CN106674143A - Method for synthesizing 3'-benzoyl-3,3'-dimethyl-spiro{bicyclo[2.2.1]heptyl-2,5'-isoxazoline} - Google Patents
Method for synthesizing 3'-benzoyl-3,3'-dimethyl-spiro{bicyclo[2.2.1]heptyl-2,5'-isoxazoline} Download PDFInfo
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- CN106674143A CN106674143A CN201611083208.XA CN201611083208A CN106674143A CN 106674143 A CN106674143 A CN 106674143A CN 201611083208 A CN201611083208 A CN 201611083208A CN 106674143 A CN106674143 A CN 106674143A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a method for synthesizing 3'-benzoyl-3,3'-dimethyl-spiro{bicyclo[2.2.1]heptyl-2,5'-isoxazoline}. The method is characterized in that camphene and acetophenone are used as raw materials, iron nitrate nonahydrate is used as an oxidant and ethyl acetate is used as a solvent; the reaction temperature is 80DEG C; after the reaction is ended, a product is washed and purified to obtain a finished product. By using iron nitrate as the oxidant, the method for synthesizing the 3'-benzoyl-3,3'-dimethyl-spiro{bicyclo [2.2.1]heptyl-2,5'-isoxazoline} has the advantages of high reaction yield and high selectivity; by adopting a one-pot method, the method has the characteristics of simple operation, simple preparation cost and good practicality.
Description
Technical field
The invention belongs to organic compound synthesis technical field, and in particular to a kind of synthesis 3 '-benzoyl -3,3- diformazans
The method of base spiral shell { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }.
Background technology
Isoxazoline and its derivant are the important heterocyclic compounds of a class, and it is not only the important synthesis in organic synthesiss
Son and intermediate, while or the compound with wide spectrum pharmacologically active and biological activity.Isoxazoline compounds conduct at present
The preparation of various biological function, such as antithrombotic reagent, inhibitors of human leukocyte elastase etc..Additionally, isoxazoline
Class compound is also widely used in the treatment of antiinflammatory, antitumor, cardiovascular and nervous system.
Camphene is a kind of bicyclic diterpene alkenes compound, in colourless or micro- citrine body, molecular formula C10H16, molecular weight
136.23,51~52 DEG C of fusing point, 158.5~159.5 DEG C of boiling point, relative density 0.84g/cm3, water is insoluble in, dichloro is soluble in
Methane, ethyl acetate, chloroform etc..Camphene is present in various natural volatile oil, but is not easy in production with fractionating process from essence
Separate in oil, thus it is industrial typically with Oleum Terebinthinae (main component pinene) admire partially acid or under active hargil is catalyzed isomery and make
.Camphene as organic synthesiss raw material, for multiple fields such as medicine, cosmetics and food service industry, additionally, in analytical chemistry
Camphene also serves as chemical reagent.
In the research that Ken-ichi Itoh et al. synthesize 3- benzoyl isooxazole quinoline derivants, from ammonium ceric nitrate
(CAN) as oxidant, Jing cycloaddition reactions synthesize isoxazoline derivative, the reaction oxidant ammonium ceric nitrate price compared with
It is high.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide a kind of synthesis 3 '-benzene first
Acyl group -3, the method for 3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- } so as to which preparation method is simple, is prepared into
This is low, and finished product yield is high.
Technical scheme：In order to realize foregoing invention purpose, the technical solution used in the present invention is：
A kind of synthesis 3 '-benzoyl -3, the method for 3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- },
In reaction vessel, add camphene, ethyl acetate, 1-Phenylethanone. and oxidant, stirring, 80-100 DEG C of temperature control to react 12-20h, knot
Filter after beam, washed twice with sodium bicarbonate solution, distilled water and saturated nacl aqueous solution respectively successively, point liquid takes organic faciess,
With anhydrous sodium sulfate drying, product is by vacuum distillation removing solvent and 1-Phenylethanone.；Purified with column chromatography, petroleum ether-acetone is
Eluent, the target components for obtaining obtain white solid product through vacuum drying；Wherein, oxidant is selected from nine nitric hydrates
Ferrum, ammonium ceric nitrate, cerous nitrate, cobalt nitrate, camphene are 1: 0.8~1.6 with the mol ratio of oxidant.
Described oxidant is Fe(NO3)39H2O, and camphene is 1: 1 with the mol ratio of Fe(NO3)39H2O.
The consumption of described 1-Phenylethanone. is 8-12mL/mol.Mol refers to material camphene amount.
The consumption of described 1-Phenylethanone. is 8mL/mol.
The side of described synthesis 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }
Method, reaction temperature are 80 DEG C.
The side of described synthesis 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }
Method, reacts 15-16h.
The side of described synthesis 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }
Method, n (camphene)：N (Fe(NO3)39H2O)=1:1.4,1-Phenylethanone. 10mL/mol, 80 DEG C of reaction temperature, response time 15h.
Beneficial effect：Compared with prior art, synthesis 3 '-benzoyl -3 of the invention, 3- dimethyl spiral shell { bicyclo-
2,5 '-isoxazoline of [2.2.1] hept- } method, adopt Fe(NO3)39H2O for oxidant, selectivity is strong, simple to operate, system
Standby low cost, when oxidant is Fe(NO3)39H2O, n (camphene): n (Fe(NO3)39H2O)=1: 1.4 (mol/mol), 8mL benzene
Ethyl ketone, solvent is ethyl acetate, during 80 DEG C of reaction temperature, 3 '-benzoyl -3,3- dimethyl spiral shells bicyclo- [2.2.1] hept- 2,
5 '-isoxazolines } yield be 77.77%.With good practicality, preferable economic benefit and social effect can be produced.
Description of the drawings
Fig. 1 is the infrared spectrum of 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }；
Fig. 2 is the mass spectrum of 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }；
Fig. 3 is the leading ion of 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- }
Fragment and fragmentation figure.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
The instrument used by following examples is：Chromatographic silica gel (200-300 mesh), silica gel plate (GF-254), U.S.'s peace are prompt
Human relations company 7890A gas chromatograpies；Agilent 5975C mass spectrograph；Nicolet380FT-IR infrared spectrometers；WNMR-1-
500MHz nuclear magnetic resonance chemical analysers.
Embodiment 1
Isoxazoline is prepared using one kettle way, 10mmol camphenes, 50mL solvents, certain are added in 100mL round-bottomed flasks
The 1-Phenylethanone. and Fe(NO3)39H2O of amount, by temperature control in assigned temperature stirring reaction.Reaction uses bicarbonate after terminating successively
Sodium solution, distilled water and saturated nacl aqueous solution are washed twice, extraction point liquid, take organic faciess, with anhydrous sodium sulfate drying, product
Solvent is removed by Rotary Evaporators.Purified with column chromatography, petroleum ether-acetone (10: 1, v/v) is eluent, target components Jing
Vacuum drying is crossed, white solid is obtained.
The Analysis and Identification of product：Infrared spectrum adopts liquid-film method.Product is carried out using gas chromatograph, mass spectrograph combination
Analyze, analysis condition is：HP-5 capillary columns (30m × 0.25mm × 0.25 μm), 60 DEG C of initial temperature, reservation 2min, 10 DEG C/min
150 DEG C are warming up to, retain 1min, 20 DEG C/min is warming up to 300 DEG C, retain 2min.Carrier gas is helium, flow velocity 1mL/min, sample introduction
Mouth temperature is 280 DEG C, and ion source temperature is 230 DEG C, and level Four bar temperature is 150 DEG C, and transmission line temperature is 280 DEG C, sample size 0.4
μ L, area normalization standard measure.1H NMR analysis conditions are：Tetramethylsilane (TMS) is internal standard, deuterated chloroform (CDCl3) for molten
Agent, Proton Resonance Frequency 500MHz.
Infrared analysiss identification is carried out to experimental product using Nicolet 380FT-IR infrared spectrometers, analysis result is as schemed
Shown in 1, as shown in Figure 1,2967.10cm-1For-CH3C-H stretching vibrations；1639.98cm-1For carbonyl C=O stretching vibrations；
1572.07cm-1And 1453.21cm-1For the skeletal vibration of aromatic ring；1363.14cm-1For-CH3C-H out-of-plane bending vibrations；
1259.45cm-1For C-O stretching vibrations；700.68cm-1For the C-H out-of-plane bending vibrations of monosubstituted phenyl ring.
GC-MS analyses are carried out to product, as a result as shown in Fig. 2 wherein molecular ion peak is m/z=283.Main ion
Fragment and fragmentation are as shown in Figure 3.
For the structure of further confirmatory test product, using nuclear magnetic resonance spectroscopy means, the 1H- of experimental product has been obtained
NMR data is as follows：δ 8.20 (d, J=10Hz, 2H, H1,5)；δ 7.57 (t, J=7.5Hz, 1H, H3)；δ 7.45 (t, J=7.5Hz,
2H, H2,4)；δ 3.20 (s, 2H, H9)；δ 2.22 (d, J=5Hz, 1H, H15)；δ 2.10 and δ .89 (m, 2H, H16)；δ1.66-δ1.53
(m, 2H, H13,14)；δ 1.40- δ 1.22 (m, 3H, H12,13,14)；δ 1.07 (s, 3H, H16)；δ δ 0.99 (s, 3H, H17)。
Final to determine, the structural formula of product is as follows：
23 '-benzoyl -3,3- dimethyl spiral shells of embodiment { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- } synthesis synthesis
The reaction of 3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazoline of bicyclo- [2.2.1] hept- } is camphene and 1-Phenylethanone., nitre
The 1,3- Dipolar Cycloaddition of sour ferrum.The present invention is used to solvent species, 1-Phenylethanone. consumption, oxidant species, oxidant respectively
The factors such as amount, reaction temperature, response time are analyzed, and course of reaction is as follows：
(1) impact of the solvent species to efficiency of pcr product
Camphene 1mmol, 1-Phenylethanone. 10mL are added, oxidant is Fe(NO3)39H2O, n (camphene): n (Fe(NO3)39H2O)
=1: 1 (mol/mol), adds quantity of solvent to be 10mL, 80 DEG C of reaction temperature, response time 16h.Different solvents are to efficiency of pcr product
And reaction selectivity affects as shown in table 1：
Impact of 1 solvent species of table to efficiency of pcr product
| Solvent species | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| Not solubilizer | 99.60 | 52.72 | 52.53 |
| Ethanol | 26.81 | 20.36 | 5.46 |
| Methanol | 0 | 0 | 0 |
| Dichloromethane | 0 | 0 | 0 |
| Ethyl acetate | 95.06 | 69.86 | 66.43 |
From table 1, different solvents are affected than larger on reaction.During with methanol, dichloromethane, ethanol as solvent, almost
Cannot get target product, not camphene almost all conversion during solubilizer, but the obvious ratio of reaction selectivity makees solvent with ethyl acetate
When it is low.Therefore, ethyl acetate is selected to make solvent more suitable.
(2) impact of the 1-Phenylethanone. consumption to efficiency of pcr product
Add camphene 1mmol, ethyl acetate 10mL, oxidant is Fe(NO3)39H2O, n (camphene): n (nine nitric hydrates
Ferrum)=1: 1 (mol/mol), 80 DEG C of reaction temperature, response time 16h.1-Phenylethanone. consumption is to efficiency of pcr product and reaction selectivity shadow
Ring as shown in table 2.
Impact of the 2 1-Phenylethanone. consumption of table to efficiency of pcr product
| 1-Phenylethanone. consumption/(mL/mol) | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| 4 | 63.80 | 42.98 | 27.42 |
| 6 | 97.53 | 68.24 | 41.92 |
| 8 | 97.62 | 77.72 | 75.87 |
| 10 | 95.09 | 69.86 | 66.43 |
| 12 | 88.57 | 68.27 | 60.46 |
From table 2, as being continuously increased for 1-Phenylethanone. consumption, camphene conversion ratio and reaction selectivity are all improved constantly,
But when the consumption of 1-Phenylethanone. reaches 8mL, continue to increase 1-Phenylethanone. consumption, the selectivity and camphene conversion ratio of target product start
Reduce.Therefore, it is appropriate that 1-Phenylethanone. consumption selects 8mL.
(3) impact of the oxidant species to efficiency of pcr product
Camphene 1mmol, ethyl acetate 10mL are added, 1-Phenylethanone. consumption is 8mL, n (camphene):N (oxidant)=1: 1
(mol/mol), 80 DEG C of reaction temperature, response time 16h.Different oxidant species are affected on the yield and reaction selectivity of product
As shown in table 3：
Impact of the 3 oxide species of table to efficiency of pcr product
| Oxidant species | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| Fe(NO3)39H2O | 95.09 | 69.86 | 66.43 |
| Ammonium ceric nitrate | 94.74 | 11.07 | 10.49 |
| Cerous nitrate | 58.77 | 54.66 | 32.12 |
| Potassium nitrate | 0 | 0 | 0 |
| Cobalt nitrate | 45.66 | 44.37 | 29.68 |
From table 3, as all there is larger difference in the difference of reaction oxidant, camphene conversion ratio and reaction selectivity.
However, it is possible to find out the conversion ratio of ferric nitrate and selectivity highest in five kinds of oxidants, therefore, reaction oxidant is with ferric nitrate
It is more suitable.
(4) impact of the oxidizer to efficiency of pcr product
Camphene 1mmol is added, ethyl acetate 10mL, 1-Phenylethanone. consumption are 8mL, and oxidant is Fe(NO3)39H2O, reaction
80 DEG C of temperature, response time 16h.Oxidizer affects as shown in table 4 to efficiency of pcr product and reaction selectivity：
Impact of 4 oxidizer of table to efficiency of pcr product
| N (camphene): n (Fe(NO3)39H2O) | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| 1∶0.8 | 58.92 | 45.17 | 26.61 |
| 1∶1 | 95.09 | 69.86 | 66.43 |
| 1∶1.2 | 96.24 | 53.93 | 51.90 |
| 1∶1.4 | 98.57 | 46.81 | 46.14 |
| 1∶1.6 | 95.06 | 49.86 | 47.40 |
From table 4, as ferric nitrate consumption is reached after 1: 1, with being continuously increased for ferric nitrate consumption, camphene conversion
Rate is basically unchanged, but continues to increase its consumption, and target product selectivity starts to drastically reduce.Therefore, n (camphene): n (nine hydrations
Ferric nitrate)=1: 1 (mmol/mmol) is conveniently.
(5) impact of the reaction temperature to efficiency of pcr product
Camphene 0.15g (1mmol), ethyl acetate 10ml are added, 1-Phenylethanone. consumption is 8ml, and oxidant is nine nitric hydrates
Ferrum, n (camphene): n (Fe(NO3)39H2O)=1: 1 (mmol/mmol), response time 16h.Differential responses temperature is to efficiency of pcr product
And reaction selectivity affects as shown in table 5.
Impact of 5 reaction temperature of table to efficiency of pcr product
| Reaction temperature/DEG C | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| 60 | 13.56 | 37.04 | 9.02 |
| 70 | 93.28 | 31.84 | 29.70 |
| 80 | 97.62 | 77.72 | 75.87 |
| 90 | 97.11 | 77.57 | 75.32 |
| 100 | 97.91 | 73.22 | 71.69 |
From table 5, as the raising of temperature, camphene conversion ratio and reaction selectivity are constantly carried in the certain temperature range
Height, after temperature reaches 80 DEG C of the reflux temperature of ethyl acetate, camphene conversion ratio is basically unchanged, and its selectivity of product is no longer improved
Reduce on the contrary, continuing raising temperature does not have essential meaning, therefore selectes 80 DEG C of preference temperatures as reaction.
(6) impact of the response time to efficiency of pcr product
Camphene 1mmol, ethyl acetate 10mL are added, 1-Phenylethanone. consumption is 8mL, and oxidant is Fe(NO3)39H2O, n (camphanes
Alkene): n (Fe(NO3)39H2O)=1: 1 (mol/mol), 80 DEG C of reaction temperature.The differential responses time is to efficiency of pcr product and reaction choosing
Selecting property affects as shown in table 6.
Impact of 6 response time of table to epoxidation reaction
| Response time/h | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| 12 | 97.49 | 70.26 | 68.50 |
| 13 | 97.61 | 72.47 | 70.74 |
| 14 | 97.54 | 73.80 | 71.98 |
| 15 | 97.98 | 75.09 | 73.52 |
| 16 | 97.62 | 77.73 | 75.87 |
| 17 | 96.63 | 71.94 | 69.51 |
| 18 | 96.92 | 71.31 | 69.11 |
| 19 | 97.00 | 70.86 | 68.73 |
| 20 | 95.426 | 66.49 | 63.45 |
From table 6, at a certain temperature, with the continuous prolongation in response time, the conversion ratio change of camphene is obvious,
But, after reaction proceeds to 16 hours, with the prolongation in response time, the selectivity of product starts constantly reduction, this be because
Start to increase for prolongation by-product over time.Therefore, the response time is that 16h is more suitable.
Embodiment 3
According to the result of embodiment 2,3 '-benzoyl -3,3- dimethyl spiral shells { 2,5 '-isoxazole of bicyclo- [2.2.1] hept-
Quinoline } synthetic reaction major influence factors have time, temperature, 1-Phenylethanone. consumption, oxidant species etc..The present invention is in fixed solvent
Under conditions of ethyl acetate, have selected more representational 3 factors has carried out L9 (34) orthogonal test (table 7), its result is such as
Shown in table 8.
7 empirical factor of table and level
8 L9 (3 of table4) orthogonal experiments
| Factor | A | B | C/℃ | D/h | Yield/% |
| 1 | 1：1 | 6 | 70 | 14 | 57.05 |
| 2 | 1：1 | 8 | 80 | 15 | 67.13 |
| 3 | 1：1 | 10 | 90 | 16 | 63.93 |
| 4 | 1：1.2 | 6 | 80 | 16 | 69.67 |
| 5 | 1：1.2 | 8 | 90 | 14 | 59.45 |
| 6 | 1：1.2 | 10 | 70 | 15 | 68.09 |
| 7 | 1：1.4 | 6 | 90 | 15 | 69.5 |
| 8 | 1：1.4 | 8 | 70 | 16 | 64.39 |
| 9 | 1：1.4 | 10 | 80 | 14 | 74.11 |
| k1 | 62.704 | 65.407 | 63.177 | 63.537 | |
| k2 | 65.737 | 63.657 | 70.303 | 68.240 | |
| k3 | 69.333 | 68.710 | 64.293 | 65.997 | |
| Extreme difference | 6.629 | 5.053 | 7.126 | 4.703 |
It can be found that the principal element of the reaction is temperature from the range analysiss of table 8, next to that oxidizer and benzene second
Ketone consumption, is finally the response time.Its suitable preparation process condition is A3B3C2D2, i.e. n (camphene)：N (Fe(NO3)39H2O)
=1:1.4,1-Phenylethanone. 10mL, 80 DEG C of reaction temperature, response time 15h.With reference to the method for embodiment 2, with this understanding steady
Qualitative experiment, its result are as shown in table 9.With this understanding, up to more than 98%, reaction selectivity also exists reaction conversion ratio
More than 78.50%, three times experimental result is all more stable.
9 stability experiment result of table
| Test number (TN) | Reaction conversion ratio/% | Reaction selectivity/% | Yield/% |
| 1 | 98.92 | 78.63 | 77.78 |
| 2 | 98.95 | 78.70 | 77.87 |
| 3 | 98.52 | 78.84 | 77.67 |
Claims (7)
1. a kind of synthesis 3'- benzoyl -3, the method for 3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- isoxazolines }, its
It is characterised by：Camphene, ethyl acetate, 1-Phenylethanone. and oxidant, stirring, 80-100 DEG C of temperature control, reaction are added in reaction vessel
12-20 h, filter after terminating, are washed twice with sodium bicarbonate solution, distilled water and saturated nacl aqueous solution respectively successively, point
Liquid, takes organic faciess, and with anhydrous sodium sulfate drying, product is by vacuum distillation removing solvent and 1-Phenylethanone.；Purified with column chromatography, stone
Oily ether-acetone is eluent, and the target components for obtaining obtain white solid product through vacuum drying；Wherein, oxidant is selected from
Fe(NO3)39H2O, ammonium ceric nitrate, cerous nitrate, cobalt nitrate, camphene are 1: 0.8~1.6 with the mol ratio of oxidant.
2. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in that described oxidant is Fe(NO3)39H2O, the mol ratio of camphene and Fe(NO3)39H2O
For 1: 1.
3. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in that the consumption of described 1-Phenylethanone. be 8-12mL/mol.
4. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in that the consumption of described 1-Phenylethanone. be 8mL/mol.
5. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in that reaction temperature be 80 DEG C.
6. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in that reaction 15-16 h.
7. synthesis 3'- benzoyl -3,3- dimethyl spiral shells { bicyclo- [2.2.1] hept- 2,5'- Yi Evil according to claim 1
Oxazoline } method, it is characterised in thatn（Camphene）：n（Fe(NO3)39H2O）=1:1.4,10 mL/mol of 1-Phenylethanone., reaction temperature
80 DEG C, response time 15h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253331A (en) * | 2020-03-17 | 2020-06-09 | 南京林业大学 | Novel method for synthesizing spiroisoxazoline by using dihydrochalcone as raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100137612A1 (en) * | 2007-06-27 | 2010-06-03 | Nissan Chemical Industries, Ltd. | Method for production of 3-hydroxypropan-1-one compound for production of 2- propen-1-one compound and method for production of isoxazline compound |
| CN103980217A (en) * | 2014-05-26 | 2014-08-13 | 南京林业大学 | Pinanyl isoxazole compounds as well as synthesis method and application thereof |
-
2016
- 2016-11-30 CN CN201611083208.XA patent/CN106674143A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100137612A1 (en) * | 2007-06-27 | 2010-06-03 | Nissan Chemical Industries, Ltd. | Method for production of 3-hydroxypropan-1-one compound for production of 2- propen-1-one compound and method for production of isoxazline compound |
| CN103980217A (en) * | 2014-05-26 | 2014-08-13 | 南京林业大学 | Pinanyl isoxazole compounds as well as synthesis method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHALLY CHADHA ET AL: "Synthesis and antimicrobial evaluation of novel lipophilic derivatives of pyrazolylisoxazolines", 《INDIAN JOURNAL OF CHEMISTRY》 * |
| TAHIRA NAQVI ET AL: "Synthesis and Biological Screening of 4-(3,3-Dimethylspiro{bicyclo[2.2.1]heptan-2,5"-isoxazoline-2}-3"-yl)-2-aryl-2,3-dihydro-1H-1,5-benzodiazepines", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253331A (en) * | 2020-03-17 | 2020-06-09 | 南京林业大学 | Novel method for synthesizing spiroisoxazoline by using dihydrochalcone as raw material |
| CN111253331B (en) * | 2020-03-17 | 2022-03-08 | 南京林业大学 | Method for synthesizing spiroisoxazoline by using dihydrochalcone as raw material |
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