CN108084140A - A kind of preparation method of different chroman-4-on - Google Patents
A kind of preparation method of different chroman-4-on Download PDFInfo
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- CN108084140A CN108084140A CN201711175821.9A CN201711175821A CN108084140A CN 108084140 A CN108084140 A CN 108084140A CN 201711175821 A CN201711175821 A CN 201711175821A CN 108084140 A CN108084140 A CN 108084140A
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- different chroman
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/76—Benzo[c]pyrans
Abstract
The present invention relates to a kind of preparation methods of heterochromatic full 4 ketone, are completely dissolved in heterochromatic in organic solvent, add in catalyst nitrogen dioxide, and are passed through oxygen, and closed reactor reacts 0.5 5h at a temperature of 100 170 DEG C, and heterochromatic full 4 ketone are made.The preparation method of the present invention is using heterochromatic full and oxygen as raw material, using nitrogen dioxide as catalyst, overcomes the problem of discarded object generated in existing method is more, and synthesis is of high cost.
Description
Technical field
The present invention relates to industrial chemicals preparing technical fields, and in particular to a kind of preparation method of different chroman-4-on.
Background technology
Different chroman-4-on is a kind of important chemicals, there is certain application in terms of medicine.Heterochromatic full oxidizing process
It is the effective ways for synthesizing different chroman-4-on.In the document of early stage, this method is once using sodium hypochlorite, tert-butyl hydroperoxide
Hydrogen is oxidant.Compared with these oxidants, oxygen inexpensively, and is generated without pollutant.Therefore, this aspect in recent years
Research focuses primarily upon the reaction that oxygen is oxidant.For example, once reported Fe (OTf) in chemist in 20142/ ligand
The method of heterochromatic full aerobic oxidation under catalysis, the target product that this method obtains（Different chroman-4-on）Yield be only 40%,
And uncommon ligand is used, it is difficult to industrial applications.Fe(NO3)3·9H2O/NHPI or Fe (NO3)3·9H2O/KPF6
Also once for the catalyst of aerobic oxidation reaction.Under the action of these catalyst systems, the yield of target product is able to
It effectively improves.Chemist in 2015 is once with tetramethyl piperidine nitrogen oxides/HCl/NaNO2For catalyst system, carry out
Heterochromatic full aerobic oxidation, to prepare different chroman-4-on.The tetramethyl piperidine nitrogen oxides that this obvious catalyst system uses
Higher price, and catalyst is complex, causes application cost higher.
The content of the invention
The purpose of the present invention is deficiencies to solve above-mentioned technical problem, provide a kind of preparation method of different chroman-4-on,
Using heterochromatic full and oxygen as raw material, using nitrogen dioxide as catalyst, it is more to overcome the discarded object generated in existing method, integrates
The problem of of high cost.
The deficiency of the present invention to solve above-mentioned technical problem, used technical solution are：A kind of system of different chroman-4-on
Preparation Method is completely dissolved in heterochromatic in organic solvent, adds in catalyst nitrogen dioxide, and is passed through oxygen, closed reactor, in 100-
0.5-5h is reacted at a temperature of 170 DEG C, different chroman-4-on is made, synthetic route is as follows：
；
As a kind of further optimization of the preparation method of different chroman-4-on of the present invention：The pressure of oxygen is 1- in reaction process
25atm。
As a kind of further optimization of the preparation method of different chroman-4-on of the present invention：In reaction process nitrogen dioxide with
The ratio between heterochromatic full amount of substance is：0.1-0.4:1.
As a kind of further optimization of the preparation method of different chroman-4-on of the present invention：The organic solvent is acetonitrile, first
Benzene, N,N-dimethylformamide or N-Methyl pyrrolidone.
Advantageous effect
（1）The preparation method of the present invention has used cheap and easily-available nitrogen dioxide catalyst, and catalyst low boiling point, can repeat
It utilizes, reduces the cost of catalyst；
（2）Product purity is high made from the preparation method of the present invention, and feed stock conversion is high, is effectively improved product quality, drops
Low production cost.
Description of the drawings：
Fig. 1 is the different chroman-4-on of product of embodiment 11H-NMR schemes；
Fig. 2 is the different chroman-4-on of product of embodiment 113C-NMR schemes.
Specific embodiment
Further technical scheme is illustrated below in conjunction with specific embodiment.
Embodiment 1
Air in the reaction tube of about 45 mL is replaced into 1atm oxygen, then adds in magneton, 2 mL acetonitriles, 0.5 mmol
Heterochromatic full and 0.1 mmol nitrogen dioxide.After reaction tube is sealed, it is placed into 140 DEG C of heating tank, under magnetic stirring
React 3h.Once reaching the reaction time, reaction system is cooled to room temperature, using gas chromatograph to scalar quantity in product progress
Analysis, the yield for drawing different chroman-4-on product are 73%.Then above-mentioned experiment is repeated, by pillar layer separation method to product
Separating-purifying is carried out, obtains different chroman-4-on product.It utilizes1H-NMR、13C-NMR determines that product structure is shown in Fig. 1 and 2.
Embodiment 2
Magneton, 2 mL acetonitriles, heterochromatic full, the 0.1 mmol nitrogen dioxide of 0.5 mmol are sequentially added in polytetrafluoroethylene (PTFE)
In the autoclave of lining, the oxygen of 5atm is passed through.After reaction kettle is sealed, it is placed into 140 DEG C of heating tank, is stirred in magnetic force
Mix lower reaction 3h.Once reaching the reaction time, reaction system is cooled to room temperature, internal standard is carried out to product using gas chromatograph
Quantitative analysis, the yield for drawing different chroman-4-on product are 66%.Then above-mentioned experiment is repeated, passes through pillar layer separation method pair
Product carries out separating-purifying, obtains different chroman-4-on product.
Embodiment 3-7
Oxygen pressure in embodiment 2 is become into 2atm, 10atm, 15atm, 20atm, 25atm, other conditions are constant, must produce
The yield of object（Gas phase internal standard）Respectively 75%, 61%, 55%, 60%, 52%.
Embodiment 8-11
By the quantitative change of the substance of the nitrogen dioxide in embodiment 1 be 0.05mmol, 0.1mmol, 0.15mmol, 0.2mmol, other
Condition is constant, draws the yield of product（Gas phase internal standard）Respectively 47%, 73%, 76%, 68%.
Embodiment 12-14
Acetonitrile in embodiment 1 is become into toluene, n,N-Dimethylformamide or N-Methyl pyrrolidone respectively, other conditions are not
Become, draw the yield of product（Gas phase internal standard）Respectively 61%, 27%, 42%.
Embodiment 15-22
By the reaction temperature in embodiment 1 become respectively 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C,
170 DEG C, other conditions are constant, draw the yield of product（Gas phase internal standard）Respectively 49%, 65%, 62%, 69%, 73%, 69%, 66%,
53%。
Embodiment 23-28
Reaction time in embodiment 1 is become into 0.5h, 1h, 2h, 3h, 4h, 5h respectively, other conditions are constant, draw product
Yield（Gas phase internal standard）Respectively 52%, 64%, 69%, 73%, 70%, 65%.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, though
So the present invention is disclosed above with preferred embodiment, however is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being without departing from technical solution of the present invention content, technical spirit pair according to the invention
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (4)
1. a kind of preparation method of different chroman-4-on, it is characterised in that：It is completely dissolved in heterochromatic in organic solvent, adds in catalyst
Nitrogen dioxide, and oxygen is passed through, closed reactor reacts 0.5-5h at a temperature of 100-170 DEG C, and different chroman-4-on is made.
2. a kind of preparation method of different chroman-4-on according to claim 1, it is characterised in that：Oxygen in reaction process
Pressure be 1-25atm.
3. a kind of preparation method of different chroman-4-on according to claim 1, it is characterised in that：Dioxy in reaction process
Changing the ratio between nitrogen and heterochromatic full amount of substance is：0.1-0.4:1.
4. a kind of preparation method of different chroman-4-on according to claim 1, it is characterised in that：The organic solvent is
Acetonitrile, toluene, N,N-dimethylformamide or N-Methyl pyrrolidone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711175821.9A CN108084140A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of different chroman-4-on |
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| CN201711175821.9A CN108084140A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of different chroman-4-on |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553601A (en) * | 2019-01-31 | 2019-04-02 | 河南科技大学 | A kind of no catalyst method prepares the process of the different chroman-4-on of 5- bromine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006079622A2 (en) * | 2005-01-28 | 2006-08-03 | Boehringer Ingelheim Pharma Gmbh & Co. Kg | Method for producing isochromane and derivatives thereof |
| CN101928244A (en) * | 2010-07-13 | 2010-12-29 | 中国药科大学 | Structural analogue and derivative of isochromanone-4 compound with cardiovascular activity, preparation method and application thereof |
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2017
- 2017-11-22 CN CN201711175821.9A patent/CN108084140A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006079622A2 (en) * | 2005-01-28 | 2006-08-03 | Boehringer Ingelheim Pharma Gmbh & Co. Kg | Method for producing isochromane and derivatives thereof |
| CN101928244A (en) * | 2010-07-13 | 2010-12-29 | 中国药科大学 | Structural analogue and derivative of isochromanone-4 compound with cardiovascular activity, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| PAOLO STRAZZOLINI等: "Oxidation of benzylic alcohols and ethers to carbonyl derivatives by nitric acid in dichloromethane", 《EUR. J. ORG. CHEM》 * |
| XINZHE TIAN等: "Nitric acid-catalyzed aerobic oxidation of benzylic sp3 C-H bonds of isochromans, xanthenes and 9-fluorenone under additive-free conditions", 《CATALYSIS COMMUNICATIONS》 * |
| ZHIGUANG ZHANG等: "Organocatalytic Aerobic Oxidation of Benzylic sp3 C-H Bonds of Ethers and Alkylarenes Promoted by a Recyclable TEMPO Catalyst", 《ORG. LETT.》 * |
| 田欣哲: "氮氧物种催化或自动氧化条件下苄基C-H键需氧氧化的研究", 《中国博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 |
|---|---|---|---|---|
| CN109553601A (en) * | 2019-01-31 | 2019-04-02 | 河南科技大学 | A kind of no catalyst method prepares the process of the different chroman-4-on of 5- bromine |
| CN109553601B (en) * | 2019-01-31 | 2020-11-10 | 河南科技大学 | Process method for preparing 5-bromoisochroman-4-ketone by catalyst-free method |
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