CN103626805B - Compound with plant growth regulating activity and preparation method thereof - Google Patents
Compound with plant growth regulating activity and preparation method thereof Download PDFInfo
- Publication number
- CN103626805B CN103626805B CN201310556141.7A CN201310556141A CN103626805B CN 103626805 B CN103626805 B CN 103626805B CN 201310556141 A CN201310556141 A CN 201310556141A CN 103626805 B CN103626805 B CN 103626805B
- Authority
- CN
- China
- Prior art keywords
- compound
- ferrocene
- atom
- fluorine atom
- plant
- 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.)
- Expired - Fee Related
Links
- NCEZEHCYDBKFPR-URLRMUCDSA-N C/C(/[C@H]1C(C)=CCC=C1)=N/O Chemical compound C/C(/[C@H]1C(C)=CCC=C1)=N/O NCEZEHCYDBKFPR-URLRMUCDSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of compound with plant growth regulating activity, this compound has the structure of logical formula I, in logical formula I, and R, R
1for the various substituting groups on phenyl ring, R represents hydrogen atom, alkyl, fluorine atom, chlorine atom, nitro, trifluoromethyl, R
1represent hydrogen atom, fluorine atom, or R, R
1for-CH=CH-CH=CH-connects 2,3 or 3,4 of phenyl ring respectively.This compound prepares by ferrocene acetophenone oxime and substituted benzene isocyanide ester being reacted.Present invention also offers the application of compound as plant-growth regulator effective constituent.
Description
Technical field
The invention belongs to pesticide field, be specifically related to a kind of compound with plant growth regulating activity and preparation method thereof.
Background technology
Oxime carbamate compounds has a lot of report in the bioactive research of agricultural chemicals field of medicaments.1971, United States Patent (USP) (US3624151A19711130) reported anilino formic acid benzaldoxime ester and has weeding activity.1981, European patent (EP24329A219810304) reports band alkyl or sulfenyl carboxylamine fat aldehyde ketone oxime ester has insecticidal activity.Sit, S.Y. in 2010; Conway, etc. CharlesM. research (the Bioorganic & MedicinalChemistryLetters (2010) of serial oxime carbamate as fatty amide hydrolase impedance agent is reported, 20 (3), 1272-1277.).2007, a patent (WO2007010546A120070125.) of World Intellectual Property Organization reported the activity that serial carboxylamine benzoquinones oxime ester has the mediated disease for the treatment of lipase.Acetylferrocene (
have another name called ferrocene ethyl ketone) and oxime research report relatively less.1961, Nesmeyanov, A.N.; Sazonova, V.A.; Bromo ferrocene and the diacetyl oxide such as Drozd, V.N react acquisition 1 ', 1-acetylferrocene under Vanadium Pentoxide in FLAKES catalysis, then prepare its oxime (DokladyAkademiiNaukSSSR (1961), 137,102-5.); 1964, Tainturier, Gerard; 1,1 '-diethyl ferrocene acetylize such as Tirouflet, Jean obtains multiple acetylizad isomer, and has synthesized corresponding oxime (Rend.1964,258 (23), 5666-8.); 1966, Schloegl, K.; Mechtler, H. etc. have prepared acetylferrocene and oxime thereof, and are reduced reduzate correspondence derivative (Chemie, 19661966,97 (1), 150-67.) corresponding to preparation.2009, a Chinese patent reports prepared antimony triphenyl acetylferrocene oxime complex compound (CN101492478A20090729).
Amino formate compounds is a lot of as the kind of commercially available agricultural chemical, its important activity substructure is-NCO-OR, the work of numerous research and development novel pesticide also focuses on (Li Wulin, the synthesis of amino formate compounds and application on amino formate compounds.Xianning College's journal, 2006,26, (3): 64 ~ 66; Liu Yifeng etc., the application of amino formate compounds, chemistry circular, 2002,3,167-171).Do not find that research acetylferrocene oxime and carbamate being spliced into carboxylamine ferrocene acetophenone oxime is reported in the research report of numerous carbamate and ferrocene acetophenone oxime.
Summary of the invention
The object of the invention is according to novel pesticide molecular design method, the active substructure had in certain bioactive molecule is spliced, obtain and there is different bioactive novel substance.The invention provides the substituted-phenyl carboxylamine ferrocene acetophenone oxime ester cpds that a class has no bibliographical information, and provide its preparation method and purposes.
New compound provided by the invention has the structure that general formula is (I):
In logical formula I, R, R
1for the various substituting groups on phenyl ring, wherein R represents hydrogen atom, alkyl, fluorine atom, chlorine atom, nitro, trifluoromethyl, R
1represent hydrogen atom, fluorine atom; Or R, R
1for-CH=CH-CH=CH-connects 2,3 or 3,4 of phenyl ring respectively.
Preferably, R represents the fluorine atom on 2, R
1represent the fluorine atom on 4 or 5.
Invention further provides the preparation method of compound, it is the step that the compound of (II) reacts that the method comprises ferrocene acetophenone oxime and general formula,
In logical formula II, R, R
1for the various substituting groups on phenyl ring, wherein R represents hydrogen atom, alkyl, fluorine atom, chlorine atom, nitro, trifluoromethyl, R
1represent hydrogen atom, fluorine atom; Or R, R
1for-CH=CH-CH=CH-connects 2,3 or 3,4 of phenyl ring respectively.
The compound of its formula of (II) and ferrocene acetophenone oxime adopt following method to synthesize respectively:
With substituted aniline and solid phosgene Reactive Synthesis substituted benzene isocyanide ester; Reaction formula is as follows:
Solvent for use is tetrahydrofuran (THF), methylene dichloride, trichloromethane, ethyl acetate, sherwood oil etc.
Ferrocene and acetic anhydride obtain ferrocene ethyl ketone, and ferrocene ethyl ketone is obtained by reacting ferrocene acetophenone oxime with oxammonium hydrochloride again, and reaction formula is as follows:
Solvent for use is phosphonic acids, methyl alcohol, ethanol, water and tetrahydrofuran (THF) etc.
The present invention still further provides compound that general formula is (I) as the application in plant-growth regulator effective constituent.
The present invention is to dicotyledons rape, three-coloured amaranth, and monocotyledon rice, zea mexicana grass etc. have growth regulating-activity.
Accompanying drawing explanation
Fig. 1 is the 1HNMR figure of a Fluorophenylamino formic acid acetylferrocene oxime ester;
Fig. 2 schemes Fluorophenylamino formic acid acetylferrocene oxime ester 1HNMR;
Fig. 3 is that adjacent phenylfluoroform aminocarbamic acid acetylferrocene oxime ester 1HNMR schemes;
Fig. 4 is that m-benzotrifluoride aminocarbamic acid acetylferrocene oxime ester 1HNMR schemes;
Fig. 5 schemes phenylfluoroform aminocarbamic acid acetylferrocene oxime ester 1HNMR;
Fig. 6 is that O-Nitrophenylfluorone carboxylamine acetyl Ferrocene Oxime ester 1HNMR schemes;
Fig. 7 is that m-nitro aminocarbamic acid acetylferrocene oxime ester 1HNMR schemes;
Fig. 8 is that p-nitrophenyl carboxylamine acetyl Ferrocene Oxime ester 1HNMR schemes;
Fig. 9 is that 2,4 difluorobenzene aminocarbamic acid acetylferrocene oxime ester 1HNMR schemes;
Figure 10 is that 2,5-Difluorophenylamino formic acid acetylferrocene oxime ester 1HNMR schemes.
Embodiment
Below by embodiment, the present invention is specifically described.
