4-BROMO-2,6-BIS(1-METHYLETHYL)BENZENAMINE

White solid

A solution of NBS (24.59 g, 137 mmol) in DMF (160 mL) was added slowly to a solution of 2, 6-diisopropylaniline (25 g, 137 mmol) in DMF (300 mL) at 0-5°C under a nitrogen atmosphere over a period of 20 minutes. The reaction mixture was stirred at 0-5°C. After the reaction was complete, water was added and the oil suspension was stirred at rt. The aqueous layer was decanted out and the remaining oil was dissolved in ethyl acetate. The organic layer was separated, washed water and brine.Evaporation gave light brown oil (35.1 g, 100percent yield).To a stirred solution of 2, 6-diisopropylaniline (14 g, 78.97 mmol, 1.00 equiv) in N, N-dimethylformamide (200 mL) at 0° C. was added a solution of NBS (14 g, 78.65 mmol, 1.00 equiv) in N, N-dimethylformamide (100 mL) dropwise in 60 min. Synthesis of 4-bromo-2, 6-diisopropylaniline (0199) A three neck round bottom flask was charged with 2, 6-diisopropylaniline (22.96 g, 130 mmol) and DMF (Volume: 250 ml). A solution of 1-bromopyrrolidine-2, 5-dione (23.05 g, 130 mmol) in 100 ml DMF was added into reaction mixture drop wise at 0° C. After addition was over; reaction mixture was stirred for 2 days at room temperature. The reaction mixture was poured into 500 ml deionized water and extracted with 3×150 ml ether. The combined extracts were washed with 150 ml deionized water, 150 ml 10percent lithium chloride, dried over MgSO40.8 g (85 mmol) of tetra-n-butylammonium tribromide are added, at 0° C. and portionwise, to a solution of 15 g (85 mmol) of 2, 6-diisopropylphenyl-amine in 200 ml of tetrahydrofuran. Preparative Example P16Step 1 : 4-Bromo-2, 6-diisopropylaniline (PI 6a)To a solution of 2, 6-diisopropylaniline (12.5 g, 70.6 mmol) in THF was added (CA solution of 2, [6-DIISOPROPYLANILINE] (2.0 mL, 11 mmol) in methanol (80 mL) was treated dropwise with bromine (543 μL, 10.6 mmol). The solution was stirred at room temperature for 15 min. Chloroform and 0.1 N [NAOH] were added and the organic layer was dried (Na2SO4), filtered and concentrated to an orange liquid. Kugelrohr distillation [(110 °C COMMAT; ] 0.06 Torr) afforded a colorless liquid (2.22 g 79percent): 1H NMR (400 MHz) 8 1.25 (d, J= 6.4 Hz, 12H), 2. 88 (m, 2H), 3.70 (brs, 2H), 7.11 (s, 2H) [; 13C NMR 8] 22.1, 27.9, 111.0, 125.6, 134.5, 139.3 ; Anal calcd for [C12HIGBRN] : C, 56.26 ; H, 7. 08 ; Br, 31.19 ; Found, C, 56.24 ; H, 7.07 ; Br, 30.98A solution of Br2(2.1 ml, 41.0 mmol, 1.05 eq.) in CH2Cl2/MeOH (100 ml, 1:1 v/v)was added to a stirring solution of 2, 6-diisopropylaniline (7.4 ml, 39.0 mmol, 1.0 eq.) in CH2Cl2/MeOH (200 ml, 1:1 v/v) at r.t. over2 h. The orange-red solution was stirred for 1 day. The solvents were evaporated and the resultant pink solid was washed with PE and further recristallized from CH2Cl2/PE to give the title compound as light orange-red solid (7.8 g, 28.1 mmol, 72percent).1H-NMR (300 MHz, CDCl3) [ppm]: 10.08 (s, 2H), 7.36 (s, 2H), 3.80–3.62 (m, 2H), 1.29(d, J = 6.7 Hz, 12H). The analytical data are in accordance with theliterature.4-Bromo-2, 6-diisopropylaniline Apparatus set-up:A 10 L 3-necked round-bottomed flask, equipped with a mechanical overhead stirrer, nitrogen inlet and exhaust.Experimental Procedure:1. 2, 6-Diisopropyl aniline (500 g, 2.8202 mol) was dissolved in dry N, N-dimethyl formamide.It was cooled to 0 °C using an ice bath.2. N-Bromosuccinimide (501.9 g, 2.8202 mol) was added slowly portion wise.3. The reaction mixture was stirred at the room temperature for 18 h.4. After 18 h, TLC showed complete conversion of starting material.5. To the mixture, 10percent NaHCO3 solution (4 L) was added and extracted with ethyl acetate (3 x2L).6. The combined organic phase was washed with water (1 L), brine (1 L), dried over sodium sulphate and concentrated.7. The crude product was purified by silica column chromatography using 8 percent ethyl acetate in hexane as an eluent to get 540 g with 95.75 percent HPLC purity. 1H-NMR (300 MHz, CDCl3): δ[ppm] 1.26 (d, J = 6.78 Hz, 12H), 2.84 - 2.93 (m, 2H), 3.72 (br, s, 2H), 7.12 (s, 2H).5. N, N'-Bis(4-bromo-2, 6-diisopropylphenyl)-1, 6, 7, 12-tetrachloro-3, 4, 9, 10-tetracarboxylic acid diimide 10 g (0.019 mol) of 1, 6, 7, 12-tetrachloroperylene-3, 4, 9, 10-tetracarboxylic dianhydride, 24.16 g (0.094 mol) of Dry nitrogen gas was bubbled into a mixture of Apparatus set-up:A 5 L 3-necked round-bottomed flask, equipped with a mechanical overhead stirrer, nitrogen inlet and exhaust.Experimental Procedure:1. Intermediate 7 (250 g, 0.9758 mol), phenyl boronic acid (178.4 g, 1.4637 mol), potassium phosphate (827.9 g, 3.903 mol) were taken in toluene (2.5 L).2. The mixture was degassed for 30 mm.3. Pd(dba) (26.38 g, 0.0292 mol) and 5-Phos (12 g, 0.0292 mol) were added to the reaction mixture and heated to 110 °C for 36 h.4. After 36 h, TLC monitoring showed complete conversion of starting material.5. The reaction mixture was filtered through celite and the organic phase was washed with water (1 L), brine (1 L), dried over sodium sulphate and concentrated.6. The crude product (310 g) was purified thrice by flash column chromatography using7 to 10 percent ethyl acetate in hexane as an eluent to get 163 g of intermediate-8. 1H-NMR (300 MHz, CDCl3): delta [ppm] 1.34 (d, J = 6.81 Hz, 12H), 3.03 (m, 2H), 7.23-7.32 (m, 3H), 7.40 ' 7.45 (m, 2H), 7.58-7.6 1 (m, 2H).

Molecular Weight:256.18
XLogP3:4.2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:255.06226
Monoisotopic Mass:255.06226
Topological Polar Surface Area:26
Heavy Atom Count:14
Complexity:161
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes