2-Iodo-9H-fluorene

White powder

Synthesis of 2-iodofluorene: Fluorene (30.0 g, 180 mmol) was dissolved in a boiling solvent (acetic acid: water: sulfuric acid / 100:20:3(v/v/v))to prepare a first mixed solution, and then periodic acid dehydrate (8.0 g, 45 mmol) and iodine (23.0 g, 91.0 mmol) wereadded to the first mixed solution to prepare a second mixed solution. Then, the second mixed solution was stirred at65h for 4 hours to obtain a precipitate. The precipitate was filtered and then washed with a 2N aqueous sodium carbonatesolution and water to obtain crystals. The crystals were recrystallized by hexane. The yield ofthe product was 72percent.1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 3.81(2H, s, -CH2), 7.31(2H, m, Ar-H), 7.44(2H, m, Ar-H), 7.66(1H, d, Ar-H), 7.73(1H, d, Ar-H), 7.85(1H, s, Ar-H)Fluorene (5.0 g, 0.30 mol) was treated with iodic acid. Themixture was poured into water, and the product was filtered off, washed with water, and dried (8.1 g). A portion (1.02 g) waschromatographed on silica gel in cyclohexane, giving almost colourless 2-iodofluorene (0.73 g, 65percent), m.p. 127-128 [14].2-Iodofluorene was synthesized by iodination of fluorene (1 g, 6.02 mmol) with iodine (0.8 g, 3.2 mmol) in the presence of ortho-periodinic acid (H5IO6) (20 g, 0.88 mmol) in 80percent acetic acid aqueous solution (20 mL) at 80 °C for 4 h under nitrogen atmosphere.After cooling, the solvent was removed by decantation, and a brown solid was obtained. This was dissolved in toluene and washed with 5percent NaHSO3aqueous solution to remove the remaining iodine. Then, the resulting solid was purified by alumina column chromatography using toluene as an eluent, to obtain 8(the chemical structure in Scheme 2).Yield: 1.05 g (60percent).1H NMR (CDCl3, 400 MHz) δH7.89 (s, 1H), 7.76 (d, J= 8.4 Hz, 2H), 7.70 (d, J= 8.4 Hz, 2H), 7.73(d, J= 8.4 Hz, 2H), 7.38-7.35 (m, 2H), 3.87 (s, 2H), MS(GC-mass): m/z292.0 [M+]; C13H9I (292.1).General procedure: To a solution of corresponding amine (1 eq) in 18percent HCl (12 mL)was added NaNO2 (1 M in H2O, 1.5 eq) at 0 C. The mixture wasstirred at 0 C for 1 h, and then NaI (2 M in H2O, 2 eq) was added.After the mixture was stirred at room temperature for 4 h, Na2SO3(4 eq) was added. The suspension was filtered to give the desiredproducts 10-12. 6.1.4.1 (Example 1-8) A flow reactor, in which a Teflon tube having an outer diameter of 1/16 inch, an inner diameter of 0.5 mm, and a length of 2 m, as a reaction section, was connected to an exit of a high-speed mixer (produced by IMM, Trade Name: SIMM-V2) having an equivalent diameter of 80 mum, was provided. To the feed inlet of the high-speed mixer, a syringe was connected via a Teflon tube having an outer diameter of 1/16 inch and an inner diameter of 0.5 mm. Into a 100 ml Erlenmeyer flask, 30 ml of a saturated sodiumbicarbonate aqueous solution, 1 ml of a saturated sodium thiosulfate aqueous solution, and 30 ml of diethyl ether were charged, and the solution was cooled to 0C on an ice-water bath while stirred with a magnetic stirrer. The high-speed mixer and the reaction section were also immersed into an ice-water bath to be cooled to 0C. The exit of the reaction section was introduced into water layer in the Erlenmeyer flask. Total amount of the active iodinating agent obtained in the above-described Reference Example was connected to the feed tube of the high-speed mixer. 166.7 mg (1.00 mmol) of fluorene was dissolved in the same amount of acetonitrile as that of the active iodinating agent, and then the resultant solution was charged into the 10 ml syringe, which was connected to the feed tube of the high-speed mixer. Each syringe was set on a syringe pump, and flow rate from each syringe was adjusted to be 3.0 ml/min. The iodinating reaction was initiated by feeding each solution into the high-speed mixer. Sum of feed linear velocity for each solution was 50.9 cm/sec. The reaction solution obtained by the reaction displayed pale yellow color. After completion of feeding solutions, the aqueous layer and the ether layer were separated. The ether layer was concentrated in vacuo, and the residue was loaded on a 10 cm silica gel column, followed by elution of reaction products from the column with 100 ml of ether. The solvent was concentrated in vacuo, and then 30 ml of a saturated sodium bicarbonate aqueous solution and 50 ml of hexane were added thereto, to carry out extraction. Two layers were separated, and the hexane layer was concentrated to dryness in vacuo, to yield 209.6 mg of a reaction product. NMR analysis and GC analysis of the reaction product gave 72.5 mg of fluorene, 124.9 mg (0.428 mmol) of (Comparative Example 1-4) Into a 50 ml round-bottom flask, 166.2 mg (1.00 mmol) of fluorene, 8 ml of acetonitrile were charged together with a stirring bar. The solution was cooled to 0C on an ice-water bath while stirred with a magnetic stirrer. Total amount of the active iodinating agent prepared in the above-described Reference Example was added thereto, and the iodinating reaction was carried out at 0C for 1 hour. The reaction solution was concentrated in vacuo, and the residue was loaded on a 10 cm silica gel column, followed by elution of reaction products from the column with 100 ml of ether. The solvent was concentrated in vacuo, and then 30 ml of a saturated sodium bicarbonate aqueous solution and 50 ml of hexane were added thereto, to carry out extraction. Two layers were separated, and the hexane layer was concentrated to dryness in vacuo, to yield 280.8 mg of a reaction product. NMR analysis and GC analysis of the reaction product gave 62.3 mg of fluorene, 178.3 mg (0.610 mmol) of 2-Iodofluorene (3 g; 10.27 mmol, 1 equiv) was dissolved in 50 mL of anhydrous tetrahydrofuran. Thesolution was cooled to 0C and 2.6 g of potassium tert-butoxide (23.16 mmol, 3equiv) was added. During the process, the transparent solution became red.After the solution had been stirred for 10 min, 1.44 g of iodomethane(23.16 mmol, 3 equiv) was added, turning the red solution milky. The solution wasreturned to room temperature and stirred for another 12 hours. After 100 mLdeionized water was added, the solution was extracted with ethyl acetate (100mL X 3). The combined organic solution was then dried over magnesium sulfate, and filtered off. The filtrate was condensed under vacuum to obtain a viscousliquid. Further purification by column chromatography (all n-hexane) on silicagel afforded 3.0 g of product 1 in a yield of 91%. 1H NMR (300 MHz, CDCl3, delta) 1.47(s, 6H), 7.34-7.36(m, 2H), 7.40-7.45(m, 1H) 7.48(s, 1H), 7.64-70(m, 2H), 7.75-7.76(m, 1H)[Step 1] Synthesis of 2-iodo-9, 9-dimethylfluorene A synthesis method of 2-iodo-9, 9-dimethylfluorene is described. A synthesis scheme of 2-iodo-9, 9-dimethylfluorene is shown in (D-1). 25 g (86 mmol) of 2-2: Synthesis of 9, 9-dimethyl-1 g (3.44mmol) of Synthesis 20 parts of General procedure: N-butylammonium bromide (2.9 mmol, 0.9 g), potassium hydroxide (143.8 mmol, 8.1 g) was dissolved in 8 mL of water and heated to 65 C in an oil bath. 2-Iodo-9H-indole (14.4 mmol, 4.2 g) and 1-bromo alkane (86.1 mmol) were dissolved in 15 mL of toluene, and then a toluene solution was added to the above aqueous solution and reacted at 65 C for 2 hours. After the completion of the reaction, the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, and concentrated under reduced pressure on a rotary evaporator, and the residue was purified by column chromatography (petroleum ether).

Precursor for organic electroluminescent devices.

Molecular Weight:292.11
XLogP3:4.8
Exact Mass:291.97490
Monoisotopic Mass:291.97490
Heavy Atom Count:14
Complexity:213
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes