CN104892540A - Simple preparation method of naphthoxazine ketone derivative - Google Patents
Simple preparation method of naphthoxazine ketone derivative Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 naphthoxazine ketone Chemical class 0.000 title claims abstract description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 12
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- FBXGQDUVJBKEAJ-UHFFFAOYSA-N 4h-oxazin-3-one Chemical class O=C1CC=CON1 FBXGQDUVJBKEAJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 claims description 4
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 4
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 4
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 claims description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 2
- 235000014493 Crataegus Nutrition 0.000 claims description 2
- 241001092040 Crataegus Species 0.000 claims description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002608 ionic liquid Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 238000010992 reflux Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- 230000002378 acidificating effect Effects 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 150000004904 1,3,5-trioxanes Chemical class 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000001820 anti-cytotoxin effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a simple preparation method of a naphthoxazine ketone derivative and belongs to the field of an ionic liquid catalysis technology. In the preparation reaction, molar ratio of aromatic aldehyde to beta-naphthol to urea is 1:1:1; molar weight of an acidic ionic liquid catalyst is 5-10% of molar weight of aromatic aldehyde; volume (ml) of a reaction solvent 90% ethanol water is 4-6 times larger than molar weight (mmol) of aromatic aldehyde; reaction pressure is an atmospheric pressure; and reflux reaction lasts for 50-110 min. After the reaction is finished, preparation comprises steps as follows: cooling to room temperature until a lot of solids separate out, crushing the solids, standing, carrying out suction filtration, washing a filter residue with 90% ethanol water, and carrying out vacuum drying to obtain a product. In comparison with a preparation method by the use of other acidic ionic liquid catalyst, the method provided by the invention has characteristics as follows: catalytic activity of the catalyst is high; biodegradability is good; utilization rate of raw materials is high; reaction conditions are mild; and operations during the whole preparation process are simple and convenient. The method provided by the invention is convenient for industrial large-scale application.
Description
Technical field
The invention belongs to ionic liquid-catalyzed technical field, be specifically related to a kind of method of simple preparation Nai Bing oxazinone derivative.
Background technology
Heterogeneous ring compound is at occurring in nature ubiquity, and closely bound up with the life of people, has caused the very large interest of people in the past few decades.And the Nai Bing oxazinone derivative of Han You oxazinone structural unit is extensively present in and has in bioactive natural product, there is important pharmacology and biologic activity, the effects such as antitumor, anti-inflammatory, antimycotic and anticytotoxin can be played.This compounds is synthesized by the three components one pot reaction of 2-Naphthol, aldehyde and urea usually, but adopts the shortcomings such as traditional inorganic acid catalyst ubiquity long reaction time, productive rate are not high enough, poisonous and harmful, aftertreatment is loaded down with trivial details, environmental pollution is serious.Therefore, develop a kind of green, prepare the method for Nai Bing oxazinone derivative efficiently, quickly and easily and become many organic synthesis worker questions of common concern.
Acidic ion liquid, particularly more stable to water and air bronsted acid ionic liquid, is applied in the preparation process of Nai Bing oxazinone derivative because it has the features such as kind is many, active site density is high, uniform intensity distribution, active sites not easily run off.Such as Fang Dong etc. have employed the salt acidic ionic liquid of sulfuric acid hydrogenation 1-propanesulfonic acid yl pyridines containing a sulfonate radical as catalyzer, effectively the reaction of catalysis aromatic aldehyde, 2-Naphthol and urea generation three components " one kettle way " a series of Nai Bing oxazinone derivative can be prepared in the absence of a solvent, wherein acidic ionic liquid catalysts can recycle (synthesis [P] of functionalized ion liquid solvent-free catalysis Nai Bing oxazinone derivative, application number: 201210272622.0) after steaming desolventizes.
The structural matrix of the acidic ion liquid that aforesaid method adopts is the pyridine structure of difficult for biological degradation, and this is contrary with the policy of green chemical industry.In addition, synthesis naphthalene and the reaction of oxazinone derivative owing to being inhomogeneous reaction, need to be heated to more than 150 DEG C and could effectively overcome phase interface resistance thus reaction can be carried out smoothly, reaction conditions is harsher; Again, acidic ionic liquid catalysts needs to desolventize process do steaming before recycling, and process is comparatively complicated and power consumption is higher, and reaction solvent can not recycle, and wastes larger; Finally, although what adopt in above-mentioned synthetic method is uninanned platform, but in order to product is separated with imidazolyl acidic ionic liquid catalysts in last handling process, have employed relatively complicated 95% ethanol that adds and separate out the separation such as product, washing and purification step, add its difficulty in industrial applications.
Summary of the invention
The object of the invention is to overcome in prior art and utilize presence of acidic ionic liquid catalyst to prepare naphthalene and there is ionic liquid not readily biodegradable in oxazinone derivative process, temperature of reaction is higher, the shortcomings such as raw material availability is low, aftertreatment is complicated, and provide that a kind of readily biodegradable, reaction conditions are gentle, Atom economy is high, aftertreatment simply and easily acidic ion liquid make green catalyst, 90% aqueous ethanolic solution makes the method that Nai Bing oxazinone derivative is prepared in catalysis under solvent condition.
The structural formula of acidic ionic liquid catalysts used in the present invention is:
The method of a kind of simple preparation Nai Bing oxazinone derivative provided by the present invention, its chemical equation is:
Wherein aromatic aldehyde (I) in reaction, the mol ratio of 2-Naphthol (II) and urea (III) is 1:1:1, the molar weight of acidic ionic liquid catalysts is 5 ~ 10% of aromatic aldehyde used, reaction solvent 90% aqueous ethanolic solution in the volume of milliliter for aromatic aldehyde is in 4 ~ 6 of the molar weight of mmole times, reaction pressure is a normal atmosphere, back flow reaction 50 ~ 110min, room temperature is cooled to after reaction terminates, a large amount of solid is had to separate out, pulverize solid, leave standstill, suction filtration, gained filter residue 90% aqueous ethanolic solution washs, pure Nai Bing oxazinone derivative (IV) is obtained after vacuum-drying.Filtrate is directly used in without the need to any process to be reacted next time, and can reuse at least 5 times, its product yield does not have obvious reduction.
The present invention's aromatic aldehyde used is any one in phenyl aldehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-tolyl aldehyde, p-bromobenzaldehyde, o-methoxybenzaldehyde, aubepine, 3-bromobenzaldehyde, NSC 43794.
The synthetic method of acidic ionic liquid catalysts used in the present invention, with reference to associated materials (A convenient approach for the synthesis of 1,3,5-trioxanes under solvent-free conditions at room temperature, Monatshefte f ü r Chemie Chemical Monthly, 2014,145 (6): 1017 ~ 1022).
Compared with the synthetic method that the present invention and other acidic ion liquid make catalyzer, have the following advantages:
1, containing two-SO
3the acidity of the acidic ion liquid of H is high, and catalytic activity is high, and usage quantity is less;
2, reaction raw materials utilization ratio is high, and Atom economy is better;
3, reaction solvent can recycle, cost-saving, protection of the environment;
4, catalyzer is easy to biological degradation, friendly to human and environment;
5, reaction conditions is gentleer, energy-saving consumption-reducing;
6, whole preparation process aftertreatment is simple, is convenient to industrialization scale operation.
Embodiment
Substantive features of the present invention and unusual effect can be embodied from following embodiment; but they do not impose any restrictions the present invention; those skilled in the art's content according to the present invention makes some nonessential improvement and adjustment, all belongs to protection scope of the present invention.Below by embodiment, the present invention is further illustrated, and wherein in embodiment, the test of reaction product characterizes and uses the model of German Bruker company to be the nuclear magnetic resonance analyser of AVANCE-II 300MHz; It is the model of German Bruker company is Bruker tensor 37 FT-IR infrared spectrometer that examination of infrared spectrum characterizes what adopt, KBr compressing tablet; The fusing point of reaction product adopts capillary tube technique to measure.
Embodiment 1
1mmol phenyl aldehyde, 1mmol 2-Naphthol, 1mmol urea and 0.06mmol acidic ion liquid are joined respectively fill 4ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 52min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-phenyl naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 88%.Reuse after directly adding phenyl aldehyde, 2-Naphthol and urea in filtrate.
