CN103570672A - Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound - Google Patents
Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound Download PDFInfo
- Publication number
- CN103570672A CN103570672A CN201310574554.8A CN201310574554A CN103570672A CN 103570672 A CN103570672 A CN 103570672A CN 201310574554 A CN201310574554 A CN 201310574554A CN 103570672 A CN103570672 A CN 103570672A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- benzoyl hydrazine
- preparation
- thiphene ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JQETXKWSZCMXLF-UHFFFAOYSA-N C/C=S(\c1c(C(OC)=O)[s]cc1)/NC(Nc1nc(OC)nc(C)n1)=O Chemical compound C/C=S(\c1c(C(OC)=O)[s]cc1)/NC(Nc1nc(OC)nc(C)n1)=O JQETXKWSZCMXLF-UHFFFAOYSA-N 0.000 description 1
- GUHPRPJDBZHYCJ-UHFFFAOYSA-N CC(C(O)=O)c1ccc(C(c2ccccc2)=O)[s]1 Chemical compound CC(C(O)=O)c1ccc(C(c2ccccc2)=O)[s]1 GUHPRPJDBZHYCJ-UHFFFAOYSA-N 0.000 description 1
- PFFIDZXUXFLSSR-UHFFFAOYSA-N CC(C)CC(C)c([s]cc1)c1NC(c1c[n](C)nc1C(F)(F)F)=O Chemical compound CC(C)CC(C)c([s]cc1)c1NC(c1c[n](C)nc1C(F)(F)F)=O PFFIDZXUXFLSSR-UHFFFAOYSA-N 0.000 description 1
- JLYFCTQDENRSOL-UHFFFAOYSA-N CC(COC)N(C(CCl)=O)c1c(C)[s]cc1C Chemical compound CC(COC)N(C(CCl)=O)c1c(C)[s]cc1C JLYFCTQDENRSOL-UHFFFAOYSA-N 0.000 description 1
- PZWFKJJHYNRILD-UHFFFAOYSA-N CC(c1c([Si+](C)(C)C)[s]c(C)c1C)=O Chemical compound CC(c1c([Si+](C)(C)C)[s]c(C)c1C)=O PZWFKJJHYNRILD-UHFFFAOYSA-N 0.000 description 1
- NQRFDNJEBWAUBL-UHFFFAOYSA-N CCc1c(C(NC(c2ccc[s]2)C#N)=O)[s]c(NCC)n1 Chemical compound CCc1c(C(NC(c2ccc[s]2)C#N)=O)[s]c(NCC)n1 NQRFDNJEBWAUBL-UHFFFAOYSA-N 0.000 description 1
- KDWQYMVPYJGPHS-UHFFFAOYSA-N Cc(cccc1C)c1N(Cc([s]cc1)c1OC)C(CCl)=O Chemical compound Cc(cccc1C)c1N(Cc([s]cc1)c1OC)C(CCl)=O KDWQYMVPYJGPHS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
Abstract
The invention discloses a benzoyl hydrazine compound containing a thiophene ring, and a preparation method and an application of the compound. A structural general formula of the compound is shown as Formula I or Formula II described in the specification. The preparation method of the benzoyl hydrazine compound containing the thiophene ring comprises the step that a Formula IV compound reacts with tertiary butyl hydrazine dihydrochloride in the presence of a diluent and an acid-binding agent. The benzoyl hydrazine compound containing the thiophene ring has an obvious control effect on armyworm, plutella xylostella and mosquito larva, can be applied to plant pest damage control serving as an agricultural insecticide, has an inhibitory effect on an HL-60 human leukemia cell, a BGC-823 human gastric cancer cell, a Bel-7402 human liver cancer cell and a KB human nasopharynx cancer cell, and has an application prospect in antineoplastic activity.
Description
Technical field
The invention belongs to the synthetic field of heterogeneous ring compound, particularly a kind of containing thiphene ring benzoyl hydrazine compounds and its preparation method and application.
Background technology
In recent years, heterogeneous ring compound occupies very consequence in novel ultra-high efficiency agricultural chemicals initiative, when searching novel structure has bioactive compound, design and synthetic various heterogeneous ring compounds are one of very important approach, already become quite active field ((a) new heterocyclic pesticide-sterilant, Song Baoan chief editor, Chemical Industry Press, 2009; (b) new heterocyclic pesticide-sterilant, Song Baoan, Jin Linjiang chief editor, Chemical Industry Press, 2010; (c) new heterocyclic pesticide-weedicide, Song Baoan, Wu Jian chief editor, Chemical Industry Press, 2011).In heterogeneous ring compound, sulfur heterocyclic compound more and more receives investigator's concern, thiophenes is wherein efficient because having, low toxicity, good biological activity and the various feature of structural changes, agricultural chemicals and medical aspect have a wide range of applications, be the focus and emphasis of organic chemistry research always.
Aspect medical, the microbiotic that contains thiphene ring often has better curative effect than the microbiotic that contains phenyl ring.Some anti-inflammation and analgesic drugs evident in efficacy as: sutoprofen (1), sufentanil (2), tiaprofenic acid (3) etc. are the derivative of thiophene.
Aspect agricultural chemicals, up to the present, there have been 3 compounds that contain thiphene ring successfully to be developed and become sterilant, they are respectively: the Guardian (ethaboxam of Korea S LG chemical company exploitation in 1994,4), the Silthiopham (silthiopham, 5) of Monsanto Company's exploitation in 1994, the pyrrole metsulfovax (penthiopyrad, 6) of 1996 Nian You Mitsui chemical companies exploitation.
3 compounds containing thiophene-based are successfully developed as weedicide, they are respectively: the thifensulfuron methyl (thifensulfuron of 1979 Nian You du pont company (Du Pont) exploitation, 7), the dimethenamid (dimethenamid of nineteen eighty-two Switzerland Shandeshi company (Sandoz Ltd.) exploitation, 8) and the thenylchlor (thenylchlor, 9) of day nineteen eighty-three Bender mountain (Tokuyama) Co., Ltd. exploitation.
Application aspect sterilant, can trace back to French Russell in 1974---You Ke good fortune company Development and Production containing the thiophene chrysanthemum ester derivative chrysanthemum ester (kadathrin, 10) that overcomes the enemy.Early 1980s, carried out the research of thiophenes insecticidal activity abroad, find that these compounds have significant photoactivation toxic action to mosquitos and flies ovum, larva.Lepidoptera pest is also shown obvious photoactivation toxicity and growing of its larva played to restraining effect.1987, the Philips-Duphar B.V. company of Holland developed sterilant thicyofen (thicyofen, 11), has mechanism of action novelty, and to features such as people and animals' low toxicities, this compound also has good fungicidal activity simultaneously.Thereby caused scientific research personnel to thiophene derivants the extensive concern as sterilant.
Because thiphene ring itself has good biological activity, and thiphene ring has aromaticity, and in its sulphur atom, sp2 track exists a pair of lone-pair electron, can participate in the formation of hydrogen bond in organism, increases the interaction between giving and accepting, and contributes to improve biological activity.Thiophene-based structure is started late on pesticide research, and therefore, the thiophenes of practical application is fewer.
Summary of the invention
The object of the present invention is to provide a kind of thiphene ring benzoyl hydrazine compounds that contains, this compound has good biological activity, can be for agricultural insecticide or anti-tumor activity inhibitor.
Another object of the present invention is to provide the described preparation method containing thiphene ring benzoyl hydrazine compounds.
Another object of the present invention is to provide the described application containing thiphene ring benzoyl hydrazine compounds.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A thiphene ring benzoyl hydrazine compounds, described have suc as formula structure shown in I or formula II containing thiphene ring benzoyl hydrazine compounds:
Described R base is one or more, and described R base is alkyl or the alkoxyl group that hydrogen, halogen, nitro, hydroxyl, carbonatoms are 1～4.
As a kind of preferred version, described R base is preferably hydrogen, 4-methoxyl group, 2-chloro, 3-chloro, 4-chloro, 4-bromo, 4-methyl, 2-is fluorine-based, 3-is fluorine-based, 4-is fluorine-based, 2, and 4-bis-is fluorine-based, 2, and 6-bis-is fluorine-based, 2-nitro, 3-nitro or 4-nitro.
As a kind of more preferably scheme, described R base more preferably 2-chloro, 3-chloro, 4-chloro, 2-is fluorine-based, 3-is fluorine-based, 4-is fluorine-based, 2,4-bis-is fluorine-based or 2,6-bis-is fluorine-based.
A described preparation method containing thiphene ring benzoyl hydrazine compounds, comprises the steps:
S1. under thinner exists, compound and SOCl shown in formula III
2reaction, preparation formula IV compound;
S2. under thinner and acid binding agent existence, formula IV compound reacts with tertiary butyl hydrazine hydrochloride, and separation obtains formula I and formula II compound;
Described R base is one or more, and described R base is alkyl or the alkoxyl group that hydrogen, halogen, nitro, hydroxyl, carbonatoms are 1～4.
The i.e. following reaction of experience:
The preparation method of formula III compound can carry out with reference to prior art; for example; R is that the phenyl substituted thiophene formic acid of hydrogen can be starting raw material from thiophenic acid; through Meerwein arylation reaction make (referring to: for example; (a) J.Agric.Food Chem.; 2012,60 (47), 11649-11656; (b) Eur.J.Med.Chem., 2010,45 (12), 5576-5584; (c) Collection Czechoslov Chemical Communication, 1974,39 (3), 767-771).The thiophenic acid that the phenyl that all the other R make for other substituting group replaces also can prepare with reference to aforesaid method.
Tertiary butyl hydrazine generally exists with the form of hydrochlorate.As a kind of preferred version, the described preparation method containing thiphene ring benzoyl hydrazine compounds is preferably, first thinner is mixed with tertiary butyl hydrazine hydrochloride, slowly add part acid binding agent, tertiary butyl hydrazine is discharged, slowly add again compound shown in formula IV and remaining acid binding agent, temperature reaction.
Described thinner is inert organic solvents, as a kind of preferred version, described thinner is selected from benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin, ether, diisopropyl ether, dioxan, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile, butyronitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ethyl acetate, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
As a kind of more preferably scheme, described thinner is selected from benzene, toluene or tetrahydrofuran (THF).
The carrying out that is conducive to reaction under the existence of acid binding agent.As a kind of preferred version, described acid binding agent is preferably sodium hydroxide, salt of wormwood, sodium ethylate, triethylamine, Trimethylamine 99, Tributylamine, pyridine, N, accelerine, N, N-dimethyl benzylamine, N-methyl piperidine, N-methylmorpholine, N, N-dimethyl aminopyridine, diazabicyclooctane, Diazabicyclononene or diazabicylo undecylene.
As a kind of most preferably scheme, described acid binding agent most preferably is sodium hydroxide.
S2. in, the temperature of reaction that formula IV compound reacts with tertiary butyl hydrazine hydrochloride can be carried out according to the selection of thinner under wider scope, is preferably 0～160 ℃.As a kind of more preferably scheme, more preferably 0～30 ℃.
S2., in, the reaction times that compound shown in formula IV reacts with tertiary butyl hydrazine hydrochloride is 3～15 hours.More preferably 10 hours.
As a kind of preferred version, in S1., the mol ratio of compound shown in thinner, formula III and SOCl2 is preferably: 40～80:1～1.5:1～3.
As a kind of more preferably scheme, in S1., the mol ratio of compound shown in thinner, formula III and SOCl2 more preferably: 60:1:1.5.
As a kind of preferred version, in S2., the mol ratio of compound shown in thinner, formula IV and tertiary butyl hydrazine hydrochloride is preferably: 40～80:1～1.5:1～5.
As a kind of more preferably scheme, in S2., the mol ratio of compound shown in thinner, formula IV and tertiary butyl hydrazine hydrochloride more preferably: 60:1:2.5.
Described containing the application of thiphene ring benzoyl hydrazine compounds in preparing agricultural insecticide or anti-tumor activity inhibitor.
The preparation method of compound of the present invention is simple, and productive rate is high, the experiment proved that, it has good preventive effect to lepidopteran and Diptera pest.This compounds has good restraining effect to the growth of tumour cell simultaneously.As a kind of preferred version, described agricultural insecticide for insect be mythimna separata, small cabbage moth or mosquito larvae; Described anti-tumor activity inhibitor for tumor cell line be human leukemia cell line (HL-60), SGC-7901 (BGC-823), Bel7402 (Bel-7402) or CNE cell line (KB).
