2-Iodo-4-methylaniline

Milky white solid

Step 1: General procedure: To a stirred solution of the substrate (1 mmol) in CHGeneral procedure: General procedure for the iodination of aryl amines under solvent-free conditions.DBDABCODCI (0.5 mmol) and aryl amine (1 mmol) were triturated together in a porcelainmortar at room temperature. After completing reaction which monitored by TLC, the ethylacetate added to mixture and filtered, the organic layer washed with 5percent aqueous sodiumthiosulfate, and dried over MgSO4. The solvent was removed in vacuum and the crude mixturewas purified by column chromatography using ethyl acetate and hexane mixture and analyzedby m.p. and 1H NMR spectroscopy.A solution of para-toluidine (11; 1.61 g, 15 mmol) and NaHCO3 (3.78 g, 45 mmol) inH20/CH2CI2 1:2 (90 mL) was treated with 12 (3.81 g, 15 mmol) at 0 00 under Ar and stirred at25 00 for 22 h. The layers were separated, and the aqueous layer was extracted with CH2CI2(2x 30 mL). The combined organic layers were washed with brine (lx 40 mL) and evaporated.Flash column chromatography (Si02; hexane/EtOAc 100:0 to 95:5) yielded 2-iodo-4-methylaniline (2.95 g, 84percent) as a brown oil.Rf = 0.22 (Si02; hexane/EtOAc 95:5, UV 254 nm); 1 H NMR (400 MHz, CDCI3): d 7.47 (dd, J =1.4, 0.7 Hz, 1 H; H—C(3)), 6.95 (dd, J = 8.1, 1.9 Hz, 1 H; H—C(S)), 6.68 (d, J = 8.1 Hz, 1 H; H—C(6)), 4.05—2.57 (br. s, 2 H; NH2), 2.20 ppm (s, 3 H; Me).This was prepared following a modified literature reported procedure.2-Iodo-4-Methylaniline (21) General procedure: An aromaticamine (1 mmol), nanomagnetic-supported sulfonic acid (c-Fe2O3–SO3H)(0.65 g), NaNO2 (2 mmol, 0.138 g), and 0.2 mL of H2O were homogenized bygrinding in a mortar with a pestle for a few minutes. Formation of a reddishbrowngas was observed as soon as H2O was added. The diazotization reactionlasted for approximately 5–30 min. Next, KI (2.5 mmol, 0.415 g) was added tothe diazonium salt and grinding was continued for 10–20 min. After completionof the reaction, the mixture was triturated with EtOAc (5 mL). The c-Fe2O3–SO3K was separated from the solution using a magnetic bar. The organic layerwas treated with aq 10percent Na2SO3 (15 mL), then dried over anhydrous Na2SO4.After evaporation of the solvent, the crude product was afforded. Purifiedproducts were obtained by recrystallization from ethanol or by flashchromatography (n-hexane–EtOAc, 95:5).A typical procedure was followed for one-pot synthesis of substituted 2-iodoaniline and 2-iodoacetanilide from substituted aniline. A mixture of 5 g of substituted aniline 1–6 shown inTable 1, granulated iodine (1 mol. equiv.) and copper(II) acetate(1 mol. equiv.) were stirred in 50 mL of glacial acetic for 30 min.The reaction mixture was refluxed for 12 h with constant stirring at 120 C. Then the reaction mixture was allowed to cool at room temperature. The precipitate of copper(I) iodide was removed byfiltration and the filtrate was poured into water and extracted with chloroform (3 50 mL). The combined chloroform extracts were washed with sodium hydrogen carbonate solution, sodium thiosulfate solution, distilled water and dried with anhydrous sodium sulfate.A crude semi-solid mass was obtained after removal of solvent. The crude product was purified by column chromatographyon silica gel using n-hexane/ethyl acetate as eluant (4:1) and compounds 7–24 were isolated.

Molecular Weight:233.05
XLogP3:2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:232.97015
Monoisotopic Mass:232.97015
Topological Polar Surface Area:26
Heavy Atom Count:9
Complexity:94.9
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes