Preparation method of dibenzo [g, p] condensed dinaphthalene compound
A compound and equation technology, which is applied in the field of preparation of dibenzo[g,p] condensed dinaphthyl compounds, can solve the problems of high raw material manufacturing costs, many reaction intermediates and by-products, and difficulties in the separation and purification of finished products.
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[0060] The present invention provides a method for preparing the compound of formula 1, comprising: subjecting the compound of formula 7 to ring-closing reaction in the presence of an inorganic Lewis acid and an oxidizing agent to prepare the compound of formula 1, and the reaction equation is as follows:
[0061]
[0062] Wherein, R is selected from C1~C5 alkyl;
[0063] R 1 Selected from H, Cl, Br, C1~C5 alkyl, C1~C5 alkoxy, or phenyl;
[0064] R 2 Selected from H, Cl, Br, C1~C5 alkyl, C1~C5 alkoxy, or phenyl;
[0065] R 3 It is selected from H, Cl, Br, C1-C5 alkyl, C1-C5 alkoxy, or phenyl. The inventors of the present invention have provided a new preparation method of dibenzo[g,p] condensed dinaphthyl compound through a large amount of practical research. In the preparation method, an inorganic Lewis acid and an oxidizing agent are used to coordinate an arylation reaction. The compound of formula 7 can undergo ring closure to generate a large conjugated aromatic ri...
Embodiment 1
[0109] Preparation of phenanthrene-9-boronic acid:
[0110] Add 12.5g (0.514mol) metal magnesium and a grain of iodine to a 2000ml four-necked bottle, dissolve 120g (0.467mol) of 9-bromophenanthrene in 600ml THF, add it to a constant pressure dropping funnel, and add 50ml of this mixture dropwise to In the reaction flask, heat to initiate the format, after the initiation, control the temperature between 35°C and 65°C and add the remaining 9-bromophenanthrene solution dropwise, and then reflux and keep warm for 1 hour. Gas chromatography monitors the completion of the reaction of the raw materials. Lower the temperature of the system to -40°C, add dropwise a solution of 63g (0.607mol) trimethyl borate dissolved in 240ml THF, control the temperature to less than -25°C, keep it at this temperature for 1 hour after the dropwise addition, and then naturally rise to room temperature, Add hydrochloric acid dropwise to adjust PH = 1, separate layers, distill off THF under reduced pres...
Embodiment 2
[0113] Preparation of 6-methylphenanthrene-9-boronic acid:
[0114] Add 2.4g (0.100mol) metal magnesium, a grain of iodine, and 10ml MTHF into a 500ml four-necked bottle, dissolve 27.1g (0.100mol) of 6-methyl-9-bromophenanthrene in 27ml MTHF and 108ml toluene, and add constant pressure In the dropping funnel, drop 10ml of this mixture into the reaction bottle, heat to initiate the format, after the initiation, control the temperature between 50°C and 80°C and add the remaining 6-methyl-9-bromophenanthrene solution dropwise, and the dropwise Reflux for another 1 hour. Lower the temperature of the system to -40°C, add 10.9g (0.105mol) trimethyl borate dropwise, control the temperature to less than -25°C, keep warm at this temperature for 1 hour after the dropwise addition, and then naturally rise to room temperature, add hydrochloric acid dropwise to adjust the pH =1, separate layers, evaporate MTHF under reduced pressure, add water for beating, suction filtration, filter cake ...
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