1,2-dihydro-1-phenyl naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.218 ~ 220 DEG C; IR (KBr): 3294,1728,1514cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=6.17 (d, J=2.1Hz, 1H), 7.22 ~ 8.01 (m, 11H), 8.85 (brs, 1H)
Embodiment 2
1mmol o-chlorobenzaldehyde, 1mmol 2-Naphthol, 1mmol urea and 0.06mmol acidic ion liquid are joined respectively fill 6ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 73min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 85%.Reuse after directly adding o-chlorobenzaldehyde, 2-Naphthol and urea in filtrate.
1,2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.250 ~ 252 DEG C; IR (KBr): 3238,3122,1726,1394,1231cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=6.48 (d, J=2.9Hz, 1H), 7.16 ~ 8.03 (m, 10H), 8.86 (brs, 1H)
Embodiment 3
1mmol 3-bromobenzaldehyde, 1mmol 2-Naphthol, 1mmol urea and 0.07mmol acidic ion liquid are joined respectively fill 6ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 82min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-(3-bromophenyl) naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 83%.Reuse after directly adding 3-bromobenzaldehyde, 2-Naphthol and urea in filtrate.
1,2-dihydro-1-(3-bromophenyl) naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.232 ~ 234 DEG C; IR (KBr): 3265,3159,1744,1712,1221cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=6.23 (d, J=2.9Hz, 1H), 7.17 ~ 8.02 (m, 10H), 8.88 (brs, 1H)
Embodiment 4
1mmol NSC 43794,1mmol 2-Naphthol, 1mmol urea and 0.09mmol acidic ion liquid are joined respectively fill 5ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 96min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-(3-p-methoxy-phenyl) naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 81%.Reuse after directly adding NSC 43794,2-Naphthol and urea in filtrate.
1,2-dihydro-1-(3-p-methoxy-phenyl) naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.202 ~ 204 DEG C; IR (KBr): 3211,3134,1749,1599,1261cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=6.15 (d, J=2.9Hz, 1H), 6.73 ~ 7.94 (m, 10H), 8.86 (brs, 1H)
Embodiment 5
1mmol p-tolyl aldehyde, 1mmol 2-Naphthol, 1mmol urea and 0.10mmol acidic ion liquid are joined respectively fill 5ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 89min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-(4-aminomethyl phenyl) naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 82%.Reuse after directly adding p-tolyl aldehyde, 2-Naphthol and urea in filtrate.
1,2-dihydro-1-(4-aminomethyl phenyl) naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.166 ~ 168 DEG C; IR (KBr): 3230,3135,1716cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=2.23 (s, 3H), 6.14 (d, J=2.4Hz, 1H), 7.12 ~ 7.98 (m, 10H), 8.82 (brs, 1H)
Embodiment 6
1mmol 4-chloro-benzaldehyde, 1mmol 2-Naphthol, 1mmol urea and 0.07mmol acidic ion liquid are joined respectively fill 6ml 90% aqueous ethanolic solution (volume ratio) with in the 25ml single port bottle of stirrer and prolong.Heating reflux reaction 85min, TLC (thin plate chromatography) detect, and raw material point disappears, be cooled to room temperature, there is a large amount of solid to separate out, pulverize solid, leave standstill, suction filtration, pure 1,2-dihydro-1-(4-chloro-phenyl-) naphtho-[1,2-e] [1 is obtained after the washing of gained filter residue 90% aqueous ethanolic solution, vacuum-drying, 3] oxazine-3-ketone, yield is 87%.Reuse after directly adding 4-chloro-benzaldehyde, 2-Naphthol and urea in filtrate.
1,2-dihydro-1-(4-chloro-phenyl-) naphtho-[1,2-e] [1,3] oxazine-3-ketone: m.p.208 ~ 210 DEG C; IR (KBr): 3221,3144,1736cm
-1;
1h NMR (300MHz, DMSO-d
6): δ=6.24 (s, 1H), 7.29 ~ 8.03 (m, 10H), 8.84 (brs, 1H)
Embodiment 7
With embodiment 1 for probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid reuses 5 times, and the yield change of product 1,2-dihydro-1-phenyl naphtho-[1,2-e] [1,3] oxazine-3-ketone is in table 1.
Embodiment 8
With embodiment 2 for probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid reuses 5 times, product 1, [the yield change of 1,3] oxazine-3-ketone is in table 2 for 2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e].
Embodiment 9
With embodiment 3 for probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid reuses 5 times, product 1, [the yield change of 1,3] oxazine-3-ketone is in table 3 for 2-dihydro-1-(3-bromophenyl) naphtho-[1,2-e].
Table 1, the acidic ion liquid active replica test result in preparation 1,2-dihydro-1-phenyl naphtho-[1,2-e] [1,3] oxazine-3-ketone
| Acidic ion liquid access times | Yield (%) |
| 1 | 88 |
| 2 | 86 |
| 3 | 86 |
| 4 | 87 |
| 5 | 85 |
| 6 | 85 |
Table 2, acidic ion liquid are in preparation 1,2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e] [the active replica test result in 1,3] oxazine-3-ketone
| Acidic ion liquid access times | Yield (%) |
| 1 | 85 |
| 2 | 83 |
| 3 | 84 |
| 4 | 86 |
| 5 | 83 |
| 6 | 84 |
Table 3, acidic ion liquid are in preparation 1,2-dihydro-1-(3-bromophenyl) naphtho-[1,2-e] [the active replica test result in 1,3] oxazine-3-ketone
| Acidic ion liquid access times | Yield (%) |
| 1 | 83 |
| 2 | 81 |
| 3 | 82 |
| 4 | 83 |
| 5 | 81 |
| 6 | 81 |
As can be seen from table 1,2,3: acidity of catalyst ionic liquid is recycling preparation 1,2-dihydro-1-phenyl naphtho-[1,2-e] [1,3] oxazine-3-ketone, 1,2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e] [1,3] oxazine-3-ketone and 1,2-dihydro-1-(3-bromophenyl) naphtho-[1,2-e] [1, yield in the process of 3] oxazine-3-ketone is in a slight decrease, but the amplitude of reduction is all smaller.Therefore, this acidity of catalyst ionic liquid can be recycled in preparation Nai Bing oxazinone derivative process, and its catalytic activity does not have obvious reduction.
Claims (3)
1. a simple preparation naphthalene the method for oxazinone derivative, it is characterized in that, aromatic aldehyde in described preparation feedback, the mol ratio of 2-Naphthol and urea is 1:1:1, the molar weight of acidic ionic liquid catalysts is 5 ~ 10% of aromatic aldehyde used, reaction solvent 90% aqueous ethanolic solution in the volume of milliliter for aromatic aldehyde is in 4 ~ 6 of the molar weight of mmole times, reaction pressure is a normal atmosphere, back flow reaction 50 ~ 110min, room temperature is cooled to after reaction terminates, a large amount of solid is had to separate out, pulverize solid, leave standstill, suction filtration, gained filter residue 90% aqueous ethanolic solution washs, pure Nai Bing oxazinone derivative is obtained after vacuum-drying,
The structural formula of described acidic ionic liquid catalysts is:
2. the method for a kind of simple preparation Nai Bing oxazinone derivative as claimed in claim 1, it is characterized in that, described aromatic aldehyde is any one in phenyl aldehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-tolyl aldehyde, p-bromobenzaldehyde, o-methoxybenzaldehyde, aubepine, 3-bromobenzaldehyde, NSC 43794.
3. the method for a kind of simple preparation Nai Bing oxazinone derivative as claimed in claim 1, it is characterized in that, the filtrate after described suction filtration is without the need to reusable at least 5 times of any process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510260743.7A CN104892540B (en) | 2015-05-20 | 2015-05-20 | Simple preparation method of naphthoxazine ketone derivative |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN114085194A (en) * | 2021-12-08 | 2022-02-25 | 青岛科技大学 | Preparation method of 2- (2-hydroxyphenyl) -4H- [1,3] -benzoxazine-4-one |
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| CN102010335A (en) * | 2009-09-08 | 2011-04-13 | 盐城师范学院 | Method for synthesizing tributyl citrate under catalysis of functional ionic liquid |
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| CN102010335A (en) * | 2009-09-08 | 2011-04-13 | 盐城师范学院 | Method for synthesizing tributyl citrate under catalysis of functional ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114085194A (en) * | 2021-12-08 | 2022-02-25 | 青岛科技大学 | Preparation method of 2- (2-hydroxyphenyl) -4H- [1,3] -benzoxazine-4-one |
| CN114085194B (en) * | 2021-12-08 | 2023-07-18 | 青岛科技大学 | Preparation method of 2- (2-hydroxyphenyl) -4H- [1,3] -benzoxazine-4-one |
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