CN1333205A - Fluoro substituted diphenylamine devirant - Google Patents
Fluoro substituted diphenylamine devirant Download PDFInfo
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- CN1333205A CN1333205A CN 00104469 CN00104469A CN1333205A CN 1333205 A CN1333205 A CN 1333205A CN 00104469 CN00104469 CN 00104469 CN 00104469 A CN00104469 A CN 00104469A CN 1333205 A CN1333205 A CN 1333205A
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- nitro
- trifluoromethyl
- chloro
- fluorine
- aniline
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Abstract
The present invention relates to a group of N-(2'-halo-6'-nitro-4'-trifluoromethylphenyl)-2,3,4,6-substituted aniline, and is characterized by that it is made of 3,4-dihalo-5-nitrotrifluomethylbenzene and 2,3,4,6-substituted aniline,and heated in the presence of acid-binding agent and solvent to make them produce reaction to obtain liquid reaction product, them making said liquid reaction product undergo the processes of water-washing, extracting, drying, distillating and recrystallizing so as to obtain the invented product. Its biological activity determination shows that its possesses higher biological activity for common injurious insects, domestic fly and pathogenic bacteria, so that it is effective active component for preparing and producing pesticide, acaricide, fungicide and sanitary chemicals.
Description
The present invention relates to the initiative of the new fluorine-containing substituted diphenylamine amine organic compound of one group of biologically active, particularly relate to one group of new N-(2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2 that has as (I) general structure, 3,4, synthetic, the biological activity determination of 6-substituted aniline derivative and as agricultural, industry and domestic hygiene with medicament.
X=Y=F, CI, Br, I or H in the formula; R
1, R
2, R
3=H, NO
2, CN, F, CI, Br, I, CF
3, OCH
3, OCF
3, COOCH
3Or C
1-C
4Alkyl.
As everyone knows, the use year after year of agricultural insecticide, miticide and sterilant, itself can develop immunity to drugs worm, mite and bacterium gradually, makes medicament lose effectiveness, and makes crop impaired.Thereby the continuous pesticide new variety of efficient, the low toxicity of research and development, low residue of agricultural chemicals circle, replace the old kind that has produced resistance, adapt to the constantly agricultural demand of development.
The inventor promptly is based on this thinking, by a large amount of experiment screenings, has obtained structural formula compound shown in (I), this is one group of fluorine-containing substituted diphenylamine aminated compounds, extensive biological activity determination by us shows, this compounds, particularly wherein contain-F ,-CI ,-CF
3,-OCF
3Has higher biological activity etc. substituent diphenylamine derivatives, and this class is fluorine-containing, in the diphenylamine derivatives of chlorine substituent, again with N-shown in (II) structural formula (2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the amino benzenes derivates that 6-replaces is active better.In this back one class, 2,2 '-two chloro-6 shown in (III) structural formula, 6 '-dinitrobenzene-4,4 '-two trifluoromethyl pentanoic then are that the first-selection that we research and develop one of is represented.
Y=F, CI, Br, I or H in the formula; R
1, R
2, R
3=H, NO
2, CN, F, CI, Br, I, CF
3, OCH
3, OCF
3, COOCH
3Or C
1-C
4Alkyl.
N-of the present invention (2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the preparation method of the aniline that 6-replaces is by 3,4-dihalo--5-nitro-trifluoromethylbenzene and 2,3,4, the aniline that 6-replaces was with mol ratio reacting by heating in the presence of acid binding agent and solvent of 1: 1.Temperature of reaction and reaction times look raw materials used kind is different with medium and change to some extent, and general temperature of reaction is controlled under the solvent refluxing temperature, and the reaction times was at 5-24 hour.Reacting available following reaction formula represents:
X=Y=F, CI, Br, I or H in the formula; R
1, R
2, R
3=H, NO
2, CN, F, CI, Br, I, CF
3, OCH
3, OCF
3, COOCH
3Or C
1-C
4Alkyl.
Suitable methyl alcohol, ethanol, propyl alcohol, benzene,toluene,xylene, ethylene glycol monomethyl ether, tetrahydrofuran (THF), dimethyl formamide, methyl-sulphoxide, acetonitrile or the oil of mirbane of being dissolved with in the reaction, wherein best with the dimethyl formamide effect.
The usage quantity of solvent, then the visual response raw material is different and different, and the common solvent consumption is controlled at 2-5 times of raw material charging capacity.
For promoting successful reaction to carry out, need to add acid binding agent in the reaction, to eliminate the HX that produces in the reaction.Acid binding agent can be a mineral alkali, also can be organic bases.The inorganic acid binding agent that is suitable for is alkali metal hydroxide, carbonate or acid carbonate, as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or sodium bicarbonate, saleratus etc.The organic acid binding agent that is suitable for is the nitrogenous organic base compound of band lone-pair electron on the nitrogen-atoms, gives repeated exhortations as triethylamine, quinoline etc.
The consumption of acid binding agent is raw material 3,4-dihalo--5-nitro trifluoromethylbenzene feed intake molar weight 1-1.3 doubly.
After reaction finishes,, extract with esters extractants such as ethyl acetate or butylacetates again through washing, reactor product enters the organic extractant phase layer, after separation is anhydrated mutually, wash with water again, thoroughly to remove remaining acid binding agent and inorganic salt, then separating obtained extraction liquid is added anhydrous sodium sulphate or calcium chloride siccative drying, fractionation by distillation is removed extraction agent and is got the solids crude product, again with the sherwood oil recrystallization or add the mixed liquid of ethyl acetate with sherwood oil and make developping agent, carry out column chromatography, promptly get highly finished product of the present invention.
By the made N-of the inventive method (2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the aniline highly finished product that 6-replaces, be made into 5% missible oil with acetone and emulsifying agent, with pickling process commonly used in the biological activity determination, the Potter spray method, dipping feeding method and topical application, to common insect on the agricultural, as bollworm, mythimna separata, Nilaparvata lugen (brown planthopper), worm such as two-spotted spider mite and citrus red mite (crm), mite and rice sheath blight disease, germs such as sclerotinia rot of colza and sanitary insect pest housefly carry out biological activity determination, show that product of the present invention is to these agriculture common worms, mite, bacterium etc. all show very high biological activity, be that agricultural insecticide is produced in preparation, miticide, the effective active component of sterilant and domestic hygiene medication, the formula technique that available pesticide industry is commonly used, be mixed with various preparations, comprise pulvis, granule, finish, emulsion, aqueous suspension or microcapsule etc., also can carry out composite with the agricultural chemicals of other kind, to enlarge use range and result of use, be widely used in agricultural insecticide, miticide and sterilant also can be used for domestic hygiene sterilant and industrial sterilant.
N-of the present invention (2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the aniline that 6-replaces is the new compound of end discovery still in the existing document, manufacture method is simple and easy to do, have very high biological activity, have good development prospect aspect agricultural, industry and the domestic hygiene medication.
For illustrating the present invention more specifically, enumerate specific examples below.
Embodiment 12,2 '-two chloro-6,6 '-dinitrobenzene-4,4 '-two trifluoromethyl pentanoic
Thermometer is being housed, in the 100ml reaction flask of agitator and reflux condensing tube, add 5.2 gram (0.02 moles) 3,4-two chloro-5-nitro-trifluoromethyl toluenes, 4.81 gram (0.02 mole) 2-chloro-6-nitro-4-5-trifluoromethylaniline, 50 milliliters of dimethyl formamides, 82% potassium hydroxide 1.64 grams (0.024 mole), reflux 8 hours, reaction solution poured in 200 ml waters stir, with 200 milliliters of ethyl acetate extractions, behind the standing demix, separate and remove lower aqueous layer, use 200 milliliters of moisture secondary washing extraction liquids again, after water layer is removed in separation, add 30 gram anhydrous sodium sulfate dryings, distillation, remove extraction agent, product was with 9: 1 sherwood oil: ethyl acetate developping agent column chromatography, yellow solid product 4 grams, 114.2 ℃-114.7 ℃ of fusing points, yield 43.1%, product and through nucleus magnetic resonance (1HNMR), ultimate analysis and mass spectrum (MS) are analyzed with conclusive evidence.Analytical results is as follows: 1HNMR (TMS, CDCl
3, δ
Ppm):
7.855，7.857，7.860，7.861(q，2H)；8.312，8.314，
8.315,8.317,8.319 (m, 2H); 9.954 (s, 1H) ultimate analysis C
14H
5Cl
2F
6N
4O
6=464
Calculated value %C36.20H1.08 N9.05
Measured value %C36.31H1.12 N8.97 MS 463M
+
The biological activity determination of product:
With above-mentioned prepared 2,2 '-two chloro-6,6 '-dinitrobenzene-4,4 '-two trifluoromethyl pentanoic, be made into 5% missible oil with acetone and tween-80 emulsifying agent, carry out biological activity determination, test target, method and result are as follows: [1] exemplifies cotton mite and citrus red mite (crm) to the biological activity of mite class.
Cotton one-tenth mite: bottle is inserted leaf dipping method.LC
50Be 0.36～0.33mg/L; LC
90Be 0.89～1.02mg/L;
Cotton children (if) mite: the Potter spray method.LD
50Be 0.0058～0.0068 μ ga.i./cm
2LD
90Be 0.0202～0.0305 μ g a.i./cm
2
Cotton ovum hatching inhibiting rate: Potter spray method.LD
50Be 0.0190～0.0203 μ g a.i./cm
2LD
90Be 0.0390～0.0447 μ g a.i./cm
2
Citrus red mite (crm) becomes mite: bottle is inserted leaf dipping method.LC
50Be 0.1747～0.2069mg/L; LC
90Be 0.4077～0.5401mg/L.[2], exemplify mythimna separata and bollworm to the biological activity of lepidopteran class.
Mythimna separata 3 instar larvaes: dipping feeding method.LC
50Be 8.24mg/L; LC
90Be 15.68mg/L.
Bollworm 3 instar larvaes: topical application.LC
50Be 4.7mg/L.[3] to the biological activity of plant hopper, exemplify Nilaparvata lugen (brown planthopper).
Nilaparvata lugen (brown planthopper) nymph in 3 age: potted plant rice seedling spray method.LC
50Be 10.66mg/L; LC
90Be 39.23mg/L.[4] to the biological activity of Phytophthira, exemplify aphis craccivora.
Aphis craccivora becomes aphid: pickling process.Concentration is 250mg/L, and mortality ratio is greater than 90%.[5] to the biological activity of fly class, exemplify housefly.
Housefly becomes fly: spray method.Concentration is 200mg/L, and mortality ratio is greater than 90%.[6] fungicidal activity exemplifies Rhizoctonia solani Kuhn.
Rhizoctonia solani Kuhn: potted plant rice seedling bacterination process.Concentration is 1000mg/L, and preventive effect is 100%.
Embodiment 2
Except that the 2-chloro-6-nitro-4-5-trifluoromethylaniline in embodiment 1 preparation being changed in the table 1 the corresponding substituted aniline of structural formula, other all prepares by embodiment 1 operation, and accordingly result is as shown in table 1.For making comparisons, example 1 product is also listed in wherein.
Table 1
Claims (14)
1. one group of fluorine-containing substituted diphenylamine aminated compounds is characterized in that N-shown in structural formula (I) (2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the aniline that 6-replaces:
X=Y=F, CI, Br, I or H in the formula; R
1, R
2, R
3=H, NO
2, CN, F, CI, Br, I, CF
3, OCH
3, OCF
3, COOCH
3Or C
1-C
4Alkyl.
2. fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 is characterized in that N-shown in structural formula (II) (2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the aniline that 6-replaces:
Y=F, CI, Br, I or H in the formula; R
1, R
2, R
3=H, NO
2, CN, F, CI, Br, I, CF
3, OCH
3, OCF
3, COOCH
3Or C
1-C
4Alkyl.
3. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to 2,2 '-two chloro-6,6 '-dinitrobenzene-4,4 '-two trifluoromethyl pentanoic.
4. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2-methyl-4-N-methyl-p-nitroaniline.
5. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2-methyl-4-chloroaniline.
6. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2-methyl-formiate base aniline.
7. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-3-5-trifluoromethylaniline.
8. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-4-cyano-aniline.
9. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 ,-chloro-6 '-nitro-4 '-trifluoromethyl)-4-Iodoaniline.
10. a fluorine-containing substituted diphenylamine aminated compounds as claimed in claim 1 or 2 is characterized in that referring to N-(2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-3-fluoroaniline.
A 11. N-as claimed in claim 1 (2 '-chloro-6 '-nitro-4 '-trifluoromethyl)-2,3,4, the preparation method of the aniline that 6-replaces is characterized in that by 3 4-dihalo--5-nitro trifluoromethylbenzene and 2,3,4, aniline reacting by heating in the presence of acid binding agent and solvent that 6-replaces, reaction solution is through washing, the esters extractant extraction, the siccative drying, extraction agent is removed in distillation, and the sherwood oil recrystallization makes.
12. preparation method as claimed in claim 11, it is characterized in that by 3,4-two chloro-5-nitro trifluoromethylbenzenes and 2,3,4, aniline reacting by heating in the presence of acid binding agent and solvent that 6-replaces, reaction solution is through washing, and esters extractant extracts, the siccative drying, extraction agent is removed in distillation, and the sherwood oil recrystallization makes.
13. one kind as preparation method as described in claim 11 or 12, it is characterized in that reaction is methyl alcohol, ethanol, propyl alcohol, benzene,toluene,xylene, ethylene glycol monomethyl ether, tetrahydrofuran (THF), dimethyl formamide, methyl-sulphoxide, acetonitrile or oil of mirbane with solvent; Reaction is the organic compound of alkali metal hydroxide, carbonate, acid carbonate or band lone-pair electron with acid binding agent.Used esters extractant is ethyl acetate, butylacetate; Used siccative is anhydrous sodium sulphate or calcium chloride.
14. N-(2 '-halogen-6 '-nitro-4 '-trifluoromethyl)-2 according to claim 1,3,4, the aniline that 6-replaces, it is characterized in that it is mixed with pulvis, granule, finish, aqueous suspension, emulsion, microcapsule as active constituent, or with other kind agricultural chemicals carry out composite, as agricultural insecticide, miticide, sterilant, domestic hygiene sterilant and industrial sterilant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104469 CN1184191C (en) | 2000-07-10 | 2000-07-10 | Fluoro substituted diphenylamine devirant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104469 CN1184191C (en) | 2000-07-10 | 2000-07-10 | Fluoro substituted diphenylamine devirant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1333205A true CN1333205A (en) | 2002-01-30 |
| CN1184191C CN1184191C (en) | 2005-01-12 |
Family
ID=4577344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00104469 Expired - Fee Related CN1184191C (en) | 2000-07-10 | 2000-07-10 | Fluoro substituted diphenylamine devirant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184191C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199095A (en) * | 2010-03-22 | 2011-09-28 | 中国中化股份有限公司 | Substituted diphenylamine compounds and preparation and application thereof |
| EP2826474A1 (en) * | 2012-03-14 | 2015-01-21 | Sinochem Corporation | Use of substituted diphenylamine compounds in preparing anti-tumour drugs |
-
2000
- 2000-07-10 CN CN 00104469 patent/CN1184191C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199095A (en) * | 2010-03-22 | 2011-09-28 | 中国中化股份有限公司 | Substituted diphenylamine compounds and preparation and application thereof |
| WO2011116671A1 (en) * | 2010-03-22 | 2011-09-29 | 中国中化股份有限公司 | Substituted diphenylamine compounds, preparation method and use thereof |
| CN102762530A (en) * | 2010-03-22 | 2012-10-31 | 中国中化股份有限公司 | Substituted diphenylamine compounds, preparation method and use thereof |
| CN102199095B (en) * | 2010-03-22 | 2014-04-09 | 中国中化股份有限公司 | Substituted diphenylamine compounds and preparation and application thereof |
| CN102762530B (en) * | 2010-03-22 | 2014-07-02 | 中国中化股份有限公司 | Substituted diphenylamine compounds, preparation method and use thereof |
| US9061967B2 (en) | 2010-03-22 | 2015-06-23 | Shenyang Research Institute Of Chemical Industry Co., Ltd. | Substituted diphenylamine compounds, preparation method and use thereof |
| EP2826474A1 (en) * | 2012-03-14 | 2015-01-21 | Sinochem Corporation | Use of substituted diphenylamine compounds in preparing anti-tumour drugs |
| EP2826474A4 (en) * | 2012-03-14 | 2015-04-08 | Sinochem Corp | Use of substituted diphenylamine compounds in preparing anti-tumour drugs |
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| Publication number | Publication date |
|---|---|
| CN1184191C (en) | 2005-01-12 |
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Assignee: ZHEJIANG HETIAN CHEMICAL Co.,Ltd. Assignor: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd. Contract record no.: 2011330000800 Denomination of invention: Fluorinated substituted two aniline derivatives Granted publication date: 20050112 License type: Exclusive License Open date: 20020130 Record date: 20110624 |
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