The synthesis of embodiment 13-Fluorophenylamino formic acid acetylferrocene oxime ester
(1) synthesis of ferrocene ethyl ketone
Take 5.59g (30mmol) ferrocene to join in 250mL twoport flask, then measure 24mL (254mmol) diacetyl oxide and join in flask, then measure 7mL (containing H
3pO
4121mmol) 85% phosphoric acid slowly joins in flask.Be warming up to 75 ~ 80 DEG C and react about 10min, then immediately flask is placed in ice bath and cools, and add about 30mL frozen water in flask.Cooling is neutralized to neutrality with the 25%NaOH aqueous solution in a moment, has a large amount of yellow-brown solid to separate out, and filter after continuing cooling for some time, a certain amount of frozen water of filter cake washs, and dries.Crude product is purified (methylene dichloride/sherwood oil (60 ~ 90) wash-out, steams solvent, and obtain safran solid state ferrocene ethyl ketone product 5.30g, productive rate 77.1%(is in ferrocene) through column chromatography for separation, fusing point 83 ~ 85 DEG C.
(2) synthesis of ferrocene acetophenone oxime
Taking 1.75g (25mmol) oxammonium hydrochloride joins in 50mL twoport flask, and dissolve with 7mL distilled water, aqueous solution 8mL being contained 1.41g (25mmol) NaOH joins in flask.Take 2.29g (10mmol) ferrocenyl methyl ketone, be added drop-wise in above solution with after about 17mL anhydrous alcohol solution, stirring reaction.After dropwising, be warming up to backflow, TLC detection reaction terminal (1mL methylene dichloride adds 2 anhydrous methanols and makes developping agent) after reacting about 3h.Stopped reaction, reaction solution has a large amount of yellow strip crystal to separate out after being placed in ice bath freezing standing for some time, suction filtration, the a certain amount of frozen water of filter cake washs, vacuum-drying must obtain ferrocene acetophenone oxime 2.35g, and productive rate 96.3%(is in ferrocene ethyl ketone), fusing point 168 ~ 170 DEG C (decomposition).
(3) synthesis of 3-fluorophenyl isocyanide ester
Take 1.485g (5mmol) solid phosgene (BTC) and be placed in the there-necked flask that agitator, thermometer, dropping funnel, reflux condensing tube (reflux condensing tube being connected to drying tube and device for absorbing tail gas) are housed, make it be dissolved in 50ml ethyl acetate completely.In the cryosel baths of-5 DEG C are cold, slowly drip to reaction system the ethyl acetate solution that 40ml is dissolved with 1.2g (10mmol) 3-fluoroaniline equably through constant pressure funnel, cryosel bath keeps the temperature of reaction system to be no more than 0 DEG C.Carry out precipitation yellow mercury oxide with dropping, about 2h drips, and drips follow-up continuous insulation reaction 1h, then back flow reaction 5h.After reaction terminates, logical N in reaction system
2, blown out by phosgene unnecessary in system, reaction solution is orange-yellow, and drag still has a small amount of yellow mercury oxide, filters out yellow mercury oxide, and filtrate is used for next step reaction.
(4) synthesis of target compound 3-Fluorophenylamino formic acid acetylferrocene oxime ester
Be obtained by reacting corresponding target compound with 3-fluorophenyl isocyanide ester with ferrocene acetophenone oxime, reaction formula is as follows:
Take 0.72g (3mmol) ferrocene acetophenone oxime and 0.18g (1.5mmol) DMAP joins in 50mL twoport flask, dissolve with the methylene dichloride of 20mL drying.Slowly be added drop-wise in above solution under room temperature after being dissolved by the methylene dichloride of obtained 3-fluorophenylisocyanate 10mL drying, dropwise rear TLC detection reaction liquid (ferrocene acetophenone oxime contrasts, and methylene dichloride makes developping agent), result shows to react completely.Crude by column chromatography separating-purifying (100 ~ 200 order silica gel fix phase, methylene dichloride/sherwood oil wash-out), elutriant is spin-dried for solvent, dry yellow solid product 3-fluoroanilino formic acid acetylferrocene oxime ester 0.50g, productive rate 44.2%.
Synthesized other intermediate and target compound according to aforesaid method, the substituted radical of each target product is as shown in table 1.
Various substituting group on phenyl in the part of compounds molecule of table 1 the present invention synthesis
Embodiment 2: plant growth regulating activity is tested
With reference to " People's Republic of China's agricultural industry criteria farm-chemical indoor determination test rule (weedicide) Plating (NY/T1155.1-2006) ", test new compound to dicotyledons rape, three-coloured amaranth, the plant growth regulating activity of monocotyledon rice, zea mexicana grass.
Often kind of compound arranges 12.5mg/L, 25mg/L, 50mg/L, 100mg/L tetra-concentration gradients.Take 25mg sample to be dissolved in 4mLDMSO and to obtain the former medicine that concentration is 6250mg/L, get this solution of 2mL, be diluted to 125mL with the tween-80 aqueous solution of 0.1%, obtain the liquid that concentration is 100mg/L, then by this method obtain successively concentration be 50,25, the liquid of 12.5mg/L.
Two filter paper are placed in each culture dish, culture dish measures 2 ~ 3mL liquid and soak into filter paper in culture dish after carrying out mark, then select 10 germinate consistent plant seeds be placed in each culture dish, each drug concentration arrange 4 parallel, arrange simultaneously clear water contrast and solvent control.The culture dish handled well is placed in constant temperature culture indoor, is cultivate 5 days under the dark condition of 26 DEG C in temperature, measures that the root of each test plant is long and stem is long after 5 days with graduated scale.
In following table, negative value is Promoting plant growth, on the occasion of being suppression plant-growth.
The impact that table 2 target compound grows paddy rice and barnyard grass
The impact that table 3 target compound grows rape and three-coloured amaranth
The object of the invention is the various carbamate compounds reported in prior art and acetylferrocene oxime to splice to obtain a kind of compound with plant growth regulating activity newly, therefore, R substituent in this new compound is except being the methyl in embodiment, it can also be other various alkyl, as propyl group, isobutyl-, octyl group etc., those skilled in the art easily expect that R also has the purposes identical with methyl when being the replacement of other alkyl, and produce identical technique effect.
In addition, because each large class plant (monocotyledons or dicotyledons) all has physiology general character, a large amount of scientific experiment tells us, if certain new compound has growth regulating-activity to a kind of plant, is then certain to there is growth regulating-activity to the many kind of plant in such plant.Therefore, this specification sheets will not enumerate the growth regulating-activity of compound to other plant.
Claims (4)
1. general formula is the compound with plant growth regulating activity of (I):
In logical formula I, R represents hydrogen atom, methyl, fluorine atom, chlorine atom, nitro, trifluoromethyl, R
1represent hydrogen atom, fluorine atom, or R, R
1for-CH=CH-CH=CH-connects 2,3 or 3,4 of phenyl ring respectively.
2. compound as claimed in claim 1, is characterized in that: R represents the fluorine atom on 2, R
1represent the fluorine atom on 4 or 5.
3. prepare a method for compound described in claim 1 or 2, it is characterized in that comprising midbody compound that general formula is (II) and the step that ferrocene acetophenone oxime is reacted,
In logical formula II, R represents hydrogen atom, methyl, fluorine atom, chlorine atom, nitro, trifluoromethyl, R
1represent hydrogen atom, fluorine atom, or R, R
1for-CH=CH-CH=CH-connects 2,3 or 3,4 of phenyl ring respectively.
4. the compound described in claim 1 or 2 is as the application in plant-growth regulator effective constituent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310556141.7A CN103626805B (en) | 2013-11-11 | 2013-11-11 | Compound with plant growth regulating activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310556141.7A CN103626805B (en) | 2013-11-11 | 2013-11-11 | Compound with plant growth regulating activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626805A CN103626805A (en) | 2014-03-12 |
| CN103626805B true CN103626805B (en) | 2016-03-30 |
Family
ID=50208284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310556141.7A Expired - Fee Related CN103626805B (en) | 2013-11-11 | 2013-11-11 | Compound with plant growth regulating activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626805B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146350B (en) * | 2016-07-21 | 2017-10-20 | 华南理工大学 | A kind of new method of synthesizing amino formic acid oxime ester derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053296A (en) * | 1975-10-02 | 1977-10-11 | Bayer Aktiengesellschaft | Ferrocene derivative for supplying plants with iron |
-
2013
- 2013-11-11 CN CN201310556141.7A patent/CN103626805B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053296A (en) * | 1975-10-02 | 1977-10-11 | Bayer Aktiengesellschaft | Ferrocene derivative for supplying plants with iron |
Non-Patent Citations (2)
| Title |
|---|
| 含二茂铁基新型植物生长调节剂的合成与生物活性研究;宋扬扬;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110815;第16页 * |
| 新型含二茂铁基的1,3,4-噻二唑类化合物的合成及其生物活性测试;袁庆;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110815;第33页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626805A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626805B (en) | Compound with plant growth regulating activity and preparation method thereof | |
| CN101544633B (en) | Synthesis technology for methyl thiadiazole formamide | |
| Liu et al. | Synthesis and bioactivities of α-aminophosphonate derivatives containing benzothiazole and thiourea moieties | |
| CN105712975A (en) | Pyrazole amide compound containing 1,2,3-triazole ring and application of pyrazole amide compound containing 1,2,3-triazole ring | |
| CN104072455B (en) | 6-aroyl acetyl oxygen base Aurone compound and the application on pesticide thereof | |
| CN107459490A (en) | The Carbox amide of azophenlyene 1 and its application | |
| Jin et al. | Synthesis and herbicidal activity of novel dialkoxyphosphoryl aryl methyl 2-(4, 6-dimethoxypyrimidin-2-yloxy) benzoate derivatives | |
| CN107188858A (en) | The formyl piperazine compound of azophenlyene 1 and its application | |
| CN106432245B (en) | A kind of 1,2,4- triazole derivatives of the structure containing benzopyrazines and its preparation method and application | |
| CN109232456B (en) | 3-methyl-4-nitro-5- (2-aryl-2-trifluoromethyl) cyclopropyl isoxazole compound and preparation method thereof | |
| CN103030607B (en) | Thiadiazole-containing amide derivative, and preparation and application thereof as plant growth regulator | |
| CN102863357B (en) | Compound having plant growth regulating activity and preparation method thereof | |
| CN106234385B (en) | A kind of application of 1,2,4- triazole derivatives of the structure containing benzopyrazines as fungicide | |
| CN110156867A (en) | A kind of carbamic acid Cortex Phellodendri ketoxime ester and the preparation method and application thereof | |
| CN108719301A (en) | A kind of application of 1- methyl -3- Trifluoromethyl-1s H- pyrazoles -4- amide derivatives in preparing herbicide | |
| CN110194749B (en) | Method for synthesizing 3-trifluoro (difluoro) methyl-1, 2, 4-triazole-5-ketone compound | |
| CN106243109A (en) | A kind of 1,2,4 triazole derivatives containing methyl benzopyrazines structure and its preparation method and application | |
| EP3733660B1 (en) | N-alkyl-n-cyanoalkylbenzamide compound and use thereof | |
| CN115583922B (en) | Fluorine-containing N- (3- (benzoxazol-2-yl) phenyl) amide compound and preparation method and application thereof | |
| CN103058955B (en) | Thiadiazole thiourea derivative as well as preparation and application thereof as plant growth regulator | |
| CN110372674B (en) | Preparation and application of pyrazole compound containing benzotriazole unit | |
| CN102718722A (en) | Preparation and application research of water-soluble and oil-soluble novel aryloxy phenoxy carboxylate derivatives | |
| CN114957113B (en) | 2-chloroquinoline-3-formaldehyde oxime-O- (N-p-fluorophenyl) carbamate and preparation method and application thereof | |
| CN101565417A (en) | Benzenesulfonyl carboxamide and preparation method thereof | |
| CN115650972B (en) | Sophoridine derivative and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160330 Termination date: 20161111 |