9-Bromo-9-phenylfluorene

Yellow Crystalline Solid

(1) Prepare a 10L reactor, add 6L of toluene first, and stir; at 20-25°C, Slowly add 9-phenyl-9-fluorenol (1kg, 3.87mol), stir and dissolve, the solution was milky white;(2) Add a solution of 48percent HBr (2.9L, 25.5mol) in one portion at 20-25°C.The reaction solution was light yellow and cloudy;(3) The reaction solution was heated to 50-60°C in a water bath, and the reaction was continued for 48 h and the color of the solution was gradually deepened;(4) GC confirmed the reaction, the main raw material 9-phenyl-9-sterol content of 3percent, the termination of the reaction;(5) Remove the water bath, cool to room temperature, and transfer the reaction solution to a 20L reactor for post-treatment: stirring and standing.The layers were separated; the lower aqueous phase was extracted once with 2 L of toluene, and the organic toluene solution was combined and washed sequentially with 4 L saturated sodium carbonate solution, 4 L water, once with 4 L saturated brine, and finally with the organic phase. 100G anhydrous magnesium sulfate dehydrated and dried;(6) After drying for 4 hours, the mixture was suction-filtered, and the filter cake was discarded. The filtrate was concentrated at 45° C. and concentrated to dryness to give a white solid.1.1kg, GC test purity content 96percent;(7) Recrystallization purification of 9-bromo-9-phenyl hydrazine: 1.1 kg of crude product is added to a 10 L reaction vessel, and 7 L of hexene is added.Alkane, stirring, and then heated to reflux, the solution was transparent, and then added 50G activated carbon decolorization, stirring 30min, 65 °C hot pressure filtration, naturally cooled to room temperature, the final ice salt bath was cooled to -5 ~ -10 °C, set aside for 4h The white crystals were obtained by suction filtration, and the wet weight was 1.25 kg. After vacuum drying at 50° C. for 12 hours, 1.02 kg of a yellow crystalline powder was obtained. The purity of the GC was 99percent, MP: 99 to 100° C., and the total yield was 82percent.(3) 250mL three-necked flask, 0.02 mol of intermediate W1 was added, Dissolved in 50 ml of toluene, Slowly add 48percent HBr aqueous solution (40ml)The reaction was stirred at 25 ° C for 24 hours, After the reaction liquid separation, The aqueous phase is extracted with toluene, After combining the organic phases with anhydrous sodium sulfate, Suction filtration, The filter cake was rinsed with ethyl acetate, The filtrate and rinse were swirled to solventless, After the silica gel column, Intermediate M1 was obtained, HPLC purity 99.4percentYield 73.5percent.250mL three-necked bottle, add 0.02mol intermediate W1, Dissolved in 50 ml of toluene, 48percent HBr aqueous solution (40 ml) was slowly added dropwise.Stir the reaction at 25 °C for 24 hours, Separating after the reaction, The aqueous phase is extracted with toluene.The organic phases were combined and dried over anhydrous sodium sulfate and suction filtered.The cake was rinsed with ethyl acetate and the filtrate and rinse were evaporated to solvent-free.The silica gel column gave intermediate Ml-I, HPLC purity 99.4percent, yield 73.5percent.

A bulky amine protecting reagent reported to be 6000 times more stable to acid than the trityl group

Molecular Weight:321.2
XLogP3:5.4
Rotatable Bond Count:1
Exact Mass:320.02006
Monoisotopic Mass:320.02006
Heavy Atom Count:20
Complexity:322
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes