CN108623581A - A method of preparing piperazine Nino peace compound - Google Patents
A method of preparing piperazine Nino peace compound Download PDFInfo
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention belongs to organic synthesis fields, and in particular to a kind of synthetic method of piperazine Nino peace (penicinotam) compound.Using aniline and ethyoxyl methylene malonic acid, diester is starting material through condensation reaction to the present invention, and Gould Jacob react to form quinoline female ring, and 2 (1 (tertbutyloxycarbonyls) 1 are made using bromo and suzuki reactionH2 base of pyrroles) 4 chloroquinoline, 3 Ethyl formate intermediate, target product piperazine Nino peace finally is prepared by ring closure reaction.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to a kind of new side of the synthesis of piperazine Nino peace compound shown in Formulas I
Method.
Background technology
Document Shao, Chang-Lun; Wang, Chang-Yun; Gu, Yu-Cheng; Wei, Mei-Yan;
Pan, Jia-Hui; Deng, Dong-Sheng; She, Zhi-Gang; Lin, Yong-Cheng. Bioorganic & Medicinal Chemistry Letters(2010), 20 (11) disclose bioactive natural product in 3284-3286.
The structure and insecticidal activity of penicinotam.
Chinese patent CN 2009100183213 discloses compound as follows as insecticide.
Abe, Masaki; Imai, Tetsuya; Ishii, Naoki; Usui, Makio. Synthesis of
quinolactacide via an acyl migration reaction and dehydrogenation with
manganese dioxide, and its insecticidal activities. Bioscience, Biotechnology, and Biochemistry (2006), 70 (1), discloses following compound in 303-306, and one
The synthetic method of kind quinolactacide.
In view of the unique chemical constitutions of bioactive natural product penicinotam and physiological activity, has and carry out structure in a deep going way
Optimization and the significance structure optimization of pharmacodynamic study and the significance of pharmacodynamic study.Currently, the conjunction of such compound
Though being had been reported that at method, existing method and step is cumbersome, and process is complicated, of high cost, reacts third used in agents useful for same
Ketone cyanhydrin is severe poisonous chemicals, very big to human body and environmental hazard.
To meet industrialization demand, the present invention develops a variation route for being totally different from existing synthetic method, is used for
In high yield, high-purity, at low cost formula I structural compounds.With aniline ethyoxyl methylene malonic acid, diester is the present invention
Through condensation reaction, Gould-Jacobs reacts to form quinoline female ring starting material, and 2- is made using bromo and suzuki reaction
(1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formate intermediates, finally pass through transesterification and letter
Target product piperazine Nino peace (penicinotam) is prepared in single substitution reaction.
Invention content
Present invention aims at the synthetic methods for providing I quinolinone compounds of formula, include the following steps：
It is including following present invention aims at the synthetic method for providing I quinolinone compounds piperazine Nino of formula and pacifying (penicinotam)
Step：
Aniline and ethyoxyl methylene malonic acid second diester are condensed at high temperature, are reacted through Gould-Jacobs and are generated compound 2：
；
It reacts i solvent for use and is selected from dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, ring
Hexanone, acetonitrile, pyridine, phenol, DMF, DMSO, reaction temperature are solvent for use boiling temperature, and the reaction time is 0.5h~for 24 hours；
It reacts ii solvent for use and is selected from ethylene glycol monomethyl ether, diphenyl ether, methyl phenyl ethers anisole, 2,4- dibromos methyl phenyl ethers anisole, 2,5- difluoroanisoles, 2,6-
The fluoro- 5- bromoanisoles of difluoroanisole, 2,6- Banairs, 2-, 2- fluoroanisoles, 2- fluoro thioanisoles, 2- aminodiphenyls
The chloro- 4- fluoroanisoles of thioether, 2-, the chloro- 5- fluoroanisoles of 2-, 2- chloroethylethyls thioether, 2- chloroethyl methyl ethers, 2- chloroethyls
Diphenyl sulfide, 2- chlorine thioanisole, the bromo- 4- fluoroanisoles of 2-, phenylate, paraffin oil one or several kinds of reaction temperatures arrived for room temperature
Reflux, reaction time are 0.5h~for 24 hours.
（2）Compound 3 is prepared under halogenating agent effect in compound 2:
；
Halogenating agent wherein used is selected from thionyl chloride, oxalyl chloride, one or more of phosphorus trichloride or phosphorus pentachloride, solvent
For be selected from dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine,
One or more of phenol, DMF, DMSO, temperature are the boiling temperature of solvent for use.
（3）Compound 4 is prepared in the reaction under oxidant and halogenating agent effect of compound 3:
；
Wherein reaction i and ii is one pot reaction；It reacts oxidant used in i and is selected from hydrogen peroxide, ammonium dichromate, potassium hyperchlorate, height
Potassiumiodate, perchloric acid, potassium peroxydisulfate, anhydrous sodium peroxide, liquor natrii hypochloritis, performic acid, peracetic acid, benzoyl hydroperoxide,
Chloroperoxybenzoic acid, ozone, one or more of wears this Martin reagent at tertbutanol peroxide, and solvent is dioxane, tetrahydrochysene
It is a kind of in furans, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO
Or it is several, temperature is room temperature to reflux, and the reaction time is 0.5h~for 24 hours, reacts halogenating agent used in ii selected from bromine water, pentabromo- oxygen phosphorus
In, phosphorus tribromide, 3- bromobenzenes methyl sulfone, 3- methyl-bromobenzoates, dibromo sulfoxide, carbon tetrabromide, parabromobenzoic acid methyl esters, oxygen bromination
One or more of phosphorus, solvent be dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene,
One or more of in cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, temperature is room temperature to reflux, the reaction time for 0.5h~
24h。
（4）Compound 4 couples instead with (1- (tertbutyloxycarbonyl) -1H- pyrroles -2- bases) boric acid through Suzuki under alkaline condition
Compound 5 should be prepared：
；
Wherein alkaline reagent be selected from natrium carbonicum calcinatum, potassium carbonate, cesium carbonate, lithium carbonate, ammonium carbonate, calcium hydroxide, sodium hydroxide,
Potassium hydroxide, cesium hydroxide, magnesium hydroxide, barium hydroxide, ammonium hydroxide, basic zinc carbonate, basic magnesium carbonate, sodium methoxide, sodium ethoxide,
One or more of potassium tert-butoxide/sodium；Catalyst is palladium powder, palladium carbon, palladium, palladium oxide, palladium nitrate, palladium sulfate, dibromo
Change palladium, palladium dydroxide, palladium bichloride, palladium, tetra-triphenylphosphine palladium, triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides (II),
Bis- (tri-tert-butylphosphine) two palladiums (I) of dibromo, bis- (three adjacent toluene phosphines) palladium chlorides (II), bis- (methyldiphenyl phosphine) palladium chlorides
One or more of (II), solvent is dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene
One or more of in alkane, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, water, reaction temperature is boiling of the room temperature to selected solvent
Rise temperature, the reaction time is 0.5h~for 24 hours.
（5）The prepare compound 6 under bronsted acid hot conditions of compound 5：
；
Wherein it is bronsted acid be hydrogen bromide, sulfurous acid, hypophosphorous acid, fluoboric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, silico-tungstic acid,
Boric acid, acid iodide, phosphoric acid, periodic acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, phosphorous acid, polyphosphoric acids, fluoboric acid,
One kind or several in fluorophosphoric acid, hydrofluoric acid, hydroiodic acid, sulfamic acid, pyrophosphoric acid, phosphoric acid, phosphorus molybdenum acid solution, p-methyl benzenesulfonic acid
Kind, solvent dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine,
It is one or more of in phenol, DMF, DMSO, water, between reaction temperature is 50 DEG C~200 DEG C, reaction time 0.5h~48h.
（6）Compound 6 carries out ring closure reaction under alkaline condition, high temperature and obtains target product piperazine Nino peace
(penicinotam):
；
Wherein alkaline reagent be selected from natrium carbonicum calcinatum, potassium carbonate, cesium carbonate, lithium carbonate, ammonium carbonate, calcium hydroxide, sodium hydroxide,
Potassium hydroxide, cesium hydroxide, magnesium hydroxide, barium hydroxide, ammonium hydroxide, basic zinc carbonate, basic magnesium carbonate, sodium methoxide, sodium ethoxide,
One or more of potassium tert-butoxide/sodium, solvent is dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, pungent
One or more of in alkane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, water, reaction temperature is room temperature selected by
The boiling temperature of solvent, time are 0.5h~for 24 hours.
Specific implementation mode
Some examples are given below in order to further verify the present invention, these examples are entirely illustrative, they know use
To specifically describe the present invention, is not construed as limitation of the present invention.
Embodiment
4- oxyquinoline -3- Ethyl formates
Weigh aniline (1.02 mL, 0. 011 mol) and diethyl ethoxymethylenemalonate（0.5-2 eq）It is added in ethyl alcohol,
It is heated three hours at 100-200 DEG C, is cooled to room temperature, phenetole is added, 30min is heated at 100-200 DEG C, is cooled to room temperature,
After reaction, ice water is added, ethyl acetate extracts (100mL × 2), merging organic phase, organic phase saturated common salt water washing,
Anhydrous sodium sulfate is dried, filtering, organic phase concentration, and it is white solid 1.6g that residue obtains product through silica gel column chromatography（76% production
Rate）；
ESI-MS m/z 218.32 [M+H]+
1H NMR (500 MHz, DMSO-d 6 ): 10.62 (brs, 1H), 8.80 (s, 1H), 8.46-7.78 (m,
4H), 4.10 (q, J=7.1 Hz, 2H), 1.30 (t, J=7.1 Hz, 3H).
4- chloroquinoline -3- Ethyl formates
Weigh 4- oxyquinoline -3- Ethyl formates（1.6g, 7.3mmol）It is dissolved in tetrahydrofuran, phosphorus oxychloride is then added
（0.5-10 eq）After mixing, heats one hour, after reaction pour into reaction solution in ice water, with unsaturated carbonate hydrogen at 100 DEG C
Potassium solution adjusts pH to neutrality, and ethyl acetate extracts (100mL × 2), merging organic phase, organic phase saturated common salt water washing,
Anhydrous sodium sulfate is dried, filtering, organic phase concentration, and it is white solid 1.1g that residue obtains product through silica gel column chromatography（64% production
Rate）；
ESI-MS m/z 237.42 [M+H]+
1H NMR (500 MHz, DMSO-d 6) δ12.56（s, 1H）, 8.57(s, 1H), 8.19 (d, J=8.0Hz,
1), 7.74 (dd, J=8.0,7.0Hz 1H), 7.68 (d, J=8Hz, 1H), 7.45 (t, J=7Hz, 1H), 4.25 (q, J
=7Hz, 2H), 1.31 (t, J=7Hz, 3H).
The bromo- 4- chloroquinolines -3- Ethyl formates of 2-
It weighs 4- chloroquinoline -3- Ethyl formates (1.1 g, 4.7 mmol) and is dissolved in chloroform (20 mL), room temperature is added thereto
It is stirred at room temperature 4 hours after 85% benzoyl hydroperoxide (0.5-2 eq), tribromo oxygen phosphorus (0.5-2 eq) is added toward reaction solution stirs afterwards
1 hour, reaction solution is poured into ice water after reaction, with unsaturated carbonate potassium solution tune pH value to 8, ethyl acetate extraction (100
ML × 2), merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration, residual
It is white solid (1.1 g, 74% yield) that object obtains product through column chromatography；
ESI-MS m/z: 316.0 [M+H]+
1H NMR (500 MHz, CDCl3) δ 8.32-8.19 (m, 1H), 8.15-8.04 (m, 1H), 7.91-7.81
(m, 1H), 7.78-7.68 (m, 1H), 4.56 (q,J = 7.1 Hz, 2H), 1.49 (t, J = 7.1 Hz,
3H) 。
2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formates
Weigh the bromo- 4- chloroquinolines -3- Ethyl formates of 2- (1.1g, 3.2 mmol) and (1- (tertbutyloxycarbonyl) -1HPyrroles -2-
Base) boric acid (0.69 g, 3.3 mmol) is dissolved in Isosorbide-5-Nitrae-dioxane (15 mL), be added thereto cesium carbonate (4.0g,
6.5 mmol) and palladium (360 mg, 0.3 mmol), reaction solution is 75oIt is stirred under C 3 hours, it after reaction will reaction
Liquid pours into ice water, is extracted with ethyl acetate (100 mL × 2).Merge organic phase, organic phase saturated common salt water washing is anhydrous
Sodium sulphate is dried, filtering, organic phase concentration, and it is that (734 mg, 53% receives colorless oil that residue obtains product through column chromatography
Rate)；
ESI-MS m/z: 345.2 [M+H]+
1H NMR (500 MHz, CDCl3), δ 11.65 (s, 1H), 11.59 (s, 1H), 8.07 (d, J=7.6
Hz, 1H), 7.77-7.61 (m, 2H), 7.36 (t, J=7.3 Hz, 1H), 7.13 (s, 1H), 6.49 (d,
J=2.5 Hz, 1H), 6.33-6.18 (m, 1H), 4.14 (q, J=7.1 Hz, 2H), 1.14 (t, J=
7.1 Hz, 3H) 。
4- oxos -2- (1HPyrroles -2- bases)-Isosorbide-5-Nitrae-dihydroquinoline -3- Ethyl formates
By 2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formates (643 mg, 1.7 mmol) are molten
In acetic acid (10 mL), ethyl alcohol (6 mL), water（5ml）After be warming up to 80oC reacts 18 hours, and vacuum distillation removes acetic acid, second
Alcohol, gained residue are diluted with water, and are adjusted to neutrality with unsaturated carbonate potassium solution, ethyl acetate extracts (100 mL × 2), is associated with
Machine phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration.Residue must be produced through column chromatography
Object is pale yellow colored solid object (258mg, 54% yield)；
ESI-MS m/z 283.82 [M+H]+;
1H NMR (500 MHz, DMSO-d6) δ 16.12 (s, 1H), 12.40 (s, 1H), 11.81 (s, 1H),
8.25 (d, J=8.0 Hz, 1H), 7.95-7.78 (m, 2H), 7.60-7.48 (m, 1H), 7.15 (d, J=
1.4 Hz, 1H), 6.82 (s, 1H), 6.33-6.24 (m, 1H).
Piperazine Nino is pacified
By 4- oxos -2- (1HPyrroles -2- bases)-Isosorbide-5-Nitrae-dihydroquinoline -3- Ethyl formates (50 mg, 0.18 mmol), potassium carbonate
(10 mg, 0.054 mmol) is dissolved in acetonitrile 20mL, 60 DEG C of stirring 12h and adds iodomethane（10 μL,0.20 mmol）.Instead
Reaction solution is poured into ice water after answering, with dilute hydrochloric acid solution tune pH value to neutrality, ethyl acetate extraction（50mL×2）, close
And organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration, residue is through silicagel column
Chromatograph product be yellow solid（34 mg, 68% yield）,
1H NMR (500 MHz, DMSO-d 6) δ 8.20 (dd, J=8.0,1.6Hz, 1H), 7.89 (d, J=8.0,
1.6Hz, 1H), 7.78(ddd, J = 8.0,8.0,1.6Hz ,1H), 7.51 (ddd, J = 8.0,8.0,1.6Hz ,
1H),7.47（dd, J = 3.0,1.0Hz,1H）, 7.0 (dd, J = 3.5,1.0Hz, 1H), 6.45 (dd,J=3.0,
1.0Hz, 1H), 3.9（s,1H）.
Claims (9)
1. the fully synthetic preparation method of the quinolinones compound piperazine Nino amine with Formulas I structure with Formulas I structure,, which is characterized in that by compound and its derivative shown in following synthetic route formula I comprising step
Suddenly：
Step（1）:Two ester condensation of aniline and ethyoxyl methylene malonic acid second, reacts to form compound 2 through Gould-Jacobs;
Step（2）:The prepare compound 3 under halogenating agent effect of compound 2;
Step（3）:Compound 4 is prepared under oxidant and halogenating agent effect in compound 3;
Step（4）:Compound 5 is prepared through Suzuki coupled reaction under 4 alkaline condition of compound;
Step（5）:Compound 6 is obtained by the reaction in compound 5 under the conditions of acidic high-temperature;
Step（6）:Compound of formula I is obtained by the reaction in compound 6 under alkaline condition；
。
2. synthetic method described in claim 1, it is characterised in that step（1）Middle reaction i and ii is one pot reaction；React i
Solvent for use be selected from dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile,
Pyridine, phenol, DMF, DMSO, reaction temperature are solvent for use boiling temperature, and the reaction time is 0.5h~for 24 hours；It reacts used in ii
Solvent is selected from ethylene glycol monomethyl ether, diphenyl ether, methyl phenyl ethers anisole, 2,4- dibromos methyl phenyl ethers anisole, 2,5- difluoroanisoles, 2,6- difluorobenzene first
The fluoro- 5- bromoanisoles of ether, 2,6- Banairs, 2-, 2- fluoroanisoles, 2- fluoro thioanisoles, 2- diaminodiphenyl sulfides, 2-
The chloro- 5- fluoroanisoles of chloro- 4- fluoroanisoles, 2-, 2- chloroethylethyls thioether, 2- chloroethyl methyl ethers, 2- chloroethyls diphenyl sulfide,
The bromo- 4- fluoroanisoles of 2- chlorine thioanisole, 2-, phenylate, paraffin oil one or several kinds of reaction temperatures be room temperature to flow back, instead
It is 0.5h~for 24 hours between seasonable.
3. synthetic method described in claim 1, it is characterised in that step（2）In halogenating agent used be selected from thionyl chloride, oxalyl
Chlorine, one or more of phosphorus trichloride or phosphorus pentachloride, solvent are selected from dioxane, tetrahydrofuran, benzene, toluene, first
One or more of alcohol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, temperature are
The boiling temperature of solvent for use.
4. synthetic method described in claim 1, it is characterised in that step（3）Middle reaction i and ii is one pot reaction；React i
Oxidant used be selected from hydrogen peroxide, ammonium dichromate, potassium hyperchlorate, potassium metaperiodate, perchloric acid, potassium peroxydisulfate, anhydrous sodium peroxide,
Liquor natrii hypochloritis, peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, ozone, wears in this Martin reagent performic acid
One or more, solvent be dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone,
One or more of in acetonitrile, pyridine, phenol, DMF, DMSO, temperature is room temperature to reflux, and the reaction time is 0.5h~for 24 hours, is reacted
Halogenating agent used in ii in bromine water, pentabromo- oxygen phosphorus, phosphorus tribromide, 3- bromobenzenes methyl sulfone, 3- methyl-bromobenzoates, dibromo sulfoxide,
One or more of carbon tetrabromide, parabromobenzoic acid methyl esters, phosphorus oxybromide, solvent are dioxane, tetrahydrofuran, benzene, first
It is one or more of in benzene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, temperature
For room temperature to reflux, the reaction time is 0.5h~for 24 hours.
5. synthetic method described in claim 1, it is characterised in that step（4）Neutral and alkali reagent is selected from natrium carbonicum calcinatum, carbonic acid
Potassium, cesium carbonate, lithium carbonate, ammonium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, hydroxide
One or more of barium, ammonium hydroxide, basic zinc carbonate, basic magnesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide/sodium；Catalyst
For palladium powder, palladium carbon, palladium, palladium oxide, palladium nitrate, palladium sulfate, dibrominated palladium, palladium dydroxide, palladium bichloride, palladium, four or three
Phenylphosphine palladium, triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides (II), bis- (tri-tert-butylphosphine) two palladiums (I) of dibromo, bis- (three
Adjacent toluene phosphine) palladium chloride (II), one or more of bis- (methyldiphenyl phosphine) palladium chlorides (II), solvent is dioxy six
Ring, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF,
One or more of in DMSO, water, reaction temperature is the boiling temperature that room temperature arrives selected solvent, and the reaction time is 0.5h~for 24 hours.
6. synthetic method described in claim 1, it is characterised in that step（5）In bronsted acid be hydrogen bromide, it is sulfurous acid, secondary
Phosphoric acid, fluoboric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, silico-tungstic acid, boric acid, acid iodide, phosphoric acid, periodic acid, hydrofluoric acid, hydrochloric acid, sulphur
Acid, nitric acid, formic acid, acetic acid, phosphorous acid, polyphosphoric acids, fluoboric acid, fluorophosphoric acid, hydrofluoric acid, hydroiodic acid, sulfamic acid, burnt phosphorus
One or more of acid, phosphoric acid, phosphorus molybdenum acid solution, p-methyl benzenesulfonic acid, solvent dioxane, tetrahydrofuran, benzene, toluene, first
It is one or more of in alcohol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone, acetonitrile, pyridine, phenol, DMF, DMSO, water, reaction temperature
Between degree is 50 DEG C~200 DEG C, reaction time 0.5h~48h.
7. synthetic method described in claim 1, it is characterised in that step（6）The middle preferred iodomethane of reaction reagent, alkaline reagent
Selected from natrium carbonicum calcinatum, potassium carbonate, cesium carbonate, lithium carbonate, ammonium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
In caesium, magnesium hydroxide, barium hydroxide, ammonium hydroxide, basic zinc carbonate, basic magnesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide/sodium
One or more, solvent be dioxane, tetrahydrofuran, benzene, toluene, methanol, ethyl alcohol, hexane, octane, hexamethylene, cyclohexanone,
It is one or more of in acetonitrile, pyridine, phenol, DMF, DMSO, water;Reaction temperature is boiling temperature of the room temperature to selected solvent, when
Between for 0.5h~for 24 hours.
8. synthetic method described in claim 1, it is characterised in that Formulas I compound obtained is used to prepare medical medicine.
9. synthetic method described in claim 1, it is characterised in that Formulas I compound obtained is used to prepare agricultural sterilization, kills
Worm, herbicide.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691368A (en) * | 2009-08-25 | 2010-04-07 | 中国海洋大学 | Dehydration methylate of quinolinone alkaloid derivative and preparation method and application |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691368A (en) * | 2009-08-25 | 2010-04-07 | 中国海洋大学 | Dehydration methylate of quinolinone alkaloid derivative and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| CHANG-LUN SHAO 等: "Penicinoline, a new pyrrolyl 4-quinolinone alkaloid with an unprecedented ring system from an endophytic fungus Penicillium sp.", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| MASAKI ABE等: "Synthesis of Quinolactacide via an Acyl Migration Rection and Dehydrogenation with Manganese Dioxide,and Its Insecticidal Activities", 《BIOSCIENCE,BIOTECHNOLOGY,BIOCHEMISTRY》 * |
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