CN103626805A - Compound with plant-growth regulating activity and preparation method of compound - Google Patents
Compound with plant-growth regulating activity and preparation method of compound Download PDFInfo
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- CN103626805A CN103626805A CN201310556141.7A CN201310556141A CN103626805A CN 103626805 A CN103626805 A CN 103626805A CN 201310556141 A CN201310556141 A CN 201310556141A CN 103626805 A CN103626805 A CN 103626805A
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Abstract
The invention discloses a compound with plant-growth regulating activity. The compound has a structure in a genera formula (I), wherein in the general formula (I), R and R1 are various substituent groups on a benzene ring; R represents a hydrogen atom, alkyl, a fluorine atom, a helium atom, nitryl and trifluoromethyl; R1 represents the hydrogen atom and the fluorine atom, or R and R1 are -CH=CH-CH=CH- and is respectively connected with the second and third bits or the third and fourth bits of the benzene ring. The compound is prepared from ferrocene ethyl ketoxime reacting with substituted benzene isocyanide acid ester. The invention also provides application of the compound as an effective component of a plant growth regulator.
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 reports in the bioactive research of agricultural chemicals field of medicaments.1971, United States Patent (USP) (US3624151A19711130) reported that anilino formic acid benzaldoxime ester has weeding activity.1981, European patent (EP24329A219810304) reported that band alkyl or sulfenyl carboxylamine fat aldehyde ketone oxime ester have insecticidal activity.Sit in 2010, S.Y.; Conway, Charles M. etc. has reported that serial oxime carbamate is as research (the Bioorganic & Medicinal Chemistry Letters (2010) of fatty amide hydrolase impedance agent, 20 (3), 1272-1277.).The a patent (WO2007010546A120070125.) of 2007 Nian， World Intellectual Property Organizations has reported that serial carboxylamine benzoquinones oxime ester has the activity for the treatment of lipase Jie mediated diseases.Acetylferrocene (
have another name called ferrocene ethyl ketone) and the research report of oxime relatively less.1961, Nesmeyanov, A.N.; Sazonova, V.A.; Drozd, V.N etc. react acquisition 1 ', 1-acetylferrocene with bromo ferrocene under Vanadium Pentoxide in FLAKES catalysis with diacetyl oxide, then prepare its oxime (Doklady Akademii Nauk SSSR (1961), 137,102-5.); 1964, Tainturier, Gerard; Tirouflet, Jean etc. are with 1, the acetylize of 1 '-diethyl ferrocene obtains multiple acetylizad isomer, and synthesized corresponding oxime (Rend.1964,258 (23), 5666-8.); 1966, Schloegl, K.; Mechtler, H. etc. have prepared acetylferrocene and oxime thereof, and reduced reduzate corresponding to preparation corresponding derivative (Chemie, 19661966,97 (1), 150-67.).2009, a Chinese patent was reported and has been 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 pesticides also focuses on (Li Wulin, the synthetic and application of amino formate compounds 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).In the research report of numerous carbamates and ferrocene ethyl ketone oxime, do not find that the research that acetylferrocene oxime and carbamate is spliced into carboxylamine ferrocene ethyl ketone oxime reports.
Summary of the invention
The object of the invention is according to novel pesticide molecular design method, the active substructure having in certain bioactive molecule is spliced, obtain and there are different bioactive novel substances.The invention provides the substituted-phenyl carboxylamine ferrocene ethyl ketone oxime ester compound that a class has no bibliographical information, and its preparation method and purposes are provided.
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 respectively 2,3 or 3,4 of phenyl ring.
As preferred version, R represents the fluorine atom on 2, R
1represent the fluorine atom on 4 or 5.
The present invention further provides the preparation method of compound, the method comprises the step that compound that ferrocene ethyl ketone oxime and general formula are (II) reacts,
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 respectively 2,3 or 3,4 of phenyl ring.
The compound of its formula of (II) and ferrocene ethyl ketone oxime are to adopt respectively following method synthetic:
With substituted aniline, react synthesizing substituted isocyanide ester with solid phosgene; 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 reacts with oxammonium hydrochloride and obtains ferrocene ethyl ketone oxime again, and reaction formula is as follows:
Solvent for use is phosphonic acids, methyl alcohol, ethanol, water and tetrahydrofuran (THF) etc.
The present invention also further provides compound that general formula is (I) in the application as in plant-growth regulator effective constituent.
The present invention is to dicotyledons rape, three-coloured amaranth, and monocotyledon rice, zea mexicana grass etc. has growth regulating-activity.
Accompanying drawing explanation
Fig. 1 is the 1HNMR figure of a fluorophenyl carboxylamine acetyl Ferrocene Oxime ester;
Fig. 2 schemes fluorophenyl carboxylamine acetyl Ferrocene Oxime ester 1HNMR;
Fig. 3 is adjacent phenylfluoroform aminocarbamic acid acetylferrocene oxime ester 1HNMR figure;
Fig. 4 is m-benzotrifluoride aminocarbamic acid acetylferrocene oxime ester 1HNMR figure;
Fig. 5 schemes phenylfluoroform aminocarbamic acid acetylferrocene oxime ester 1HNMR;
Fig. 6 is O-Nitrophenylfluorone carboxylamine acetyl Ferrocene Oxime ester 1HNMR figure;
Fig. 7 is m-nitro aminocarbamic acid acetylferrocene oxime ester 1HNMR figure;
Fig. 8 is p-nitrophenyl carboxylamine acetyl Ferrocene Oxime ester 1HNMR figure;
Fig. 9 is 2,4 difluorobenzene aminocarbamic acid acetylferrocene oxime ester 1HNMR figure;
Figure 10 is 2,5-difluorophenyl carboxylamine acetyl Ferrocene Oxime ester 1HNMR figure.
Embodiment
Below by embodiment, the present invention is specifically described.
Synthesizing of embodiment 13-fluorophenyl carboxylamine acetyl Ferrocene Oxime ester
(1) ferrocene ethyl ketone is synthetic
Take 5.59g (30mmol) ferrocene and 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 ℃ of about 10min of reaction, then immediately flask be placed in to ice bath cooling, and add about 30mL frozen water in flask.Coolingly with the 25%NaOH aqueous solution, be neutralized to neutrality in a moment, have a large amount of brown color solids to separate out, continue to filter after cooling for some time, filter cake washs with a certain amount of frozen water, dries.Crude product is purified (methylene dichloride/sherwood oil (60～90) wash-out, steams solvent, obtains safran solid state ferrocene ethyl ketone product 5.30g, and productive rate 77.1%(is in ferrocene) through column chromatography for separation, 83～85 ℃ of fusing points.
(2) ferrocene ethyl ketone oxime is synthetic
Take 1.75g (25mmol) oxammonium hydrochloride and join in 50mL twoport flask, with 7mL distilled water, dissolve, the aqueous solution that 8mL is contained to 1.41g (25mmol) NaOH joins in flask.Take 2.29g (10mmol) ferrocenyl methyl ketone, with being added drop-wise in above solution after about 17mL anhydrous alcohol solution, stirring reaction.After dropwising, be warming up to backflow, react TLC detection reaction terminal (1mL methylene dichloride adds 2 anhydrous methanols and makes developping agent) after about 3h.Stopped reaction, reaction solution is placed in ice bath has a large amount of yellow strip crystal to separate out after freezing standing for some time, suction filtration, filter cake washs with a certain amount of frozen water, vacuum-drying must obtain ferrocene ethyl ketone oxime 2.35g, and productive rate 96.3%(is in ferrocene ethyl ketone), 168～170 ℃ of fusing points (decomposition).
(3) 3-fluorophenyl isocyanide ester is synthetic
Take 1.485g (5mmol) solid phosgene (BTC) and be placed in the there-necked flask that agitator, thermometer, dropping funnel, reflux condensing tube (being connected to drying tube and device for absorbing tail gas on reflux condensing tube) are housed, make it be dissolved in 50ml ethyl acetate completely.In the cryosels baths of-5 ℃ are cold, through constant pressure funnel, slowly to reaction system, drip the ethyl acetate solution that 40ml is dissolved with 1.2g (10mmol) 3-fluoroaniline equably, cryosel is bathed and is kept the temperature of reaction system to be no more than 0 ℃.With dropping, separate out yellow mercury oxide, about 2h drips, and drips follow-up continuous insulation reaction 1h, then back flow reaction 5h.After reaction finishes, in reaction system, lead to N
2, phosgene unnecessary in system is blown out, reaction solution is orange-yellow, and drag still has a small amount of yellow mercury oxide, filters out yellow mercury oxide, and filtrate is for next step reaction.
(4) target compound 3-fluorophenyl carboxylamine acetyl Ferrocene Oxime ester is synthetic
With 3-fluorophenyl isocyanide ester, obtain corresponding target compound with the reaction of ferrocene ethyl ketone oxime, reaction formula is as follows:
Take 0.72g (3mmol) ferrocene ethyl ketone oxime and 0.18g (1.5mmol) DMAP joins in 50mL twoport flask, the methylene dichloride dry with 20mL dissolves.After the 3-fluorophenyl isocyanic ester making is dissolved with the dry methylene dichloride of 10mL, under room temperature, be slowly added drop-wise in above solution, dropwise rear TLC detection reaction liquid (ferrocene ethyl ketone oxime contrast, methylene dichloride is made developping agent), result shows to react completely.Crude product is purified in (100～200 order silica gel fix phase, methylene dichloride/sherwood oil wash-out) through column chromatography for separation, and elutriant is spin-dried for solvent, dry yellow solid product 3-fluoroanilino formic acid acetylferrocene oxime ester 0.50g, the productive rate 44.2% of obtaining.
According to aforesaid method, synthesized other intermediate and target compound, the substituted radical of each target product is as shown in table 1.
Various substituting groups on phenyl in the synthetic part of compounds molecule of table 1 the present invention
Embodiment 2: plant growth regulating activity experiment
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.
Every kind of compound arranges 12.5mg/L, 25mg/L, 50mg/L, tetra-concentration gradients of 100mg/L.Taking 25mg sample is dissolved in and in 4mL DMSO, obtains the former medicine that concentration is 6250mg/L, get this solution of 2mL, with 0.1% the tween-80 aqueous solution, be diluted to 125mL, obtain the liquid that concentration is 100mg/L, then by this method, obtain successively that concentration is 50,25, the liquid of 12.5mg/L.
In each culture dish, place two filter paper, culture dish is carried out and is measured 2～3mL liquid after mark and in culture dish, soak into filter paper, then select 10 consistent plant seeds that germinate and be placed in each culture dish, each drug concentration arrange 4 parallel, clear water contrast and solvent control are set simultaneously.The culture dish of handling well being placed in to constant temperature culture indoor, is to cultivate 5 days under the dark condition of 26 ℃ 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 inhibition plant-growth.
The impact of table 2 target compound on paddy rice and barnyard grass growth
The impact of table 3 target compound on rape and three-coloured amaranth growth
The object of the invention is the various carbamate compounds of reporting in prior art and the splicing of acetylferrocene oxime to obtain a kind of new compound with plant growth regulating activity, therefore, R substituting group in this new compound is except being the methyl in embodiment, 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 while being other alkyl replacement, 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 experiments are told us, if certain new compound has growth regulating-activity to a kind of plant, being certain to has 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 of (I):
In logical formula I, 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 respectively 2,3 or 3,4 of phenyl ring.
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. a method of preparing compound described in claim 1 or 2, is characterized in that comprising that general formula is the step that the midbody compound of (II) reacts with ferrocene ethyl ketone oxime,
In logical formula II, 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 respectively 2,3 or 3,4 of phenyl ring.
4. the compound described in claim 1 or 2 is in the application as in plant-growth regulator effective constituent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146350A (en) * | 2016-07-21 | 2016-11-23 | 华南理工大学 | A kind of new method of synthesizing amino methylcarbamoyl oximino ester derivant |
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 |
|---|
| 宋扬扬: "含二茂铁基新型植物生长调节剂的合成与生物活性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 袁庆: "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", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146350A (en) * | 2016-07-21 | 2016-11-23 | 华南理工大学 | A kind of new method of synthesizing amino methylcarbamoyl oximino ester derivant |
| 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 |
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