A kind of preparation method of 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene
A technology of dihydroindene and tetramethyl, applied in the field of organic synthesis, can solve the problems of complicated operation, harsh conditions, low yield and the like
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[0039] According to the preparation method of 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene of the present invention, the method comprises:
[0040] Coupling reaction: use 1 equivalent of o-bromoacetophenone and 1-1.4 equivalents of 9,9-dimethylfluorene-2-boronic acid for coupling reaction to generate the compound shown in formula M-1;
[0041] Wittig reaction: the compound shown in formula M-1 and methyltriphenylphosphonium bromide undergo Wittig reaction to generate the compound shown in formula M-2;
[0042] Cyclization reaction: The compound represented by formula M-2 undergoes a cyclization reaction in the presence of 3 to 16 equivalents of acid, and is converted into 6,6,12,12-tetramethyl-6,12-dihydro represented by formula M Indeno[1,2-b]fluorene;
[0043]
[0044] In the preparation method of 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene of the present invention, the preparation method includes coupling reaction, Wittig reaction, ring closure re...
Embodiment 1
[0058] The synthetic route is as follows:
[0059]
[0060] According to the preparation method of 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene of the present invention, the reaction is carried out in three steps:
[0061] (1) Coupling reaction
[0062] 2000 ml there-necked flask, add 19.9 grams (0.1mol, 1eq) o-bromoacetophenone, 26.18 grams (0.11mol, 1.1eq) 9,9-dimethylfluorene-2-boronic acid, 42.4 grams (0.2mol, 2eq) Anhydrous potassium phosphate, 500ml DMF, add 1.06g (0.001mol, 0.01eq) palladium tetrakistriphenylphosphine under the protection of nitrogen, slowly heat to 70-80°C for 8 hours, cool down, add water and toluene to separate the liquid, the water layer Extract once with toluene, combine the organic layers, wash the organic layer with water, wash with saturated brine, dry over anhydrous sodium sulfate, decolorize the silica gel column, concentrate the eluate to dryness, add 300 ml of tetrahydrofuran to obtain tetrahydrofuran containing the compound s...
Embodiment 2
[0070] The synthesis method is the same as in Example 1, except that the amount of 9,9-dimethylfluorene-2-boronic acid used in the first step coupling reaction is changed to 0.12 mol to obtain 23.90 g of the product with a yield of 77.10%.
[0071] The obtained product was carried out 1 HNMR detection, 1 The HNMR spectrum analysis data is as follows: 1 HNMR (500MHz, CDCl 3 ): 8.07 (m, 2H), 7.98 (s, 2H), 7.55 (m, 2H), 7.44 (m, 2H), 7.28 (m, 2H), 1.70 (2, 12H).
[0072] The obtained product was detected by mass spectrometry, and the obtained m / e value was 310.
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