3,6-BIS(TERT-BUTYL)CARBAZOLE

gray powder

9H- carbazole (1) (5.00g, 29.9mmol) in dichloromethane, chloride t- butyl (6.6ml, 59.8mmol) and aluminum chloride (4.00 g, 29.9 mmol) was added. After stirring for 24 hours at room temperature (25 , and so forth.), Poured into ice water (100mL). And extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered to give the solvent was distilled off under reduced pressure at room temperature from the filtrate the crude product. The crude product was recrystallized from petroleum ether, 3, 6-di-tert-butyl-9H-carbazole and (2a) 6.30 g (yield: 75percent) was obtained.To a mixture of carbazole (10 g, 60 mmol), anhydrous AlCl3 (8.0 g, 60 mmol) and CH2Cl2 (200 mL) in a 500 mL three-necked flask cooled to 0 °C was added dropwise a solution of t-BuCl (13.2 mL, 120 mmol) in CH2Cl2 (40 mL). After addition, the mixture was stirred for 10 min at the same temperature, then the ice bath was removed and the reaction was continued for 24 h. The mixture was then poured into ice-water (400 mL) and extracted with CH2Cl2. The combined organic phase was dried over MgSO4. After filtered, the filtration was evaporated to resulted a grey-white crude product which was recrystallized to afford white crystals (11.6 g, 69 percent); Rf = 0.71(PE : EtOAc = 3 : 1); M. p.: 228 - 230°C, (lit. 233 - 235 °C ); 1H NMR：(CDCl3, 500 MHz)δ: 8.09 (s, 2H), 7.83 (s, 1H), 7.47 (m, 2H), 7.33 (d, J = 8.45 Hz, 2H), 1.46 (s, 18H) which is accordance with those reported in literature .The process is commenced by placing about 10 g of carbazole (CCarbazole (5.016 g, 30 mmol) and AlCl3, 6-Di-tert-butyl-9-carbazole (I). Carbazole(5.0 g, 0.03 mol) was dissolved in 100 mL of CH2Cl2, cooled to 0°, and slowly added the solution of 2-chloro-2-methylpropane (6.6 mL, 0.06 mol) in 20 mLof CH2Cl2. AlCl3 (4.0 g, 0.03 mol) was introduced in small portions in the course of 1 h with constant stirring, and the reaction mixture was stirred for 8 h at room temperature. Then the flask was cooled with ice, 300 mL of water was added in small portions at stirring, the mixture was poured in 500 mL of water, extracted with CH2Cl2 (7 × 100 mL). The organic layer was washed with water, dried over Na2SO4, the solvent was removed on a rotary evaporator. The residue was thrice crystallized from hexane to give white crystalline powder. Yield 4.5 g (54 percent), mp 229–231C. IR spectrum, ν, cm–1: 3414 (NH), 3064 (Ph–H), 2960–2862 (CH3). 1H NMR spectrum, δ, ppm: 8.07 s (2H, Ar–H), 7.84 s (1, NH), 7.46 d (2H, Ar–H), 7.32 d(2, Ar–H), 1.45 s (18, –CH3). 13C NMR spectrum, δ, ppm: 143.2, 138.0, 123.5, 123.3, 116.1, 110.0, 34.7, 32.1. Mass spectrum, m/z: 279.19 [M]+. Found, percent: C85.25; H 9.89; N 6.16. C20H25N. Calculated, percent: C 85.97; H9.02; N 5.01.Carbazole (5.01 g, 30 mmol) and AlClTo a solution of carbazole (6.6g, 39.5 mmol) and zinc (II) chloride (16.2 g, 118.8 mmol) in nitromethane (100.0 ml) was added dropwise 2 -chloro-2- methylpropane (11.1 g, 120.0 mmol) under nitrogen a tmosphere and stirring. The addition of 2 -chloro-2-methylpropane was carried out over a 15 minute period. The mixture was stirred at room temperature for 24 hours. Water (100.0 ml) was then added. The product was extracted with dichloromethane (3 x 60. 0 ml). The organic layer was washed with water (3 x 100.0 ml), and then dried with MgSO (2) Carbazole (1.0 g, 6 mmol, 1.0 eq) and ZnCl2 (2.45 g, 18 mmol, 3.0 eq) were dissolved in 20 mL of nitromethane and protected with nitrogen. After stirring at room temperature for several minutes, Chlorinated tert-butane (1.7 g, 18 mmol, 3.0 eq) was injected with a syringeThe reaction system at room temperature for 5h. TCL plate test reaction, the reaction is complete, add water quenching, dichloromethane extraction 2 times, fullAnd salt water washing 2-3 times, anhydrous sodium sulfate drying. The solvent was dried under reduced pressure to give a crude product which was separated on silica gel and separated from silica gelParticle size of 200-300 mesh, eluent ratio of ethyl acetate / petroleum ether = 1: 20, the product 3, the yield of 40percent.ZnCl3a. Preparation of 3, 6-bis(l, l-dimethylethyl)-9H-carbazole. Synthesis of N-(4-fluorophenyl)-3, 6-bis[3, 6-tert-butyl-(carbazol-9-yl)]- carbazole3, 6-bis(tert-butyl) carbazole - tBuCzTo a suspension of 244 g (1.79 mol, 3.0 eq) of ZnClSynthetic Example 5Carbazole (61 .4g, 0.368 mol), anhydrous zinc chloride (Strem, 100.0 g, 0.734 mol), and 1210 ml nitromethane that was dried over activated 4A sieves overnight, was charged to an oven dried 2 liter pot with a mechanical stirrer, addition funnel and nitrogen inlet, t-butyl chloride (81 .1 ml, 0.734mol) was added drop wise at room temperature and the reaction was stirred overnight. The reaction was tracked by LCMS. After completion 200ml methanol was added and the mixture was stirred for one hour. Solvent was removed by rotoevaporation and the mixture was taken up in methylene chloride and washed with water. The methylene chloride was reduced to about 100g and about 300ml of methanol was added and the resulting mixture was stirred overnight and the precipitated solid was then filtered and dried for the first crop of product. The mother liquor was reduced and combined with hexanes for a second crop of product. 64.5g yield of off white solid

Molecular Weight:279.4
XLogP3:6.7
Hydrogen Bond Donor Count:1
Rotatable Bond Count:2
Exact Mass:279.198699802
Monoisotopic Mass:279.198699802
Topological Polar Surface Area:15.8
Heavy Atom Count:21
Complexity:336
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes