CN1125509A - Plant-growth regulationg agent (shuangxiaosu) and its preparation - Google Patents
Plant-growth regulationg agent (shuangxiaosu) and its preparation Download PDFInfo
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Abstract
The chemical compound or its salt, whose structural formula is shown in its patent specification, may be used as plant growth regulator or phytocide. Its preparing process and usage are disclosed.
Description
The present invention relates to the compound of coordinate plant growth and control weed growth, its Preparation method and use.
In a European patent 0059226 in 1981, disclose two, three and four replacement N-nitroanilins and its inorganic and organic salt and can promote blooming of ornamental plants, cereal crop, legume crop, cotton and sunflower, increase the armpit branch and improve tree crown, these salt are the dose of crop yield and the co-inhibitor of lodging, its energy formula (I) and (Ia) as follows:
In this patent documentation, mention the R in two general formulas especially
7Be meant hydrogen, C
1-C
12Optical activity alkyl with halogen atom or cyano group (CN), C
3-C
4Alkylene, C
3-C
4The alkynes base, low-grade carboxylic acid's methyl esters or benzene alkyl (
N is 0,1,2, or 3) and substituted benzene alkyl, obviously, R
7Do not refer to any acyl group; Simultaneously, this patent is pointed out, works as n=0, R
7, R
3, R
5During=H, general formula I can form inorganic or organic salt, and these salt can be used general formula (II) expression:
X
+Be alkali metal ion, or a kind of quaternary ammonium ion, can represent by general formula (IIIa):
N
+RaRbRcRd(IIIa)
This patent has an additional restrictions for the 5th page, that is: when general formula I n a) be zero, R
3And R
5All be hydrogen, R
2, R
4And R
6When being the former grade of halogen substituting group, X
+Do not comprise the alkali metal ammonium, uncle's ammonium (H
3N
+Rd), secondary ammonium (H
2N
+RaRb) tertiary amine (HNRaRbRc) and quaternary ammonium (NRaRbRcRd), each is C for Ra-Rd
1-C
12Alkyl, C
2-C
4Hydroxyalkyl etc.Also can not be any two heterocyclic quaternary ammonium ions that are combined into ring among the Ra-Rd, as
On more widely used plant growth regulator at present, mainly be 1, (domestic popular name helps strong plain 1-lupetidine drone chloride, and mepiquat chloride is regulated pyridine, english abbreviation: DMPC) belong to the quaternary growth inhibitor, use on cotton and have physiologically active preferably, its shortcoming is influential to the fiber quality of cotton, and this compound effect on paddy rice is not good simultaneously, another kind of is widely used paclobutrazol on paddy rice, (or claims PP
333), its chemical name is: 1-(4-chlorphenyl)-4,4-dimethyl-2-(1,2, the 4-triazol-1-yl)-penta-3-alcohol belong to the triazole type plant growth inhibitor, but this compound result of use on cotton is not good.
Task of the present invention is synthetic a kind of new compound that had not only had coordinate plant growth but also can control weed growth, its synthetic method and unifacial leaf and dicotyledon had the purposes of broad spectrum activity.
The present invention is achieved in that a kind of compound with coordinate plant growth and tool herbicidal activity, and this compound belongs to the compound or its salt that has N-nitroanilin, and (I) is as follows for its general formula:
Wherein: R can be the aromatic series sulfonyl
, Ar wherein
-Can be phenyl or substituted-phenyl, or naphthyl and substituted naphthyl), also can be the aliphatic sulfonyl
R wherein
4Be C
1-C
2Alkyl or substituted alkyl), also can be alicyclic sulfonyl (R is six carbon or five carbocyclic rings), also can be the heterocycle sulfonyl that contains a nitrogen heteroatom, or the thioesters acyl group
R wherein
5 -Can be
C
1-C
8Straight chained alkyl or phenyl or substituted-phenyl); R represents the heterocycle sulfonyl, and its general formula is
R wherein
6Such as claim 1 definition.
R can be carbamoyl or substituted-amino formoxyl, and its general formula is
R wherein
7And R
8Can be hydrogen, or C
1-C
4Various alkyl or substituted alkyl also can be phenyl or substituted-phenyl, R
7And R
8Can be identical also can be different, R
7And R
8Also can be combined into 5-membered heterocycles or six element heterocycles and amino substituent thereof.
R can be phosphide acyl group or sulfo-phosphide acyl group, as
The same R of definition
7And R
8, the substituting group of substituted alkyl and substituted-phenyl comprises halogen atom, amino, nitro, hydroxyl, methoxyl group, carboxyl, ester group (COOR
10) sulfonic group or sulfonate group (SO
2R
11), the substituting group on the substituted-phenyl also comprises C
1-C
4Alkyl and haloalkyl, R
10And R
11Be C
1-C
2Alkyl;
R can be C
1-C
10Carboxylic acyl radical or its substituted acyl, its substituting group comprises halogen atom, carboxyl or amino, also can be benzene alkanoic acid acyl group (
N is 0,1,2 or 3) and, replace the benzoic acid acyl group, or contain the heterocyclic carboxylic acid acyl group of a nitrogen heteroatom);
When R is above various acyl group, R
1, R
2, R
3Can be hydrogen or halogen atom, R
1, R
2, R
3Can all be halogen atom, perhaps wherein two or one be halogen atom.If fluorine is arranged, no more than one; Perhaps one of them is C
1-C
4Alkyl or substituted alkyl, hydroxyl, methoxyl group, nitro, amino or substituted-amino or amide groups
, sulfonic group, sulfonate group, carboxyl or ester group, R
12With R
8Define identical; Its general formula (II) is:
The present invention also comprises N-nitro-2,4, and 6-trichloroaniline sodium salt is as chlorination N, the N-lupetidine drone (help strong plain, the casing coupling ammonium) and the synergist of chlorination 2-ethyl trimethyl ammonium chloride (chlormequat CCC) use, mixed proportion (mol ratio) is 0.1-1: 1, best proportioning is 1: 1.
Wherein work as R
1, R
2, R
3All be chlorine, R
+Be N, N-lupetidine drone
The present invention further specifies by the following technical programs:
2,4, the preparation of 6-trichloroaniline (intermediate):
(1) reaction such as the halo of aniline, sulphur generation, nitre generation, alkyl generation, carboxyl generation, amino generation, hydroxyl generation is undertaken by the historical document method.
(2) the nitration method on the amino: patent documentation US.4643755 method is that substituted aniline is dissolved in the glacial acetic acid, drip 90% nitric acid after, drip acetic anhydride again, the productive rate of N-nitro substituted aniline only 38%.
The method of preparation of the present invention (intermediate) is:
(1), makes the nitryl acetic anhydride with fuming nitric aicd and acetic anhydride;
(2) substituted aniline is dissolved in the glacial acetic acid, makes the substituted aniline acetum;
(3) the nitric acid acetic anhydride is added drop-wise in the substituted aniline acetum;
(4) treat that (3) step reaction is finished after, add absolute ethyl alcohol (or methyl alcohol), destroy excessive nitric acid acetic anhydride, it is transformed into ethyl nitrate and glacial acetic acid, recovered under reduced pressure ethyl nitrate or glacial acetic acid.
The productive rate of the N-nitro substituted benzene of this method preparation can reach more than 80%.
(5) its each reaction is as follows:
(1) N-nitration reaction:
(2) esterification:
(3) salt-forming reaction:
In organic solvent, and there is acid binding agent to exist, allows N-nitro substituted aniline and quaternary amine or alkali metal and alkaline earth metal hydroxide react.Its reaction equation is:
In the formula: R
+Be the quaternary amine ion, alkali metal and alkaline-earth metal ions, h
-Be OH
-Or X
-(Cl
-, Br
-), n is 1,2.This acid binding agent is trimethylamine, acetate or carbonate.Organic solvent is meant carbon tetrachloride, chloroform, C
1-C
4Saturated monohydroxy alcohol, C
2-C
4Saturated monocarboxylic acid and C
1-C
5Ester, acetone that saturated monohydroxy alcohol generates.
(4) N-acylation reaction:
(1) N-sulfonylation:
In organic solvent, when acid binding agent exists, N-nitro substituted aniline and sulfonic acid chloride reaction, reaction equation is:
In the formula: the definition that the definition of R such as specification are given, wherein the implication of organic solvent and acid binding agent is also with aforementioned.Organic solvent also comprises benzinum (60-90 ℃), benzene, vinylbenzene, oxolane, N, dinethylformamide and ether in addition.
(2) N-carbamylization:
With N-nitro substituted aniline and phosgene reaction, growth N-nitro-N-chloroformyl substituted aniline, the latter generates product with various primary amine or secondary amine reaction again.Its reaction equation:
In the formula: R
7, R
6Definition such as specification in the definition of being given.
(3) N-phosphide (or sulfo-phosphide) acylation reaction:
In organic solvent, when acid binding agent exists, N-nitro substituted aniline and phosphide (sulfo-phosphide) acyl chloride reaction, or behind primary amine (aliphatic) or amino-acid ester and phosphide (sulfo-phosphide) acyl chloride reaction, carry out the N-nitration reaction again, its reaction equation:
R
13-NH
2Represent fat primary amine and amino acid and ester thereof or fat primary amine or amino acid and ester thereof and phosgene reaction to generate isocyanates, again with fatty primary secondary amine or aromatic secondary amine generation addition reaction after, carry out the N-nitration reaction again
R
14, R
15Table C
1-C
4Aliphatic group or phenyl and substituted-phenyl.
Preparation is (embodiment) for example:
Synthesizing of example 1:N-nitro-2,4,6-dg chloroaniline
(1) raw material and proportioning
The material name molal quantity
2,4,6-trichloroaniline 1
Glacial acetic acid 5.2
Acetic anhydride 1.63
Fuming nitric aicd 1.57
Methyl alcohol 1.18
The consumption of raw material can be by increasing with equimultiple.
(2) in proportion fuming nitric aicd is added drop-wise in the acetic anhydride that cools off with ice-water bath, generates acetyl nitric acid, be stored in the storage tank standby;
(3) in proportion trichloroaniline is added in the glacial acetic acid, drip again,, after having reacted, drip methyl alcohol, stir about 30 minutes with the frozen water cooling in acetyl nitric acid.The pressure reducing and steaming ethyl nitrate, ethyl acetate reclaims glacial acetic acid.After the residue cooling, add frozen water, stir, filter, wash 1-2 time, drain with frozen water, solids dissolves with 5%NaOH, the elimination residue, and filtrate is neutralized to PH=4 with 2N hydrochloric acid, promptly there are a large amount of N-nitrotrimethylolmethane hydrogen aniline to separate out, filter, wash with frozen water, suction filtration is to doing, oven dry (about 80 ℃) promptly gets product, and productive rate is more than 80%.
Synthesizing of example 2:N-nitro-N-benzenesulfonyl first-2,4,6-trichloroaniline,
Add a certain amount of benzene sulfonyl chloride in the diethyl ether solution of N-nitrotrimethylolmethane chloroaniline, the cold bath cooling slowly drips triethylamine, stirring reaction 2 hours, filter, wash product, productive rate is 42%.Acetone-ethyl alcohol recrystallization gets pure product.
Synthesizing of example 3:N-nitro-N-methylamino formyl-2,4,6-trichloroaniline
N-nitro-2,4,6-trichloroaniline are dissolved in the toluene, under cryogenic conditions (below 10 ℃), fed phosgene 3-4 hour, placement is spent the night, and methylamine is fed in the reactant mixture, and distillation is reclaimed toluene and got product.
Synthesizing of example 4:N-nitro-N-benzyl-2,4,6-trichloroaniline
Drip benzyl chloride in the dimethyl sulfone solution of a certain amount of N-nitro-trichloroaniline, stirring reaction is 16 hours under the normal temperature, then reactant mixture is poured in the cold water into extracted by ether.Ether
Subordinate list 1: He Cheng several plant growth regulator (economic benefits and social benefits element) as stated above
Structural formula, fusing point and elementary analysis
Subordinate list 2: the plant growth regulator (economic benefits and social benefits element) that other several embodiment of the present invention synthesize
Compound title, structural formula and fusing point analysis
Solution is water, rare NaOH, water washing respectively, uses anhydrous MgSO again
4Dry.Boil off ether, get salmon liquid, place, separate out crystalline product, productive rate 41%.With absolute ethyl alcohol be recrystallized pure product.
Synthesizing of example 5:N-nitro-2,4,6 trichloroanilines-N '-(2-chloroethyl) leptodactyline
A certain amount of N nitro-trichloroaniline sodium salt and 2-chloroethyl trimethyl ammonium chloride are dissolved in respectively in an amount of ethanol, mix stirring reaction a period of time, boil off ethanol, the solid acetone solution, the elimination insoluble matter, steam acetone and get product, productive rate is more than 95%, can be further with absolute ethyl alcohol be recrystallized pure product.
Example 6:N-nitro-2,4,6-trichloroaniline-N ', synthetic (the economic benefits and social benefits element 6) of N '-lupetidin drone salt
(1) drip the 10-30%NaOH aqueous solution in the chloroformic solution of N-nitro-trichloroaniline, wait to precipitate complete back suction filtration, with water saturated chloroformic solution washed solid, suction filtration gets N-nitrotrimethylolmethane chloroaniline sodium to doing.Reaction can quantitatively be carried out.
(2) with N-nitro-trichloroaniline sodium-N, N '-lupetidin drone chloride is dissolved in respectively in the ethanol, mixes in molar ratio, removes by filter precipitation, and ethanol is reclaimed in distillation, gets product, productive rate 100%.
The compound of other embodiments of the invention and analyze data and see attached list 1 and subordinate list 2:
The N-nitro that the present invention synthesizes-N-acyl group-trisubstituted benzene amine and N-nitro-trisubstituted benzene amine salt (the plain row of economic benefits and social benefits), its formulation comprises aqua, crystal, wetting powder and emulsion, also can be other formulation.
Following animal acute toxicity test result can prove the safety of compound of the present invention or its property better.
" the chemistry security toxicological evaluation program " of issuing the city according to ecotoxicology teaching and research room of Chinese Wuhan Tongji Medical Univ. according to Ministry of Health of the People's Republic of China sees Table 3 to the plain acute toxicity evaluation result of economic benefits and social benefits:
Table 3: the plain The acute toxicity tests of economic benefits and social benefits
| Laboratory animal | Route of exposure | Sex | LD50 and 95% can sex-limited (milligram/kg body weight) |
| Big white mouse | Per os | Male and female | 1710(1260-2330) 1260(926-1710) |
| Big white mouse | Through skin | Male and female | ??＞2500 ??＞2500 |
| Big white mouse | Per os | Male and female | 3690(2710-5010) 2710(2000-3690) |
This part acute toxicity experience evaluation conclusion is thought:
1, the plain II of economic benefits and social benefits is to female, and white mouse median lethal dose great and mighty or powerful (LD50) is respectively 1710 (1260-2330) and 1260 (926-1710) mg/Kg body weight
2, the plain II of economic benefits and social benefits is to female, and white mouse per os median lethal dose great and mighty or powerful is respectively 3690 (2710-5010) and 2710 (2000-3690) mg/Kg body weight
3, the plain II of economic benefits and social benefits is to female, and white mouse great and mighty or powerful is distinguished (LD50) all greater than the 2500mg/Kg body weight through the skin median lethal dose
4, eyes mucomembranous irritant test result: under not flushing situation for the moderate excitant is arranged.
According to the toxicity grading standard, the plain II of economic benefits and social benefits belongs to the low toxicity level compound.
Above-mentioned synthetic compound or its salt can be widely used in unifacial leaf or dicotyledon, for example on the chemical regulation of paddy rice, cotton, barley, wheat, rape, fruit tree, peach and vegetables and ornamental plants, and also in the application of useful as herbicides,
Effect is given an example:
(1) application of economic benefits and social benefits element on paddy rice
The noval chemical compound that the present invention synthesizes (being example with " economic benefits and social benefits element " for sake of convenience, down together) can be applicable to early rice, semilate rice and late rice.1 leaf 1 heart-2 leaf, 2 hearts) and the period of seedling establishment foliage-spray administrated method comprises seed soaking, foliage-spray (seedling stage:.With concentration be: seed soaking is 25-50ppm (and synthetic N-nitro-2,4,6-tribromaniline and its esters medication concentration of conventional method is generally more than the 500ppm, this medicine can reduce by 10 times of usefulness concentrations) with the economic benefits and social benefits element.Method is that seed was soaked two days with clear water earlier, uses economic benefits and social benefits cellulose solution immersion treatment one day again.The rice leaf that is used for seedling stage and period of seedling establishment sprays, and is 100-500ppm with concentration.Paddy rice only need select one of above-mentioned three application methods or period to get final product.The economic benefits and social benefits element shows the physiologically active of following several respects on paddy rice:
(1) promotes seed to sprout, make early rice and late rice and late rice percentage of seedgermination improve 6.66-9.66% and 21.67-23.33% respectively.
(2) strengthen seedling quality, it is wide to show as stem foot, and white root, fresh weight, dry weight and unit height of seedling dry weight all increase, and plant height is not had obvious influence.
(3) enhancing is tillered.The processing in three medication periods all can strengthen tillers, and reaches 5% significance level.Early rice sprays medicine seedling stage and late rice period of seedling establishment spray medicine can also be eared 1-2 days ahead of time.
(4) increase effective fringe, real grain number and ripening rate are to the no evident regularity of thousand kernel weight influence.
(5) obvious effect of increasing production.Early rice on average increases production 8.66%, late rice volume increase 12.66%, and semilate rice on average increases production 12.32%.Average mu increases paddy 30-50 kilogram.
(2) application of economic benefits and social benefits element on cotton
The initial bloom stage of cotton to the plain 50-100ppm of full-bloom stage foliage-spray economic benefits and social benefits once, or same concentration in initial bloom stage and each spray of full-bloom stage once deepens the cotton leaf look, chlorophyll content increases, the dark 0.5-0.85 level of the leaf color ratio contrast (clear water) of functional leaf; The short 3.5-12.5cm of cotton plant aspect ratio concurrent control; Flower bud, flower, one-tenth peach number increase, the expulsion rate comparison is according to reducing 6.69-7.09%, the comparison of individual plant peach number is according to increasing 0.3-2.7/strain, Dan Lingchong contrast increase the 0.05-0.15 gram/, the seed cotton yield comparison is according to (clear water) volume increase 16.03-25.58 kilogram/mu, volume increase 9.14-14.58% helps strong plain (1.1-lupetidin drone chloride) volume increase 7.91-13.48%.After using the economic benefits and social benefits element, fibre length of cotton and fineness increase, and the fiber integrated quality is better than contrast (clear water) and helps strong element, and its effect is seen attached list shown in 3:
Table four: the different chemical conditioning agent is to the influence of cotton fiber quality
(1992. Hubei, Wuhan)
| Handle | 9000 series of tests results | ||||
| 2.5% span length | Fibre uniformity | Specific strength | Tensile stretch | Mic value | |
| The economic benefits and social benefits element | 29.4mm | 48.6 | ????22.7 | ????7.3 | ?5.2 |
| Help strong plain | 27.0mm | 46.9 | ????18.5 | ????5.6 | ?5.3 |
| CK (clear water) | 28.5mm | 49.5 | ????22.9 | ????7.4 | ?5.3 |
(3) application of economic benefits and social benefits element on wheat
Before jointing, successively spray the 50-100ppm economic benefits and social benefits plain three times at wheat tillering, comparison increases 29.62-20.62Kg according to (clear water) mu, volume increase 15.7%-10.93%, and difference all reaches utmost point significance level.Its volume increase reason is to increase in early days to tiller, and wheat is tillered in early days, and majority can form big fringe, and small ear is many, and seed is heavy.The plain wheat of handling of economic benefits and social benefits, many 6.87 of number of grain per ear average specific contrast, many 1.98 grams of thousand kernel weight.
(4) application of economic benefits and social benefits element on rape
Behind the rape transplant survival. successively spray the plain 100ppm of economic benefits and social benefits totally three times, establish the strong plain 100ppm of helping of spray same number and be contrast.The result shows that the economic benefits and social benefits element is handled comparison and increased 21.35Kg according to (clear water) mu, increases production 11.19%, than helping the strong plain mu of handling to increase 7.81Kg, increases production 3.82%.The main cause of its volume increase is that the greenery number is increased, and comparison is according to many 0.4-2.37 sheet, and the leaf look is deepened.Promote plant branch early estranged, individual plant angle fruit number is compared according to many 75.06/strains, many 0.11 grams of thousand kernel weight.
(5) application of economic benefits and social benefits element on the peach chemical trim
In early spring, when peach clip bud branch grows to 2-3 sheet leaf, spray four processing of economic benefits and social benefits element 100,200,500 and 100ppm, compare with the spray clear water.Result of the test shows, plain four concentration of economic benefits and social benefits are handled all has significant inhibitory effect to the peach shoot growth, and the growth rate comparison illumination of young sprout shows slow, and the shoot growth amount is all than the few 19.87%-53.3% of contrast, the branch internode shortens, and can play the effect of chemical trim.
(6) activity of weeding of economic benefits and social benefits element test
When wheat and soybean seed show money or valuables one carries unintentionally, do soil treatment with the economic benefits and social benefits element respectively, measure the fresh weight of respectively handling seedling after 20 days, obtain the fresh weight inhibiting rate, the results list 5.
Table five economic benefits and social benefits element is to the fresh weight inhibiting rate (%) of wheat and soybean seedling
| Beans | Economic benefits and social benefits element 5 | ????-18.96 | ?3.33 | ??46.21 | ??90.22 | ??100.0 |
| Cotton | Economic benefits and social benefits element 7 | ????-6.38 | ?2.44 | ??26.38 | ??43.57 | ??58.35 |
| Economic benefits and social benefits element 10 | ????15.52 | ?17.96 | ??44.27 | ??73.50 | ??100.0 | |
| Wheat | Economic benefits and social benefits element 7 | ????6.63 | ?8.17 | ??8.75 | ??13.30 | ??44.47 |
| Economic benefits and social benefits element 10 | ????1.96 | ?7.16 | ??31.04 | ??55.38 | ??76.51 |
The influence that the economic benefits and social benefits element is grown several weed growths, blade face spray in seedling stage medicine, 20 days " Invest, Then Investigate "s are cut the bright seedling of acrial part, claim fresh weight, calculate inhibiting rate %, the results list 6.
Table 6 economic benefits and social benefits element is to the preventive effect of several weeds
| Compound | The plain 7 economic benefits and social benefits elements 9 of plain 5 economic benefits and social benefits of plain 3 economic benefits and social benefits of economic benefits and social benefits | ||||
| Weeds | Concentration ppm | Acrial part fresh weight inhibiting rate % | |||
| Hard grass | ?500 | ????64.74 | ????17.30 | ||
| ?1000 | ????100.0 | ????45.48 | |||
| Amur foxtail | ?500 | ????40.24 | ????26.09 | ||
| ?1000 | ????100.0 | ????52.90 | |||
| The barnyard grass grass | ?250 | ????50.63 | ?45.54 | ||
| ?500 | ????84.30 | ?79.62 | |||
| ?1000 | ????98.53 | ?97.27 | |||
Claims (11)
1, the compound of coordinate plant growth and weeding is characterized in that this compound or its salt contains array structure down, and its general formula I is:
Wherein: R can be the aromatic series sulfonyl, aliphatic sulfonyl, or alicyclic sulfonyl; Also can be the heterocycle sulfonyl that contains a nitrogen heteroatom, or the thioesters acyl group;
R can be carbamoyl or substituted-amino formoxyl;
R can be phosphide acyl group or sulfo-phosphide acyl group.The substituting group of substituted alkyl and substituted-phenyl comprises halogen atom, amino, nitro, hydroxyl, methoxyl group, carboxyl, ester group (COOR
10) sulfonic group or sulfonate group (SO
2R
11), the substituting group on the substituted-phenyl also comprises C
1-C
4Alkyl and haloalkyl; R wherein
10And R
11Be C
1-C
2Alkyl;
R can be C
1-C
10Carboxylic acyl radical or its substituted acyl, its substituting group comprises halogen atom, carboxyl or amino, also can be benzoic acid acyl group or replacement benzoic acid acyl group, or contains the heterocyclic carboxylic acid acyl group of a nitrogen heteroatom;
When R is above various acyl group, R
1, R
2, R
3Can be hydrogen or halogen atom, R
1, R
2And R
3Can all be halogen atom or wherein two or one be halogen atom, perhaps one of them is C
1-C
4Alkyl or substituted alkyl, hydroxyl, methoxyl group, nitro, amino or substituted-amino, amide groups, sulfonic group, sulfonate group, carboxyl or ester group:
Its general formula (II) is:
Wherein work as R
1, R
2, R
3All be chlorine, R
+Be N, the N-lupetidine drone.
2, compound or its salt as claimed in claim 1 is characterized in that, in the general formula I, its general formula of aromatic series sulfonyl of R representative is:
Ar wherein
-Can be the aliphatic sulfonyl of phenyl, substituted-phenyl, naphthyl or substituted naphthyl: R representative, its general formula be:
R wherein
4Be C
1-C
2Alkyl or substituted alkyl, the thioesters acyl group of R representative, its general formula is
R wherein
5 -Can be C
1-C
8Straight chained alkyl, phenyl or substituted-phenyl; The heterocycle sulfonyl of R representative, its general formula is
R wherein
6Claim 1 defines.
3, generation as claimed in claim 1 compound or its salt, it is characterized in that, the carbamoyl or the substituted-amino formoxyl of R representative, its general formula is:
R wherein
7And R
8Can be hydrogen, C
1-C
4Various alkyl, substituted alkyl also can be phenyl, substituted-phenyl, R
7And R
8Can be identical, also can be different, R
7And R
6Can be combined into 5-membered heterocycles or six element heterocycles and amino substituent thereof.
4, as the compound or its salt of claim 1 or 3, it is characterized in that, the phosphide acyl group or the sulfo-phosphide acyl group of R representative, its general formula is
R wherein
9The same R of definition
7And R
8
5, as the compound or its salt of claim 1 or 4, wherein its general formula of benzene carboxylic acid acyl group of R representative is
N wherein is 0,1,2 or 3.
6, compound or its salt as claimed in claim 5 is characterized in that, works as R
1, R
2, R
3One of the representative amino or substituted-amino, its general formula is R
10NH-, wherein R
10Can be C
1-C
2Alkyl, its general formula of amide groups of R representative is
R wherein
11With R
10Definition identical.
7, compound or its salt as claimed in claim 1 is characterized in that, the salt of general formula (II) representative is worked as R
1, R
2, R
3All be chlorine, R
+Be Na
+This compound can be as chlorination N, the N-lupetidine drone (help strong plain casing coupling ammonium, DMPC) and the synergist of chlorination 2-ethyl trimethyl ammonium chloride (chlormequat) use, mixed proportion (mol ratio) is 0.1-1: 1, best proportioning is 1: 1.
