CN106349027B - A kind of preparation method of high-order column aromatic hydrocarbons - Google Patents
A kind of preparation method of high-order column aromatic hydrocarbons Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of high-order column aromatic hydrocarbons, it include: by 2,5- diethoxy benzylalcohol or 2,5- diethoxy benzyl bromine, with lewis acid with the molar ratio of 1:1~1.5, in 25~30 DEG C of 3~8min of reaction, after reaction, crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons (n=5~10) of gained crude by column chromatography are concentrated under reduced pressure to obtain in reaction solution.This method does not need harsh reaction condition, does not need heating or inert gas shielding, the reaction time is short, energy saving；Catalyst choice range is wide；Interminable reaction step is avoided, without completely cutting off air, one-step method high yield prepares high-order column aromatic hydrocarbons at room temperature.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of to utilize 2,5- diethoxy benzylalcohol or 2,5- diethoxy
The method that benzyl bromine prepares high-order column aromatic hydrocarbons.
Background technique
Supramolecular chemistry is the intermolecular complexity formed by non-covalent interaction of research orderly and has specific function
One emerging cross discipline of the molecule aggregate of energy, macrocyclic host are one of the important foundations for constructing supramolecular chemistry.Crown ether,
The macrocyclic hosts such as cyclodextrin and calixarenes are known respectively as the first generation, the second generation and third generation supermolecule main block compound.
The emergence and development of every generation macrocyclic host all greatly enrich the content of supramolecular chemistry, and promote oversubscription
The development of sub- chemistry.Therefore, the novel macrocyclic host compound effect that performer holds the balance in supramolecular chemistry is prepared.
2008, contraposition analog-column aromatic hydrocarbons of calixarenes was reported as a new class of macrocycle molecule by synthesis for the first time.
Column aromatic hydrocarbons is to pass through a kind of cyclic oligomer that methylene bridge is formed by connecting in the contraposition of phenyl ring by hydroquinone or Hydroquinone ether
Object is a kind of novel macrocyclic host molecule.As a kind of novel macrocyclic host molecule, column aromatic hydrocarbons is in recent years increasingly by people
Concern.
The structure of column aromatic hydrocarbons is similar to calixarenes, but it possesses higher symmetry and rigidity compared to calixarenes.This
One structure assigns its distinguished interesting physics, chemistry and host and guest's volume property.Up to the present, column [5] aromatic hydrocarbons and column [6]
Synthesis, conformation change, derivatization, host and guest's volume property and the self assembly of aromatic hydrocarbons have all been widely studied, and the height of bigger cavity
Rank column aromatic hydrocarbons, that is, column [7] aromatic hydrocarbons, column [8] aromatic hydrocarbons, column [9] aromatic hydrocarbons and column [10] aromatic hydrocarbons are then ground since its synthesis separation is more difficult
Study carefully relatively fewer.
The synthesis of column aromatic hydrocarbons and method of modifying are versatile and flexible, on synthesis path there are mainly two types of: one is synthesize first
Then cyclic annular column aromatic hydrocarbons parent is modified by parent of the methodology of organic synthesis to existing column aromatic hydrocarbons and (" is first repaired after cyclization
Decorations ")；Another kind is to be modified first synthesis precursor (i.e. monomer, aromatic hydrocarbons substrate), then uses the precursor modified, into
Target ring-type column aromatic compound needed for one-step synthesis (i.e. " cyclization after first modifying ").Wherein, in latter path, there are also two
The different synthetic strategy of kind: one is use single precursor synthesis of cyclic target product；Another kind is closed using mixing precursor
Circlewise target product.
Ogoshi (J.Am.Chem.Soc. [J], 2008,130 (15): 5022-5023) is in lewis acid (BF3·OEt2)
Catalysis is lower to have synthesized Isosorbide-5-Nitrae-diformazan pilum [5] aromatic hydrocarbons by the reaction of Hydroquinone ether and paraformaldehyde, but the reaction at room temperature
Yield is relatively low, and yield only has 22%.
Huang Fei crane (Chem.Commun., 2011,47 (45): 12340-12342) discloses a kind of water-soluble column aromatic hydrocarbons point
The preparation of son.Using Isosorbide-5-Nitrae-dibromo ethoxybenzene and paraformaldehyde as raw material, Isosorbide-5-Nitrae-dibromo is made under boron trifluoride ether catalysis
The column aromatic hydrocarbon molecule that ethyoxyl replaces, further reacts with trimethylamine, water-soluble ammonium salt can be generated.
The Chinese patent literature of 103396298 A of Publication No. CN discloses a kind of functionalization column [n] arene derivatives
Preparation method, this method are prepared for one using micro sulfonic acid as the cyclization reaction of catalyst Hydroquinone ether and paraformaldehyde
Column [n] arene derivatives of serial global function and single function.
With the development and deeply of column aromatic hydrocarbons research, people need to synthesize the column aromatic hydrocarbons of various different cavity sizes for grinding
Study carefully.This just proposes requirement to the synthesis of high-order column aromatic hydrocarbons.Currently, there are low yield, experiment conditions for the synthesis of high-order column aromatic hydrocarbons
Harsh problem, therefore, the method for preparing high-order column aromatic hydrocarbons of higher yields that can be easy is just at the task of top priority.
Summary of the invention
The purpose of the present invention is being directed to the existing method for preparing high-order column aromatic hydrocarbons, provides and a kind of utilize 2,5-
The method that diethoxy benzylalcohol or 2,5- diethoxy benzyl bromine prepare high-order column aromatic hydrocarbons.
A kind of preparation method of high-order column aromatic hydrocarbons, comprising: by 2,5- diethoxy benzylalcohol or 2,5- diethoxy benzyl bromine adds
Enter in solvent, lewis acid is added, 3~8min of reaction under the conditions of 25~30 DEG C, 2, the 5- diethoxy benzylalcohol or 2,
5- diethoxy benzyl bromine and lewis acidic molar ratio are 1:1~1.5, and after reaction, reaction solution is concentrated under reduced pressure slightly to produce
Object, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography, the knot of double diethoxy pilum [n] aromatic hydrocarbons
Structure Formulas I is as follows:
Wherein, n=5~10.
The high-order column aromatic hydrocarbons is specially column [7] aromatic hydrocarbons, column [8] aromatic hydrocarbons, column [9] aromatic hydrocarbons and column [10] aromatic hydrocarbons.
The method according to the present invention for utilizing 2,5- diethoxy benzylalcohol to prepare high-order column aromatic hydrocarbons, reaction equation is such as
Under:
With 2,5- diethoxy benzylalcohol be reaction raw materials when, the lewis acid be FeCl3、AlCl3、SnCl4Or BF3·O
(C2H5)2.Use FeCl3、AlCl3、SnCl4Or BF3·O(C2H5)2When as catalyst, the reaction time is short, it is only necessary to 3~8min
Reaction is completed, when using other lewis acids such as ZnCl2When as catalyst, reaction carries out slowly, needing 10h or more, and mesh
The yield for marking product is lower.
Preferably, 5- diethoxy benzylalcohol is added in solvent by 2, FeCl is added3, 3 are reacted under the conditions of 25~30 DEG C
~5min, 2,5- diethoxy benzylalcohols and FeCl3Molar ratio be 1:1~1.5, after reaction, reaction solution is through being concentrated under reduced pressure
Obtain crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography.
Preferably, 5- diethoxy benzylalcohol is added in solvent by 2, AlCl is added3, 3 are reacted under the conditions of 25~30 DEG C
~5min, 2,5- diethoxy benzylalcohols and AlCl3Molar ratio be 1:1~1.5, after reaction, reaction solution is through being concentrated under reduced pressure
Obtain crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography.
The method according to the present invention for utilizing 2,5- diethoxy benzyl bromine to prepare high-order column aromatic hydrocarbons, reaction equation is such as
Under:
With 2,5- diethoxy benzyl bromine be reaction raw materials when, the lewis acid be FeCl3、AlCl3、ZnCl2Or SnCl4。
Preferably, the lewis acid is ZnCl2。ZnCl2When as catalyst, the yield highest of target product, when using other roads
Lewis acid such as BF3·O(C2H5)2When as catalyst, the target product of trace can only obtain.
Preferably, 5- diethoxy benzyl bromine is added in solvent by 2, ZnCl is added2, 3 are reacted under the conditions of 25~30 DEG C
~5min, 2,5- diethoxy benzyl bromines and ZnCl2Molar ratio be 1:1~1.5, after reaction, reaction solution is through being concentrated under reduced pressure
Obtain crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography.
Preferably, 5- diethoxy benzyl bromine is added in methylene chloride by 2, FeCl is added3, under the conditions of 25~29 DEG C
React 3~5min, 2,5- diethoxy benzyl bromines and FeCl3Molar ratio be 1:1~1.5, after reaction, reaction solution is through depressurizing
It is concentrated to give crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography.
The preparation method of the high-order column aromatic hydrocarbons, reaction temperature are 25~30 DEG C, and the reaction time is 3~8min.As excellent
Choosing, reaction time are 3~5min.Between when reacted more than 5min after, double ethoxy pilum aromatic hydrocarbons (the double diethoxy pilums [7] of high-order
Aromatic hydrocarbons, double diethoxy pilums [8] aromatic hydrocarbons, double diethoxy pilum [9] aromatic hydrocarbons and double diethoxy pilum [10] aromatic hydrocarbons) yield can under
Drop；When the time extending to 10~15min, primary product is double diethoxy pilum [5] aromatic hydrocarbons and double diethoxy pilum [6] virtues
Hydrocarbon, and it is unable to get the double ethoxy pilum aromatic hydrocarbons of high-order；After the time extending to 15min, polymer easy to form is generated double
Diethoxy pilum [n] aromatic hydrocarbons (n=5~10) can also decompose, and finally be unable to get double diethoxy pilum [n] aromatic hydrocarbons.
The solvent is methylene chloride, 1,2- dichloroethanes or chloroform.Preferably, the solvent is methylene chloride.When
When solvent is methylene chloride, reaction can be carried out in room temperature, and the reaction time is short；When solvent is 1,2- dichloroethanes or chloroform
When, the yield of target product can reduce, and need to improve temperature or extend the reaction time.
In the reaction, 2,5- diethoxy benzylalcohols or 2, the concentration of 5- diethoxy benzyl bromine in a solvent be 0.05~
0.2mol/L.Preferably, 2,5- diethoxy benzylalcohols or 2, the concentration of 5- diethoxy benzyl bromine in a solvent is 0.1mol/L.
If the excessive concentration of reaction raw materials, polymer easy to form cannot get double diethoxy pilum [n] aromatic hydrocarbons, if concentration is too low,
Reaction time long low efficiency.
Compared with prior art, the invention has the following advantages: preparation method is easy, reaction condition is mild, is not required to
It heats or inert gas shielding, the reaction time is short, energy saving；Catalyst choice range is wide, and can choose
FeCl3、AlCl3The solid of cheap and easy to get in this way and non-volatile toxicity is environmentally protective as catalyst.
Specific embodiment:
Embodiment 1
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzylalcohol
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 200mL methylene chloride, and BF is added3·O
(C2H5)2(20.0~20.5mmol), mixed liquor are stirred 3~4 minutes at 30 DEG C, are washed with deionized twice, and organic phase is used
Anhydrous sodium sulfate is dry, is concentrated under reduced pressure to give crude product, crude product with flash column chromatography (petrol ether/ethyl acetate
Volume ratio=30:1) obtain double diethoxy pilum [5] aromatic hydrocarbons (0.71g, yield 19.8%), double diethoxy pilums [6] aromatic hydrocarbons
(0.27g, yield 7.5%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] virtue
Hydrocarbon (0.03g, yield 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10]
Aromatic hydrocarbons (0.06g, yield 1.7%), they are all white solid.
The characterize data of product manufactured in the present embodiment is as follows:
Double diethoxy pilum [7] aromatic hydrocarbons:
Fusing point: 154.2~155.6 DEG C
1H NMR(400MHz,CDCl3, 298K): δ 6.63 (s, 14H), 3.843.79 (m, 42H), 1.23 (t, J=
6.4Hz,42H).
13C NMR(100MHz,CDCl3,298K):δ150.4,127.8,115.2,64.3,31.1,15.0.
MS(ESI):m/z 1269[M+Na]+.
Elemental analysis: theoretical value: C, 74.13；H,7.92；Experiment value: C, 74.16；H,7.87.
Double diethoxy pilum [8] aromatic hydrocarbons:
Fusing point: 205.6~206.8 DEG C of
1H NMR(400MHz,CDCl3, 298K): δ 6.63 (s, 16H), 3.843.80 (m, 48H), 1.23 (t, J=
6.4Hz,48H).
13C NMR(100MHz,CDCl3,298K):δ150.6,127.8,114.9,64.2,30.4,15.0.
MS(ESI):m/z 1448[M+Na]+.
Elemental analysis: theoretical value: C, 74.13；H,7.92；Experiment value: C, 74.18；H,7.88.
Double diethoxy pilum [9] aromatic hydrocarbons:
Fusing point: 84.8~85.9 DEG C of
1H NMR(400MHz,CDCl3, 298K): δ 6.63 (s, 18H), 3.843.80 (m, 54H), 1.23 (t, J=
6.4Hz,54H).
13C NMR(100MHz,CDCl3,298K):δ150.4,127.9,114.9,64.1,30.0,15.1.
MS(ESI):m/z 1627[M+Na]+.
Elemental analysis: theoretical value: C, 74.13；H,7.92；Experiment value: C, 73.89；H,7.95.
Double diethoxy pilum [10] aromatic hydrocarbons:
Fusing point: 86.7~87.5 DEG C of
1H NMR(400MHz,CDCl3, 298K): δ 6.65 (s, 20H), 3.833.82 (m, 60H), 1.26 (t, J=
6.4Hz,60H).
13C NMR(100MHz,CDCl3,298K):δ150.5,127.9,114.9,64.2,30.0,15.1.
MS(ESI):m/z 1805[M+Na]+.
Elemental analysis: theoretical value: C, 74.13；H,7.92；Experiment value: C, 73.89；H,7.95.
Embodiment 2
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzylalcohol
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 300mL methylene chloride, and FeCl is added3(20.0
~20.5mmol), mixed liquor stirs 4~5 minutes at 25 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.69g, yield 19.3%), double diethoxy pilums [6] aromatic hydrocarbons (0.28g, yield are obtained
For 7.8%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.06g,
Yield is that 1.7%), they are all white solid.
Embodiment 3
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzylalcohol
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 400mL methylene chloride, and AlCl is added3(20.0
~20.5mmol), mixed liquor stirs 7~8 minutes at 25 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.80g, yield 22.3%), double diethoxy pilums [6] aromatic hydrocarbons (0.34g, yield are obtained
For 9.8%), double diethoxy pilums [7] aromatic hydrocarbons (0.06g, yield 1.6%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.04g, yield 1.1%), double diethoxy pilums [10] aromatic hydrocarbons (0.04g,
Yield is that 1.1%), they are all white solid.
Embodiment 4
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzylalcohol
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 200mL methylene chloride, and SnCl is added4(20.0
~20.5mmol), mixed liquor stirs 3~4 minutes at 28 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.82g, yield 22.9%), double diethoxy pilums [6] aromatic hydrocarbons (0.29g, yield are obtained
For 8.1%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.06g,
Yield is that 1.7%), they are all white solid.
