniline are dissolved in 125 milliliters the absolute methanol, drip 12.2 gram (0.1 mole) salicylides, at room temperature stirring reaction is after 10 minutes, filter, solid washs with absolute methanol, get 18.0 gram yellow solid product, yield 91.37% is N-(2-hydroxyl benzal) aniline [being equivalent to the intermediate (5) in the aforementioned synthetic method].
Get above-mentioned made N-(2-hydroxyl benzal) aniline 9.85 grams (0.05 mole), be dissolved in 100 milliliters of absolute methanols, at room temperature add 1.29 gram (0.034 mole) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrate and remove methyl alcohol, in residue, add 200 milliliters of chloroforms then, 150 milliliters in water stirs, and leaves standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 9.75 gram white solid product, yield 98.0% is for N-(2-hydroxybenzyl) aniline [is equivalent to the intermediate (6) in the aforementioned synthetic method.
Get top made N-(2-hydroxybenzyl) aniline 1.99 grams (10 mM), 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (10 mM), be dissolved in 100 milliliters of oxolanes, add 3.71 gram (26.84 mM) potash under the room temperature, back flow reaction 11 hours, suction filtration, solid washs with 20 milliliters of oxolanes, and mother liquor concentrates, residual product adds 10 milliliters of ethanol agitator treatings, suction filtration gets 3.00 gram white solid product, yield 89.0%, mp90.2-90.7 ℃, be N-phenyl-2-(4,6-dimethoxypyridin 2-yl) oxygen base aniline.
Elementary analysis: molecular formula C
19H
19N
3O
3Molecular weight 337
Theoretical value C67.66 H5.64 N12.46 measured value C67.70 H5.63 N12.55
Nuclear magnetic resonnance: HNMR (CDCl
3) δ (ppm) 3.81 (6H, s, OCH
3), 4.33 (2H, s, CH
2), 5.77 (1H, s, CH), 6.54-
7.47(9H,m,Ar-H)
Mass spectrum: Ms 337 (M
+)
Synthesis example 2: (R shown in the structural formula (I)
1≠ H) compound
Example: in 100 milliliters of single port bottles, add N-phenyl-2-(4,6-dimethoxypyridin-2-yl) Phenoxybenzamine 0.89 gram (2.64 mM); chloracetyl chloride 0.82 gram (7.25 mM); potash 0.55 gram (3.99 mM) and 30 milliliters of THF, back flow reaction 10 hours, suction filtration; remove solid; organic layer concentrates to such an extent that wax shape white solid 0.89 restrains yield 77.7%, mp74.5-77.8 ℃; be N-[2-(4,6-dimethoxypyridin 2-yl) oxygen base benzamido group] 2-chloro acetyl group aniline.
Elementary analysis: molecular formula C
21H
20CIN
3O
4Molecular weight 413
Theoretical value C60.94 H4.84 N10.16 measured value C60.88 H4.80 N10.31
Nuclear magnetic resonnance: HNMR (CDCl
3) δ (ppm) 3.77 (6H, s, OCH
3), 4.13 (2H, s, CH
2), 5.01 (2H, s, CH
2),
5.72(1H,s,CH),7.06-7.42(9H,m,Ar-H)。
Mass spectrum: Ms413 (M
+)
Below provide with The compounds of this invention and make the active substance component, the concrete instance of processing preparation several herbicides formulation, in these prescription examples, all " % " all refer to percentage by weight, " g ai/ha " all refers to restrain active matter/hectare.
Formulation Example 1 (wetting powder)
No. 70 materials (table 1) with 15%, 5% lignosulfonates (M
q), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% precipitated calcium carbonate mix equably, pulverizes, and promptly gets wetting powder.
Formulation Example 2 (missible oil)
No. 602, No. 70 materials with 10%, 5% farming breast No. 500 (calcium salts), 5% farming breast, 5% N-methyl 2-Pyrrolidone and 75% dimethylbenzene heated and stirred are even, promptly get missible oil.
Formulation Example 3 (granula)
No. 70 materials (table 1) with 5%, 1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) and 90% clay mix equably; pulverize; add 20 parts of water, kneading to these 100 parts of mixtures then; with the extruding granulating machine; make 14-32 purpose particle; drying promptly gets granule.
Below will test activity of weeding and the crop safety that example makes the weed killer herbicide of active component preparation to part of compounds of the present invention and carry out test evaluation by the test of giving birth to of give birth to surveying that the expert provides.Evaluation criterion is listed in table 2.