8, the method for the compound or its salt of preparation claim 1 is characterized in that, preparation intermediate N nitro-2,4, and the step of 6-trichloroaniline is:
(a), make the nitryl acetic anhydride with fuming nitric aicd and acetic anhydride; Then
(b) substituted aniline is dissolved in the glacial acetic acid, makes the substituted aniline acetum; Then
(c) the nitric acid acetic anhydride is added drop-wise in the substituted aniline acetum; Then
(d) treat that C step reaction is finished after, add absolute ethyl alcohol (or with pure), destroy excessive nitric acid acetic anhydride, it is transformed into ethyl nitrate and glacial acetic acid, recovered under reduced pressure ethyl nitrate or glacial acetic acid.
9, preparation method as claimed in claim 8; it is characterized in that, N-nitro substituted aniline is carried out sulfonylation in organic solvent, or the feeding phosgene carry out chloroformylization; or add phosphide (sulfo-phosphide) acyl chlorides and carry out the phosphide acidylate, or add carboxylic acid chloride and carry out the carboxylic acyl groupization.
10, the purposes of the compound or its salt of claim 1 is characterized in that, its purposes is the chemical regulation of monocotyledon or dicotyledon, particularly regulates about paddy rice, cotton, wheat, rape, fruit tree growth.
11, purposes as claimed in claim 10 is characterized in that this compound or its salt can be used for weed killer herbicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119117A CN1098631C (en) | 1994-12-28 | 1994-12-28 | Plant-growth regulationg agent (shuangxiaosu) and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119117A CN1098631C (en) | 1994-12-28 | 1994-12-28 | Plant-growth regulationg agent (shuangxiaosu) and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125509A true CN1125509A (en) | 1996-07-03 |
| CN1098631C CN1098631C (en) | 2003-01-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119117A Expired - Fee Related CN1098631C (en) | 1994-12-28 | 1994-12-28 | Plant-growth regulationg agent (shuangxiaosu) and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098631C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311361A (en) * | 2011-09-08 | 2012-01-11 | 华中农业大学 | A compound of N- nitro-2,4,6-trifluoroaniline, synthesis method and application thereof |
| CN105248438A (en) * | 2015-10-10 | 2016-01-20 | 北京阿格瑞斯生物技术有限公司 | Composite spraying agent for wheat and preparation method, using method and application thereof |
| CN109020841A (en) * | 2018-09-07 | 2018-12-18 | 华中农业大学 | A kind of N- nitro-N- (2,4,6- trifluorophenyl) benzenesulfonamides and application thereof |
| CN110305046A (en) * | 2019-07-03 | 2019-10-08 | 湖北省农业科学院农业质量标准与检测技术研究所 | The preparation method and its usage of N- nitro-N- (2,4,6- trifluorophenyl) benzenesulfonamides |
-
1994
- 1994-12-28 CN CN94119117A patent/CN1098631C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311361A (en) * | 2011-09-08 | 2012-01-11 | 华中农业大学 | A compound of N- nitro-2,4,6-trifluoroaniline, synthesis method and application thereof |
| CN102311361B (en) * | 2011-09-08 | 2014-02-26 | 华中农业大学 | A compound of N- nitro-2,4,6-trifluoroaniline, synthesis method and application thereof |
| CN105248438A (en) * | 2015-10-10 | 2016-01-20 | 北京阿格瑞斯生物技术有限公司 | Composite spraying agent for wheat and preparation method, using method and application thereof |
| CN109020841A (en) * | 2018-09-07 | 2018-12-18 | 华中农业大学 | A kind of N- nitro-N- (2,4,6- trifluorophenyl) benzenesulfonamides and application thereof |
| CN109020841B (en) * | 2018-09-07 | 2020-11-06 | 华中农业大学 | N-nitro-N- (2,4, 6-trifluorophenyl) benzene sulfonamide compound and application thereof |
| CN110305046A (en) * | 2019-07-03 | 2019-10-08 | 湖北省农业科学院农业质量标准与检测技术研究所 | The preparation method and its usage of N- nitro-N- (2,4,6- trifluorophenyl) benzenesulfonamides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1098631C (en) | 2003-01-15 |
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