Embodiment 5
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzyl bromine
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 200mL methylene chloride, and FeCl is added3(20.0
~20.5mmol), mixed liquor stirs 3~4 minutes at 30 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.73g, yield 20.4%), double diethoxy pilums [6] aromatic hydrocarbons (0.29g, yield are obtained
For 8.1%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.06g,
Yield is that 1.7%), they are all white solid.
Embodiment 6
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzyl bromine
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 100mL methylene chloride, and ZnCl is added2(20.0
~20.5mmol), mixed liquor stirs 3~4 minutes at 28 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.82g, yield 22.9%), double diethoxy pilums [6] aromatic hydrocarbons (0.27g, yield are obtained
For 7.8%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.06g,
Yield is that 1.7%), they are all white solid.
Embodiment 7
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzyl bromine
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 200mL methylene chloride, and SnCl is added4(20.0
~20.5mmol), mixed liquor stirs 5~6 minutes at 25 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.75g, yield 20.9%), double diethoxy pilums [6] aromatic hydrocarbons (0.29g, yield are obtained
For 8.1%), double diethoxy pilums [7] aromatic hydrocarbons (0.07g, yield 1.9%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.05g,
Yield is that 1.4%), they are all white solid.
Embodiment 8
High-order column aromatic hydrocarbons is prepared using 2,5- diethoxy benzyl bromine
2,5- diethoxy benzylalcohol (3.92g, 20.0mmol) is added in 200mL methylene chloride, and AlCl is added3(20.0
~20.5mmol), mixed liquor stirs 4~5 minutes at 26 DEG C, is washed with deionized twice, organic phase anhydrous sodium sulfate
It is dry, be concentrated under reduced pressure to give crude product, crude product with flash column chromatography (volume ratio=30 of petrol ether/ethyl acetate:
1) double diethoxy pilum [5] aromatic hydrocarbons (0.70g, yield 19.6%), double diethoxy pilums [6] aromatic hydrocarbons (0.27g, yield are obtained
For 7.8%), double diethoxy pilums [7] aromatic hydrocarbons (0.08g, yield 2.2%), double diethoxy pilums [8] aromatic hydrocarbons (0.03g, produce
Rate be 0.8%), double diethoxy pilums [9] aromatic hydrocarbons (0.06g, yield 1.7%), double diethoxy pilums [10] aromatic hydrocarbons (0.06g,
Yield is that 1.7%), they are all white solid.
Comparative example 1
Compared with Example 1, other conditions are constant, reaction time 10min, then obtain double diethoxy pilum [5] aromatic hydrocarbons
(1.20g, yield 27%), double diethoxy pilums [6] aromatic hydrocarbons (0.43g, yield 13%) they be all white solid.
Comparative example 2
Compared with Example 5, other conditions are constant, reaction time 15min, then obtain double diethoxy pilum [5] aromatic hydrocarbons
(0.49g, yield 14%), double diethoxy pilums [6] aromatic hydrocarbons (0.28g, yield 8%) they be all white solid.
By comparative example it is found that with the reaction time growth, double diethoxy pilum [n] aromatic hydrocarbons of product gradually decompose, are formed
The content of polymer, polymer gradually increases, after reaction to 10min, only double diethoxy pilum [5] aromatic hydrocarbons of product and double diethyls
Oxygroup column [6] aromatic hydrocarbons is unable to get the double diethoxy pilum aromatic hydrocarbons of high-order.
Claims (10)
1. a kind of preparation method of high-order column aromatic hydrocarbons characterized by comprising by 2,5- diethoxy benzylalcohol or 2,5- diethoxy
Base benzyl bromine is added in solvent, and lewis acid is added, and 3~8min, 2, the 5- diethoxy are reacted under the conditions of 25~30 DEG C
Benzylalcohol or 2,5- diethoxy benzyl bromine and lewis acidic molar ratio are 1:1~1.5, and after reaction, reaction solution is dense through depressurizing
Contract to obtain crude product, isolated double diethoxy pilum [n] aromatic hydrocarbons of gained crude by column chromatography, double diethoxy pilums [n]
The structural formula I of aromatic hydrocarbons is as follows:
Wherein, n=5~10；
The high-order column aromatic hydrocarbons is specially column [7] aromatic hydrocarbons, column [8] aromatic hydrocarbons, column [9] aromatic hydrocarbons and column [10] aromatic hydrocarbons.