Table 2: activity of weeding and phytotoxicity evaluating standard
Grading index | Phytotoxicity (%) | Activity of weeding comment (inhibition, deformity, albefaction etc.) | Crop safety comment (inhibition, deformity, albefaction etc.) |
0 | 0 | With contrast, anti-, eliminate | With contrast, anti-, normal |
1 | 10-20 | Gently, influential slightly, eliminate | Gently, influential slightly, can consider |
2 | 30-40 | Gently, influential, eliminate | Sensitivity, influential, eliminate |
3 | 50-60 | Sensitivity, influential, can consider further transformation | Responsive, poisoning is heavy, eliminates |
4 | 79-80 | Responsive, can consider | Extremely responsive, poisoning is heavy, eliminates |
5 | 90-100 | Extremely responsive, good | Extremely responsive, poisoning is heavy, eliminates |
Test examples 1: the activity of weeding test that cauline leaf is handled behind the seedling
Be equipped with test with the basin alms bowl of soil in (diameter 9.5cm) sow the seed of barnyard grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and kitchen garden respectively equably, overburden soil 0.5cm is thick, the basin alms bowl is placed 20-25 ℃ greenhouse cultivation 10 days.During the plant strain growth two leaf stage, each number active matter cream preparation dilute with water that similar Formulation Example 2 is prepared carries out the cauline leaf spraying and handles cultivating the examination material with the dosage of 2250g ai/ha or 750gai/ha.Routine observation is respectively handled the plant strain growth state, the symptom of being injured, and handles back 28 days, evaluates according to the standard of determining in the table 2.The results are shown in Table 3.
Table 3: the activity of weeding (dry land condition) of the back leaf surface treatment of emerging
Compound number | Dosage (g ai/ha) | The activity of weeding index | |||||
The barnyard grass grass | Lady's-grass | Eleusine indica | Leaf mustard | Amaranthus retroflexus | Kitchen garden | ||
1 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
2 | 2250 | 5 | 5 | 5 | 5 | 5 | 5 |
3 | 2250 | 5 | 5 | 5 | 5 | 5 | 5 |
10 | 750 | 2 | 0 | 3 | 0 | 4 | 0 |
11 | 750 | 0 | 0 | 0 | 0 | 4 | 0 |
14 | 750 | 3 | 3 | 4 | 0 | 4 | 0 |
15 | 750 | 5 | 5 | 5 | 4 | 5 | 5 |
Continuous table 3
Compound number | Dosage (g ai/ha) | The activity of weeding index | |||||
The barnyard grass grass | Lady's-grass | Eleusine indica | Leaf mustard | Amaranthus retroflexus | Kitchen garden | ||
16 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
17 | 750 | 5 | 5 | 5 | 2 | 5 | 5 |
20 | 750 | 5 | 4 | 4 | 4 | 5 | 4 |
21 | 750 | 5 | 4 | 4 | 4 | 4 | 4 |
22 | 750 | 5 | 4 | 4 | 5 | 4 | 4 |
24 | 750 | 5 | 4 | 4 | 5 | 4 | 4 |
34 | 750 | 5 | 5 | 5 | 4 | 5 | 5 |
35 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
36 | 750 | 5 | 5 | 5 | 4 | 5 | 4 |
37 | 750 | 5 | 5 | 5 | 5 | 5 | 4 |
38 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
40 | 750 | 3 | 2 | 2 | 2 | 3 | 3 |
42 | 750 | 1 | 1 | 0 | 1 | 4 | 0 |
44 | 750 | 5 | 5 | 5 | 4 | 5 | 5 |
46 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
49 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
51 | 750 | 5 | 5 | 5 | 4 | 5 | 4 |
54 | 750 | 0 | 0 | 0 | 0 | 0 | 3 |
55 | 750 | 5 | 5 | 5 | 4 | 5 | 5 |
56 | 750 | 5 | 4 | 4 | 5 | 5 | 5 |
Test examples 2: the activity of weeding of soil treatment test before the seedling
The seed that (diameter 9.5cm) even respectively sowing barnyard grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and kitchen garden in the native basin alms bowl are used in test is being housed, overburden soil 0.5cm is thick, each number active matter cream preparation dilute with water that similar Formulation Example 2 is prepared after 12 hours, and with 2250 or the dosage of 750g ai/ha carry out soil surface and handle cultivating the examination material.Routine observation is respectively handled the plant strain growth state, the symptom of being injured, and handles back 28 days, evaluates according to the standard of determining in the table 2, the results are shown in Table 4.
Table 4: the activity of weeding (nonirrigated farmland condition) of soil treatment before emerging
Compound number | Dosage (g ai/ha) | The activity of weeding index | |||||
The barnyard grass grass | Lady's-grass | Eleusine indica | Leaf mustard | Amaranthus retroflexus | Kitchen garden | ||
1 | 750 | 4 | 4 | 5 | 4 | 5 | 5 |
2 | 2250 | 5 | 5 | 5 | 4 | 5 | 5 |
Continuous table 4
Compound number | Dosage (g ai/ha) | The activity of weeding index | |||||
The barnyard grass grass | Lady's-grass | Eleusine indica | Leaf mustard | Amaranthus retroflexus | Kitchen garden | ||
3 | 2250 | 5 | 5 | 5 | 4 | 5 | 5 |
10 | 750 | 0 | 0 | 2 | 0 | 2 | 0 |
11 | 750 | 0 | 0 | 0 | 0 | 0 | 0 |
14 | 750 | 0 | 0 | 3 | 0 | 0 | 0 |
15 | 750 | 4 | 5 | 5 | 2 | 5 | 5 |
16 | 750 | 5 | 4 | 5 | 3 | 5 | 5 |
17 | 750 | 3 | 4 | 4 | 2 | 5 | 5 |
20 | 750 | 3 | 4 | 4 | 4 | 5 | 4 |
21 | 750 | 3 | 4 | 4 | 4 | 5 | 4 |
22 | 750 | 4 | 4 | 5 | 4 | 5 | 4 |
24 | 750 | 4 | 4 | 4 | 5 | 5 | 4 |
34 | 750 | 4 | 4 | 4 | 5 | 5 | 5 |
35 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
36 | 750 | 4 | 5 | 4 | 5 | 5 | 5 |
37 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
38 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
40 | 750 | 1 | 2 | 2 | 3 | 3 | 3 |
42 | 750 | 0 | 0 | 0 | 0 | 1 | 1 |
44 | 750 | 4 | 5 | 5 | 5 | 5 | 5 |
46 | 750 | 4 | 4 | 5 | 5 | 5 | 5 |
49 | 750 | 5 | 5 | 5 | 5 | 5 | 5 |
51 | 750 | 3 | 3 | 3 | 5 | 5 | 5 |
54 | 750 | 0 | 0 | 0 | 0 | 0 | 0 |
55 | 750 | 4 | 5 | 5 | 5 | 5 | 5 |
56 | 750 | 5 | 5 | 5 | 4 | 5 | 5 |
Test examples 3: the activity of weeding dosage gradient test that cauline leaf is handled behind the seedling
With barnyard grass grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and kitchen garden is the weeds target, carries out the test of various dose gradient.Test is provided with a grade dosage.When grassy weed growth two leaf stage, 2 leaf periods of broad leaved weed growth, 3,16, No. 17 active matter cream preparation dilute with waters that similar Formulation Example 2 is prepared, with dosage shown in the table 5 the examination material of cultivating being carried out the cauline leaf spraying handles, handled back 28 days, evaluate according to the standard of determining in the table 2, the results are shown in Table 5.
Table 5: the activity of weeding dosage gradient test that cauline leaf is handled behind the seedling
Compound number | Dosage (g ai/ha) | Herbicidal effect | |||||
The barnyard grass grass | Lady's-grass | Eleusine indica | Leaf mustard | Amaranthus retroflexus | Kitchen garden | ||
3 | 375 | 5 | 5 | 5 | 4 | 5 | 4 |
150 | 4 | 3 | 4 | 2 | 4 | 4 | |
75 | 2 | 0 | 3 | 4 | 4 | 4 | |
16 | 375 | 5 | 5 | 4 | 5 | 5 | 4 |
240 | 5 | 4 | 4 | 3 | 5 | 4 | |
124 | 4 | 4 | 4 | 3 | 5 | 2 | |
17 | 375 | 5 | 5 | 5 | 4 | 5 | 5 |
150 | 5 | 5 | 5 | 4 | 5 | 5 | |
75 | 5 | 4 | 4 | 2 | 5 | 4 |
Test examples 4: the crop safety test that cauline leaf is handled behind the seedling
Difference sowing cotton, rape seed in the 12cm basin alms bowl that test soil is housed, place 20-25 ℃ of greenhouse to grow, after waiting to grow into the regular period, each number active matter cream preparation dilute with water that similar Formulation Example 2 is prepared is with 375,150, the dosage of 75g ai/ha carries out the cauline leaf spraying to the examination material of cultivating and handle.Handle the back routine observation plant strain growth state and the symptom of being injured, handled back 28 days
Table 6: the crop safety (dry land condition) of the back leaf surface treatment of emerging
Compound number | Dosage (g ai/ha) | Crop safety | |
Rape | Cotton | ||
2 | 375 | 1 | 0 |
150 | 0 | 0 | |
75 | 0 | 0 | |
3 | 375 | 1 | 0 |
150 | 0 | 0 | |
75 | 0 | 0 | |
17 | 375 | 1 | 0 |
150 | 0 | 0 | |
75 | 0 | 0 |
Claims (5)
1, a class pyrimidines is characterized in that the 2-pyrimioxybenzyl substituted phenyl amine derivatives, shown in structural formula (I):
In the structural formula (I):
D can be identical or different groups with E, is respectively hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl or
C
1-C
4Haloalkyl;
R
1Be hydrogen, C
1-C
4Alkanoyl, C
1-C
4Alkyl halide acyl group, benzoyl group or C
1-C
4The alcoxyl acetyl group;
R
2Be hydrogen, halogen, C
1-C
4Alkyl or trifluoromethyl;
R
3Be hydrogen, halogen, C
1-C
4Alkyl, trifluoromethyl, nitro or cyano group;
R
4Be hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl, C
1-C
4Carbalkoxy, trifluoromethyl, cyano group, carboxyl
Or its alkali metal salt, alkali salt, transition metal salt or organic ammonium salt;
R
5Be hydrogen or halogen;
R
6Be hydrogen, halogen or C
1-C
4Alkyl.
2, according to the described structural formula of claim 1 (I) 2-pyrimioxybenzyl substituted phenyl amine derivatives, it is characterized in that D and E are methoxyl group in the structural formula (I), or one of them is methoxyl group, another is chlorine or methyl; R
1Be hydrogen, acetyl group, chloracetyl, dichloro-acetyl, benzoyl group or methoxy acetyl group; R
2Be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl or trifluoromethyl; R
3Be hydrogen, chlorine, fluorine, methyl, trifluoromethyl, nitro or cyano group; R
4Be hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl, methoxyl group, C
1-C
4Carbalkoxy, carboxyl or its sodium salt or sylvite; R
5Be hydrogen or chlorine; R
6Be hydrogen, methyl or ethyl.
3,, it is characterized in that middle D of structural formula (I) and E are methoxyl group according to claim 1 or 2 described 2-pyrimioxybenzyl substituted phenyl amine derivatives; R
1Be hydrogen.
4, according to the preparation method of claim 1,2 or 3 described 2-pyrimioxybenzyl substituted phenyl amine derivatives, its feature such as following reaction equation are represented:
Each substituting group representative group is as described in the claim 1,2 or 3 in the reaction equation, R
1≠ H, X are halogen or methylsulfonyl.
At first by substituted aniline (3) and salicylide (4) with 1: the mol ratio of 1.0-1.2 is dissolved in the alcoholic solvent, reacted 20-60 minute in room temperature to solvent boiling point temperature range, obtain intermediate (5), get intermediate (6) after in alcoholic solvent, adding sodium borohydride or potassium borohydride reduction again, remove desolvate back and 2-halo-4,6-substituted pyrimidines or 2-methylsulfonyl-4,6-substituted pyrimidines (7), wherein 4,6 substituting groups are described D of claim 1 and E substituting group, with 1: the mol ratio of 1.0-1.1 is reacted in ether solvent He under the alkali condition, promptly makes the R shown in structural formula (1)
1The compound of=H (2), this compounds (2) further reacts in ether solvent and under alkali condition with acyl chlorides (8) again, promptly makes the R shown in structural formula (I)
1The compound of ≠ H.
5, according to the purposes of claim 1,2 or 3 described 2-pyrimioxybenzyl substituted phenyl amine derivatives, before it is characterized in that can be used for preparing crops cotton, rape and wheat paddock and preventing and kill off the bud of grassy weed, broad leaved weed and nutgrass flatsedge, post-emergence herbicide.
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CN 00130735 CN1127293C (en) | 2000-10-16 | 2000-10-16 | 2-pyrimioxybenzyl substituted phenyl amine derivatives |
CA002425984A CA2425984C (en) | 2000-10-16 | 2001-09-13 | 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their preparation processes and uses |
US10/380,865 US6800590B2 (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-n-aryl-benzylamine derivatives,their processes and uses |
JP2002537715A JP4052942B2 (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-N-arylbenzylamine derivatives, their production and use |
EP01988710A EP1327629B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
DE60131437T DE60131437T2 (en) | 2000-10-16 | 2001-09-13 | NEW 2-PYRIMIDINYLOXY-N-ARYLBENZYLAMINE DERIVATIVES, THEIR METHOD AND USES |
MXPA03001972A MXPA03001972A (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses. |
PCT/CN2001/001395 WO2002034724A1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
BR0114812-5A BR0114812A (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-n-aryl benzylamine derivatives, their preparation and use processes |
KR10-2003-7005070A KR100511489B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
AU2002220458A AU2002220458A1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
AT01988710T ATE378320T1 (en) | 2000-10-16 | 2001-09-13 | NEW 2-PYRIMIDINYLOXY-N-ARYLBENZYLAMINE DERIVATIVES, METHODS AND USES THEREOF |
PL361309A PL216218B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
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