CN109111351A - A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer - Google Patents
A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer Download PDFInfo
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- CN109111351A CN109111351A CN201710529926.3A CN201710529926A CN109111351A CN 109111351 A CN109111351 A CN 109111351A CN 201710529926 A CN201710529926 A CN 201710529926A CN 109111351 A CN109111351 A CN 109111351A
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer, belongs to technical field of organic synthetic chemistry.Crossover coupling reaction of the present invention by research 9- phenanthrene methyl ether under a variety of oxidants, a kind of synthetic method of the breakthrough 9- alkoxy phenanthrene dimer for proposing unsymmetric structure.In the method, inventor under specific acid condition, realizes 1 of 9- alkoxy phenanthrene and the direct construction method of C-C key of 9 ' positions, has obtained a series of 9,10 '-dialkoxy -1,9 '-join phenanthrene compounds by using persulfate as oxidant.The present invention technically provides a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer, such compound can be used for the design synthesis of novel chiral ligands and photoelectric material.9,10 '-dialkoxy -1, the yield of 9 '-Lian Fei products are 53%~64%.Nmr spectrum confirms product structure, and determines the above product purity > 95%.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthesis of asymmetry 9- alkoxy phenanthrene dimer
Method.
Background technique
Phenanthrene has unique planar structure, rigid structure and conjugated system, these properties make it shine
There is important researching value in the fields such as material, asymmetric syntheses.By literature survey, applicant have observed that 9- hydroxyl is luxuriant and rich with fragrance and its spreads out
The reaction site of biology usually occurs in 10 sites, and the design feature of this and phenanthrene itself is closely related.In this reaction property
Decisive role under, 9- hydroxyl is luxuriant and rich with fragrance and its derivative usually occur at 10 in the reaction of dimer synthon it is anti-with coupling
It answers, obtains the full symmetric 9- hydroxyl phenanthrene dimer of structure, as shown in Equation 1.
Since the active site of 9- hydroxyl phenanthrene derivative is 10, after being coupled by itself symmetry, on aromatic rings
The difficulty of further derivatization is very big, thus this kind of compound in asymmetric syntheses other than being applied, it is difficult to pass through
Further derivative obtains further types of new material.
In this context, applicant is by the oxidant of research different type oxidant and reacting for 9- alkoxy phenanthrene, most
Whole discovery can get the non-of 9- alkoxy phenanthrene by using persulfate to carry out oxidative coupling to alkoxy phenanthrene under acid system
Symmetry coupled product.The discovery all has not been reported in document and previous patent.This kind of compound remains 10 work
Property site, further types of phenanthrol derivative can be obtained by further derivative, and can also be converted to more and ring structures
Big conjugated system for the research of photoelectric material, thus has important researching value and application value.
Summary of the invention
The object of the present invention is to provide a kind of synthetic methods of asymmetry 9- alkoxy phenanthrene dimer, and synthetic method is such as
Shown in formula 2:
Specific steps are as follows:
(1) the 9- alkoxy that 0.2mmol is added into Schlenk pipe under nitrogen protection is luxuriant and rich with fragrance, and appropriate organic solvent is added
And stirring is completely dissolved substrate.
(2) in 0 DEG C of addition persulfate (1.0-10.0equiv.), and trifluoroacetic acid is added by the method for injection, protected
Hold nitrogen atmosphere.
(3) 1~3h is reacted under agitation, and thin-layer chromatography detection 9- phenanthrene methyl ether completely disappears.
(4) isometric water is added into reaction system and Na is added2CO3It neutralizes, extracts later, dry organic phase passes through
Column chromatography for separation is to pure coupled product.
Detailed description of the invention
Fig. 1: 9- phenanthrene methyl ether asymmetry dimer in embodiment 11H-NMR spectrum；
Fig. 2: 9- phenanthrene methyl ether asymmetry dimer in embodiment 113C-NMR spectrogram；
Fig. 3: 9- phenanthrene ether asymmetry dimer in embodiment 21H-NMR spectrum；
Fig. 4: 9- phenanthrene ether asymmetry dimer in embodiment 213C-NMR spectrogram；
Fig. 5: 9- phenanthrene propyl ether asymmetry dimer in embodiment 31H-NMR spectrum；
Fig. 6: 9- phenanthrene propyl ether asymmetry dimer in embodiment 313C-NMR spectrogram；
Specific embodiment
Illustrations are carried out to the present invention by the way of embodiment.Specific material proportion described in embodiment,
Process conditions and its result only play a role in the invention described, and the present invention should not will not be affected by the limitation of example.
Embodiment 1
It is added into reaction system etc. and 2mL water and Na is added2CO3Aqueous solution neutralizes, and extracts later, and dry organic phase passes through column chromatography point
From pure coupled product 9 is arrived, (9,10 '-dimethoxy -1,9 '-join by 10 '-dimethoxy-1,9 '-biphenanthrene
It is luxuriant and rich with fragrance) 26.5mg, yield 64%, magnetic resonance detection purity > 95%.
Embodiment 2
The 9- ethyoxyl that 0.2mmol is added into Schlenk pipe under nitrogen protection is luxuriant and rich with fragrance (0.0444g), and 1mL toluene is added and stirs
Mixing is completely dissolved substrate.Trifluoro second is added in 0 DEG C of addition potassium peroxydisulfate (5.0equiv., 0.270g), and by the method for injection
56%, magnetic resonance detection purity > 95%.
Embodiment 3
Under the conditions of react 1~3h, 0 DEG C of temperature, thin-layer chromatography detection 9- phenanthrene methyl ether completely disappear.The 2mL water such as addition into reaction system
And Na is added2CO3Aqueous solution neutralizes, and extracts later, dry organic phase, by column chromatography for separation to pure coupled product 9,
10 '-dipropoxy-1,9 '-biphenanthrene (9,10 '-dipropoxy -1,9 '-Lian Fei) 24.9mg, yield 53%, core
Magnetic resonance detects purity > 95%.
Claims (7)
1. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer, reaction equation are shown below:
2. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer described in claim 1, steps are as follows:
(1) the 9- alkoxy that 0.2mmol is added into Schlenk pipe under nitrogen protection is luxuriant and rich with fragrance, and appropriate organic solvent is added and stirs
Mixing is completely dissolved substrate.
(2) in 0 DEG C of addition persulfate (1.0-10.0equiv.), and trifluoroacetic acid is added by the method for injection, keeps nitrogen
Gas atmosphere.
(3) 1~3h is stirred to react between 0 DEG C~70 DEG C, thin-layer chromatography detection 9- phenanthrene methyl ether completely disappears.
(4) isometric water is added into reaction system and Na is added2CO3It neutralizes, extracts later, dry organic phase, pass through column layer
Analysis is separated to pure coupled product.
3. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer as claimed in claim 2, it is characterised in that: 9- alkane
C-C key, the name of gained compound formula are formed between 1 position C-H key of oxygroup phenanthrene and 10 ' positions of 9- alkoxy phenanthrene are as follows:
9,10 '-dialkoxy-1,9 '-biphenanthrene (9,10 '-dialkoxy -1,9 '-Lian Fei),
9,10 '-dimethoxy-1,9 '-biphenanthrene (9,10 '-dimethoxy -1,9 '-Lian Fei),
9,10 '-diethoxy-1,9 '-biphenanthrene (9,10 '-diethoxy -1,9 '-Lian Fei).
4. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer as described in claim 1, it is characterised in that: used
Substrate is that 9- alkoxy is luxuriant and rich with fragrance, and R represents alkyl, H, methyl, phenanthrene represent on tricyclic structure and tricyclic structure containing alkyl, aryl,
The luxuriant and rich with fragrance structure of methyl substituents.
5. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer as claimed in claim 2, it is characterised in that: step
(2) oxidant that reaction system uses in is persulfate, including but not limited to K2S2O8、Na2S2O8、(NH4)2S2O8。
6. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer as claimed in claim 2, it is characterised in that: step
(2) temperature of reaction system is between 0 DEG C~70 DEG C in.
7. a kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer as claimed in claim 2, it is characterised in that: step
(1) solvent described in is the mixed solvent of methylene chloride or chloroform or toluene and trifluoroacetic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521365A (en) * | 2020-11-06 | 2021-03-19 | 吉林大学 | Phenanthrene ketal with novel structure and degradation method thereof |
| CN115135631A (en) * | 2020-03-19 | 2022-09-30 | 帝人株式会社 | Polycyclic aromatic hydrocarbon compound, crystal thereof, and process for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144471A (en) * | 2011-01-11 | 2012-08-02 | Ryukoku Univ | Asymmetric phosphonite compound, asymmetric synthesis catalyst, method of manufacturing asymmetric phosphonite compound, and method of manufacturing organic compound having optical activity |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144471A (en) * | 2011-01-11 | 2012-08-02 | Ryukoku Univ | Asymmetric phosphonite compound, asymmetric synthesis catalyst, method of manufacturing asymmetric phosphonite compound, and method of manufacturing organic compound having optical activity |
Non-Patent Citations (2)
| Title |
|---|
| SHINOBU TAKIZAWA,等: "Vanadium in Asymmetric Synthesis:Emerging Concepts in Catalyst Design and Applications", 《CHEM. EUR. J.》 * |
| 翁文，等: "1, 1′-联萘化合物的氧化偶联合成", 《应用化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115135631A (en) * | 2020-03-19 | 2022-09-30 | 帝人株式会社 | Polycyclic aromatic hydrocarbon compound, crystal thereof, and process for producing the same |
| CN115135631B (en) * | 2020-03-19 | 2024-06-04 | 帝人株式会社 | Polycyclic aromatic hydrocarbon compound, crystal thereof, and method for producing same |
| CN112521365A (en) * | 2020-11-06 | 2021-03-19 | 吉林大学 | Phenanthrene ketal with novel structure and degradation method thereof |
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