2. the preparation method of high-order column aromatic hydrocarbons according to claim 1, which is characterized in that with 2,5- diethoxy benzylalcohol be anti-
When answering raw material, the lewis acid is FeCl3、AlCl3、SnCl4Or BF3·O(C2H5)2。
3. the preparation method of high-order column aromatic hydrocarbons according to claim 1, which is characterized in that with 2,5- diethoxy benzyl bromine be anti-
When answering raw material, the lewis acid is FeCl3、AlCl3、ZnCl2Or SnCl4。
4. the preparation method of high-order column aromatic hydrocarbons according to claim 1, which is characterized in that the solvent be methylene chloride, 1,
2- dichloroethanes or chloroform.
5. the preparation method of high-order column aromatic hydrocarbons according to claim 1 or 4, which is characterized in that the solvent is dichloromethane
Alkane.
6. the preparation method of high-order column aromatic hydrocarbons according to claim 1, which is characterized in that the time of the reaction be 3~
5min。
7. the preparation method of high-order column aromatic hydrocarbons according to claim 1 characterized by comprising by 2,5- diethoxy benzyl
Alcohol is added in solvent, and FeCl is added3, 3~5min, 2,5- diethoxy benzylalcohols and FeCl are reacted under the conditions of 25~30 DEG C3Rub
You are than being 1:1~1.5, and after reaction, crude product is concentrated under reduced pressure to obtain in reaction solution, and gained crude by column chromatography is isolated
Double diethoxy pilum [n] aromatic hydrocarbons.
8. the preparation method of high-order column aromatic hydrocarbons according to claim 1 characterized by comprising by 2,5- diethoxy benzyl
Alcohol is added in solvent, and AlCl is added3, 3~5min, 2,5- diethoxy benzylalcohols and AlCl are reacted under the conditions of 25~30 DEG C3Rub
You are than being 1:1~1.5, and after reaction, crude product is concentrated under reduced pressure to obtain in reaction solution, and gained crude by column chromatography is isolated
Double diethoxy pilum [n] aromatic hydrocarbons.
9. the preparation method of high-order column aromatic hydrocarbons according to claim 1 characterized by comprising by 2,5- diethoxy benzyl
Bromine is added in solvent, and ZnCl is added2, 3~5min, 2,5- diethoxy benzyl bromines and ZnCl are reacted under the conditions of 25~30 DEG C2Rub
You are than being 1:1~1.5, and after reaction, crude product is concentrated under reduced pressure to obtain in reaction solution, and gained crude by column chromatography is isolated
Double diethoxy pilum [n] aromatic hydrocarbons.
10. the preparation method of high-order column aromatic hydrocarbons according to claim 1 characterized by comprising by 2,5- diethoxy benzyl
Bromine is added in methylene chloride, and FeCl is added3, 3~5min, 2,5- diethoxy benzyl bromines and FeCl are reacted under the conditions of 25~29 DEG C3
Molar ratio be 1:1~1.5, after reaction, reaction solution is concentrated under reduced pressure to obtain crude product, the separation of gained crude by column chromatography
Obtain double diethoxy pilum [n] aromatic hydrocarbons.
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| CN111303084B (en) * | 2020-03-12 | 2021-10-29 | 浙江大学 | Method for separating 2-methylfuran and 2, 5-dimethylfuran |
| CN112608245A (en) * | 2020-12-11 | 2021-04-06 | 华南理工大学 | Cationic water-soluble inclined column [6] arene and synthetic method thereof |
| CN115337913B (en) * | 2022-08-09 | 2024-03-22 | 浙江大学杭州国际科创中心 | Catechu [9] arene, and preparation method and application thereof |
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