R is that the fluorine-based formula I compound of 2,4-bis-all has obvious prevention effect to mythimna separata, small cabbage moth or mosquito larvae especially; R is that the formula I compound of 4-chloro all has obvious inhibition to Bel7402 (Bel-7402) or CNE cell line (KB).
Compared with prior art, the present invention has following beneficial effect:
The present invention discloses a kind of containing thiphene ring benzoyl hydrazine compounds, and described have good biological activity containing thiphene ring benzoyl hydrazine compounds novel structure, can be for agricultural insecticide or anti-tumor activity inhibitor.The described preparation method containing thiphene ring benzoyl hydrazine compounds is simple, and productive rate is high.Expanded the application prospect of thiophene-based structure aspect agricultural chemicals or antitumor drug.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.
The embodiment 1:N-tertiary butyl-3-(2 '-chloro-phenyl-) thiophene-2-formyl hydrazine (I-1) and N '-tertiary butyl-3-(2 '-chloro-phenyl-) preparation of thiophene-2-formyl hydrazine (II-11)
In being housed, the 50ml there-necked flask of thermometer adds 15mmol tertiary butyl hydrazine hydrochloride and 10ml methylene dichloride, stirring is cooled to 0 ℃, drip 10% (wt.) aqueous sodium hydroxide solution containing 15mmol sodium hydroxide, control rate of addition, make temperature remain on 0 ℃ of left and right.Dropwise rear stirring 30min.Maintenance system temperature, at 0 ℃, drips the dichloromethane solution that contains 7.5mmol2-chloro-phenyl-thiophene chloride and 10% (wt.) aqueous sodium hydroxide solution that contains 7.5mmol sodium hydroxide simultaneously.Control rate of addition, both are added simultaneously.Dropwise, slowly rise to room temperature, at 25 ℃ of reaction 9.5～10h.Filter, after organic layer washing, by dried over mgso, spend the night.After leaching siccative, steam solvent, obtain faint yellow solid.With silicagel column (eluent is V sherwood oil/V ethyl acetate=3/1) separation, obtain I-1 and II-1 compound, yield: 58%(I-1), 25.8% (II-1) fusing point: 187～188 ℃ (I-1), 201～202 ℃ (II-1).
According to the similar method of embodiment 1, only by the R in compound shown in formula I and II according to replacing shown in table 1, obtain product shown in corresponding formula I and II.The outward appearance of above-claimed cpd, productive rate and ultimate analysis value are all listed in table 1, and nucleus magnetic hydrogen spectrum detected result is all listed in table 2.As from the foregoing, above-claimed cpd structure is correct, is compound shown in formula I and II.
The physicochemical constant of compound shown in table 1 formula I and II and ultimate analysis data
Infrared and the proton nmr spectra data of compound shown in table 2 formula I and II
Shown in embodiment 2 formula I and II, contain the insecticidal activity of thiphene ring benzoyl hydrazine compounds to small cabbage moth
Experiment examination worm: small cabbage moth (Plutella xylostella Linnaeus), at indoor brassicaceous vegetable blade, to raise, raising condition is room temperature (27 ± 1) ℃, and humidity is 80%, and intensity of illumination is 2000lux, and light application time is 12h every day.Under indoor feeding condition, with worm age, body weight and 2 consistent instar larvaes of physiological situation, carry out the test of medicament screening active ingredients.
Proved recipe method: adopt pickling process, carry out the indoor general sieve activity test of compound.With punch tool device, clean cabbage leaves is broken into diameter 2cm leaf dish, in liquid, flood 5s, dry posterior lobe and put into the diameter 6cm culture dish that is added with moisturizing filter paper on dorsad, 10 of access small cabbage moth 2 instar larvaes, put into (27 ± 1) ℃ illumination box after adding a cover.Check result after 72h.Dead judging criterion is: touch polypide, the insect individuality that can not normally creep is considered as dead individual.
Shown in embodiment 3 formula I and II, contain the insecticidal activity of thiphene ring benzoyl hydrazine compounds to mythimna separata
Experiment examination worm: mythimna separata (Mythimna separata) 3 instar larvaes (being indoor with fresh corn leaf raising sensitive strain for many years)
Experimental technique: adopt Potter spray method, carry out the indoor general sieve activity test of compound.Take appropriate reagent agent, dissolve, then add a small amount of tween 80 emulsifying agent with dimethyl formamide, stir, add quantitative clear water, being mixed with concentration is the confession reagent liquid of 200mg/L.Test method adopts Potter spray method (seeing SCBZ/CH-HN-2000-001 bar), observes examination worm every day and grows and death condition, checks and record death condition after 6d.
Shown in embodiment 4 formula I and II, contain the insecticidal activity of thiphene ring benzoyl hydrazine compounds to mosquito larvae
Experiment examination worm: culex pipiens pallens (Culex pipiens pallens) four-age larva
Experimental technique: employing immersion method, carry out the indoor general sieve activity test of compound.By (waist chap) in 4 ages 10 larvas, put into the beaker of the standing tap water of 99.5mL (tap water is placed more than 1 month), active compound experiment repeats 4 times.Every glass of acetone liquid of putting into 0.5mL2000mg/L (2000mg/L) concentration, and do blank with 0.5mL acetone soln, add a small amount of mosquito feed and sucking-off mosquito pupa every day, and the moisture evaporating in supplementary beaker (5mL/ days), until mosquito larvae is all dead or pupate.
The compounds of this invention is prevented and treated the selection result in Table 3 to confession examination insect.
Compound shown in table 3 formula I and II is to supplying examination pest control the selection result
As can be seen from Table 3, shown in formula I and II, compound generally has good insecticidal activity, and wherein I-No. 7 compound has obvious insecticidal activity to the insect of test, approaches or surpass the preventive effect of contrast sterilant RH-5849.
Embodiment 5: the antitumor cytolytic activity of compound shown in formula I and II
For trying tumour cell: HL-60 human leukemia cell, BGC-823 gastric carcinoma cells, Bel-7402 human liver cancer cell, KB KB cell.
Sample test concentration: 10 μ M.
Test method: adopt MTT (tetramethyl-azo azoles salt) method or SRB (sulphonyl rhodamine B) method, carry out the anti-tumor activity test of compound.
Adopt MTT(J.Immunol.Methods1986,89 (2): 271-277) method, the vegetative period tumor cell line of taking the logarithm is seeded on 96 well culture plates and cultivates.After adherent, add test-compound, cultivate 72h, add MTT.After 4h, remove nutrient solution, add acidifying Virahol, after vibration, under microplate reader 570nm wavelength, measure absorbancy (OD).According to following formula, calculate inhibiting rate:
Inhibiting rate=(experimental group OD value/control group OD value) * 100%
Adopt SRB(J.Natl.Cancer Inst.1991,83 (11): 757-766) method, the vegetative period tumor cell line of taking the logarithm is seeded on 96 well culture plates, adds the test-compound of design flow after 24h.After cultivating 48h, add Tricholroacetic Acid, place 1h for 4 ℃.Then water rinses precipitation, and room temperature control is dry, adds SRB.After 10min, with 1% acetic acid, rinse, finally add 10mmol/L Tris solution, vibration is measured OD under microplate reader 540nm wavelength.According to above formula, calculate inhibiting rate.
The compounds of this invention is prevented and treated the selection result in Table 4 to confession examination tumor cell line.
Compound shown in table 4 formula I and II is to the selection result of preventing and treating for examination tumor cell line
As can be seen from Table 4, shown in formula I and II, compound generally has good anti-tumor activity, wherein I-No. 3 compound has obvious inhibition activity to Bel-7402 and KB, approach or be better than contrasting the preventive effect of Doxorubicin, the inhibition activity of chemical compounds I-2 and I-6 couple KB is better than contrasting Doxorubicin, has good application prospect.
Claims (10)
1. containing a thiphene ring benzoyl hydrazine compounds, it is characterized in that, described have suc as formula structure shown in I or formula II containing thiphene ring benzoyl hydrazine compounds:
Described R base is one or more, and described R base is alkyl or the alkoxyl group that hydrogen, halogen, nitro, hydroxyl, carbonatoms are 1～4.
2. according to claim 1 containing thiphene ring benzoyl hydrazine compounds, it is characterized in that, described R base is hydrogen, 4-methoxyl group, 2-chloro, 3-chloro, 4-chloro, 4-bromo, 4-methyl, 2-is fluorine-based, 3-is fluorine-based, 4-is fluorine-based, 2,4-bis-is fluorine-based, 2,6-bis-is fluorine-based, 2-nitro, 3-nitro or 4-nitro.
3. described in claim 1 or 2, contain a preparation method for thiphene ring benzoyl hydrazine compounds, it is characterized in that, comprise the steps:
S1. under thinner exists, compound and SOCl shown in formula III
2reaction, preparation formula IV compound;
S2. under thinner and acid binding agent existence, formula IV compound reacts with tertiary butyl hydrazine hydrochloride, and separation obtains formula I and formula II compound;
Described R base is one or more, and described R base is alkyl or the alkoxyl group that hydrogen, halogen, nitro, hydroxyl, carbonatoms are 1～4.
4. contain according to claim 3 the preparation method of thiphene ring benzoyl hydrazine compounds, it is characterized in that, described thinner is that described thinner is selected from benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin, ether, diisopropyl ether, dioxan, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile, butyronitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ethyl acetate, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
5. contain according to claim 3 the preparation method of thiphene ring benzoyl hydrazine compounds, it is characterized in that, described acid binding agent is sodium hydroxide, salt of wormwood, sodium ethylate, triethylamine, Trimethylamine 99, Tributylamine, pyridine, N, accelerine, N, N-dimethyl benzylamine, N-methyl piperidine, N-methylmorpholine, N, N-dimethyl aminopyridine, diazabicyclooctane, Diazabicyclononene or diazabicylo undecylene.
6. according to claim 3 containing the preparation method of thiphene ring benzoyl hydrazine compounds, it is characterized in that, in S2., temperature of reaction is 0～160 ℃.
7. according to claim 3 containing the preparation method of thiphene ring benzoyl hydrazine compounds, it is characterized in that, in S2., the reaction times is 3～15 hours.
8. according to claim 3 containing the preparation method of thiphene ring benzoyl hydrazine compounds, it is characterized in that compound and SOCl shown in thinner, formula III in S1.
2mol ratio be: 40～80:1～1.5:1～3;
S2. the mol ratio of compound shown in middle thinner, formula IV and tertiary butyl hydrazine hydrochloride is: 40～80:1～1.5:1～5.
9. described in claim 1 or 2, contain the application of thiphene ring benzoyl hydrazine compounds in preparing agricultural insecticide or anti-tumor activity inhibitor.
10. application according to claim 9, is characterized in that, described agricultural insecticide for insect be mythimna separata, small cabbage moth or mosquito larvae; Described anti-tumor activity inhibitor for tumor cell line be human leukemia cell line, SGC-7901, Bel7402 or CNE cell line.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310574554.8A CN103570672B (en) | 2013-11-15 | 2013-11-15 | Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310574554.8A CN103570672B (en) | 2013-11-15 | 2013-11-15 | Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103570672A true CN103570672A (en) | 2014-02-12 |
| CN103570672B CN103570672B (en) | 2015-06-17 |
Family
ID=50043457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310574554.8A Expired - Fee Related CN103570672B (en) | 2013-11-15 | 2013-11-15 | Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103570672B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105918332A (en) * | 2016-05-06 | 2016-09-07 | 烟台图文马克化工科技有限公司 | Pesticide for preventing and treating flattened eucleid |
| CN113975271A (en) * | 2021-09-02 | 2022-01-28 | 苏州大学附属第一医院 | Application of small molecular compound in preparing medicine for treating tumor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061598A (en) * | 1990-10-29 | 1992-06-03 | 石原产业株式会社 | Hydrazine class compound or its salt, its preparation method and contain the sterilant of this compounds |
| CN1628111A (en) * | 2002-02-01 | 2005-06-15 | 大日本制药株式会社 | 2-furancarboxylic acid hydrazides and pharmaceutical compositions containing the same |
| CN101402632A (en) * | 2008-11-25 | 2009-04-08 | 中国农业大学 | Aryl hydrazide compounds with antineoplastic activity |
| WO2011007722A1 (en) * | 2009-07-13 | 2011-01-20 | 大日本住友製薬株式会社 | 3-substituted-2-furancarboxylic acid hydrazide derivative and pharmaceutically acceptable salt thereof |
-
2013
- 2013-11-15 CN CN201310574554.8A patent/CN103570672B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061598A (en) * | 1990-10-29 | 1992-06-03 | 石原产业株式会社 | Hydrazine class compound or its salt, its preparation method and contain the sterilant of this compounds |
| CN1628111A (en) * | 2002-02-01 | 2005-06-15 | 大日本制药株式会社 | 2-furancarboxylic acid hydrazides and pharmaceutical compositions containing the same |
| CN101402632A (en) * | 2008-11-25 | 2009-04-08 | 中国农业大学 | Aryl hydrazide compounds with antineoplastic activity |
| WO2011007722A1 (en) * | 2009-07-13 | 2011-01-20 | 大日本住友製薬株式会社 | 3-substituted-2-furancarboxylic acid hydrazide derivative and pharmaceutically acceptable salt thereof |
Non-Patent Citations (1)
| Title |
|---|
| 崔紫宁等: "含呋喃环双酰肼类化合物的合成及杀虫活性研究", 《有机化学》, vol. 27, no. 10, 31 December 2007 (2007-12-31), pages 1300 - 1304 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105918332A (en) * | 2016-05-06 | 2016-09-07 | 烟台图文马克化工科技有限公司 | Pesticide for preventing and treating flattened eucleid |
| CN113975271A (en) * | 2021-09-02 | 2022-01-28 | 苏州大学附属第一医院 | Application of small molecular compound in preparing medicine for treating tumor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103570672B (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| HUE027959T2 (en) | Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents | |
| CN103664808B (en) | A kind of aryl 3-triazole compounds containing chlorocyclopropane and preparation method thereof and application | |
| CN101973934A (en) | 1,5-disubstituted aryl-1,4-pentadiene-3-ketoxime ether compound and preparation method thereof and insecticidal activity application | |
| CN110194726A (en) | A kind of benzamide compound and its application | |
| CN112661665B (en) | Amide compound and preparation method and application thereof | |
| CN104961728A (en) | Preparation method and application of pyridinyl methoxybiphenyl structure-containing pyrazole oxime ester compound | |
| CN106008496A (en) | S-(5-substituted-1, 3, 4-thiadiazole)-(5-substituted phenyl)-2-furancarbothioic acid ester compound, preparation method and application thereof | |
| CN108069984B (en) | Substituted five-membered heterocyclic compound containing pyrimido ring and preparation method and application thereof | |
| CN102746282B (en) | N-5-substituted phenyl-2-furoyl compounds, preparation method and application thereof | |
| CN110759913A (en) | Indolylhydrazone derivatives, preparation method thereof and application thereof in plant virus prevention and control, sterilization and disinsection | |
| JP2751309B2 (en) | Pyrazoles and insecticides, miticides, fungicides containing them as an active ingredient | |
| CN108341808B (en) | Oxadiazole pyrazole compound and application thereof | |
| CN103570672B (en) | Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound | |
| CN106432081A (en) | Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure | |
| CN109956904B (en) | Pyrazole amide compound and application thereof and bactericide | |
| CN103420884B (en) | There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism | |
| CN108059613B (en) | Pyrazole amide compound and application thereof | |
| CN113549053B (en) | Pyrazoloquine (azolyl) ether compound and application thereof | |
| CN110156685B (en) | Aromatic cyclopentenopyridine, and synthesis method and application thereof | |
| CN108148034A (en) | A kind of novel fluorine substituted urea butylcoumariii derivative and its weeding and sterilizing use | |
| CN108794461B (en) | Fluorine-containing phenyl oxadiazole pyrazole insecticidal bactericide | |
| CN107494553A (en) | Disinfectant use in agriculture and purposes derived from a kind of gallic acid | |
| JPS63225364A (en) | Aralkylaminopyrimidine derivative, its production and insecticide, miticide and fungicide containing said derivative as active component | |
| CN106045982A (en) | N'-5-(substituted-phenyl)-2-furanmethenyl-5-propyl-1H-pyrazol-3-ethyl formate compound and preparation method and application thereof | |
| CN109232534B (en) | Heterocyclic diarylamine-containing pyrazole formamide compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150617 Termination date: 20201115 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |