2-Ethyl-4-iodoaniline

Bowman et al. reported the total synthesis of ellipticine (228) involving an imidoyl radical cascade reaction (730). For this key step, the required imidoyl radical was generated from the imidoyl selanide 1290, which was obtained from ethyl 2-(4-pyridyl)acetate (1286). Reaction of 1286 with LDA, followed by addition of methyl iodide, led to the corresponding methyl derivative 1287. Treatment of 1287 with 2-iodoaniline (743) in the presence of trimethylaluminum (AlMes) afforded the amide 1288. Using Sonogashira conditions, propyne is coupled with the amide 1288 to afford the aryl acetylene 1289. The aryl acetylene 1289 was transformed to the... 

Cinnamoyl- 6-CD (6-CiO-/3-CD) was sparingly soluble in water, although most 6-substituted 6-CDs are soluble. However, 6-CiO-/3-CD was solubilized in water on the addition of adamantane carboxylic acid or p-iodoaniline which could be included in a 6-CD cavity. These results suggest that 6-CiO-/l-CD formed supramolecular polymers in the solid state, as shown in the proposed structure in Fig. 17. The X-ray powder pattern of 6-CiO-/l-CD was similar to that of the complex between p-CD and ethyl cinnamate, in which /3-CDs formed a layer structure. The crystal structure of 6-aminocinnamoyl-/3-CD (6-aminoCiO-/l-CD) is shown in Fig. 12 and we discussed the relationship between crystal packing and the substituent group in Sect. 2.8. 

To a 100-mL, two-necked flask, is added a mixture of cyclohexanone (5.9 g, 60 mmol), o-iodoaniline (4.4 g, 20 mmol), and 1,4-diazabicyclo[2.2.2]octane (DABCO) (6.7 g, 60 mmol) in N,N-dimethylformamide (DMF) (60 mL). The mixture is degassed three times via nitrogen/vacuum, followed by the addition of palladium acetate (Pd(OAc)2) (2.24 mg, 0.1 mmol) (Note 1). The mixture is degassed twice and heated at 105°C for 3 hr or until completion of the reaction (Note 2). The reaction mixture is cooled to room temperature and partitioned between isopropyl acetate (150 mL) and water (50 mL). The organic layer is separated, washed with brine (50 mL), and concentrated under vacuum to dryness. The residue is chromatographed on 50 g of silica gel using 700 mL of ethyl acetate-heptane (1 6) as the eluent to give 2.22 g of 1,2,3,4-tetrahydrocarbazole (65%) as a pale brown solid (Note 3). 

Bile pigments in bile LiChrosorb RP-8, S Jim Acetonitrile/ethyl acetate/methanol/water (30 33 45 50) with varying pH and concentration of tetrabutyl ammonium ions As 4-iodoaniline azo- 142 derivatives UV 546 nm or 365 nm ... 

In 2010, Weinreb and coworkers reported their synthesis of communesin F (17) [30]. The synthesis began with known enol triflate 37. A Suzuki-Miyaura crosscoupling with 0-nitrophenyl boronic acid (38) followed by a two-step reaction with iodoaniline 39, afforded amide 40. A one-pot displacement of the benzyl group with ethyl carbamate, amide nitrogen protection, and a subsequent intramolecular Heck reaction provided enamide 41 (Scheme 5). 

Huang [80] and Liu [81] independently described a copper-catalyzed indole synthesis involving 2-iodoaniline and allenes (e.g., ethyl buta-2,3-dienoate) in a process that involved in situ formation of an aza-Michael addition adduct (vinylogous carbamate) and intramolecular Hecklike cyclization. Both groups used similar reaction... 

Reaction Procedure (Scheme 2.86) To a Schlenk tube with a screw cap were added Pd(dba)2 (6 mg, 0.011 mmol), (Ra,5,5)-L7 (7 mg, 0.011 mmol), and 1 mL of THF. The resulting mixture was stirred for 2 h at room temperature, which was followed by sequential introduction of Ag3P04 (34 mg, 0.081 mmol), 2-iodoaniline (0.20 mmol), allene (0.81 mmol), and 1 mL of THF at room temperature. The resulting solution was stirred at 110 °C. When the reaction was completed as monitored by TLC, the solvent was evaporated under vacuum, and the residue was purified by chromatography on silica gel (eluent petroleum ether-ethyl acetate, 70 1) to afford the product as an oil the ee was determined by HPLC analysis [Chiralcel AD-H, hexane-i-PrOH = 85 15, 0.7 mL min , 230 nm]. 

Reaction Procedure (Scheme 2.92) The Pd-loaded zeolite (0.125 mmol), lithium chloride (0.5 mmol), caesium carbonate (1 mmol), AT-acetyl 2-iodoaniline (0.5 mmol), phenyl acetylene (1.0 mmol), and DMF (10 ml) were added to a sealed tube. The reaction mixture was stirred for 6 h at 140 °C. The reaction mixture was diluted with saturated aqueous ammonium chloride. The product was isolated with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. The reaction mixture was filtered and concentrated. The product was purified by silica gel column chromatography using hexane-ethyl acetate. 2-Phenyl indole was obtained as a pure product. 

Reaction Procedure (Scheme 2.117a) A mixture of 2-iodoaniline (0.46 mmol), ethyl acetoacetate (0.51 mmol), Cul (0.046 mmol), BINOL (17.5 mmol, 0.092 mmol) and CS2CO3 (0.46 mmol) in DMSO (1 mL) was stirred at room temp, for 4 h under an atmosphere of nitrogen. The mixture was partitioned between ethyl acetate and saturated NH4CI, the organic layer was washed with brine, dried with MgS04 and concentrated in vacuo. The residue was purified by preparative TLC (hexane-EtOAc, 3 1) to provide the indole. 

Scheme 2.131c) An oven-dried Schlenk tube was charged with 2-iodoaniline (0.25 mmol), CS2CO3 (0.75 mmol), Cul (0.05 mmol), and 1,10-phenanthroline (0.1 mmol). The tube was evacuated and backfilled with N2, and then 2-iodopyridine (0.3 mmol) and q lene (0.5 mL) were added. The reaction mixture was stirred at 120 °C for 12 h and then allowed to cool to room temperature. The mixture was diluted with water and extracted with ethyl acetate. The extracts were combined and then dried with anhydrous Na2S04. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography to afford the corresponding product. 

Reaction Procedure (Scheme 2.146a) 2-Iodoaniline (0.3 mmol), benzal-dehyde (0.4 mmol), sulfur powder (0.9 mmol), CuCla 2H2O (0.03 mmol), 1,10-Phen (0.03 mmol), and K2CO3 (0.6 mmol) in water (3 mL) were put into a Teflon septum screw-capped tube. The reaction mixture was stirred at 100 °C for 24 h without an inert gas atmosphere and then cooled to room temperature and extracted with ethyl acetate. The organic layer was dried over Na2S04 and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to afford the corresponding product. 

Scheme 2.146b) A mixture of 2-iodoaniline (1 mmol), benzylamine (1.2 mmol), sulfur powder (6 mmol), DABCO (2 mmol), Cu(0Ac)2 -H20 (0.02 mmol), and 1,10-phenanthroline (0.02 mmol) was stirred in DMSO (5 mL) at 100 °C. After completion of the reaction as indicated by TLC, the mixture was cooled to room temperature. Water (20 mL) was added, and the aqueous solution was extracted with ethyl acetate (3x15 mL). The organic layers were combined, dried over anhydrous MgS04, the filtrate was concentrated under vacuum and then the residue was purified by column chromatography (eluent petroleum ether-ethyl acetate, 10 1 to 14 1) on silica gel to provide the desired product. 

Reaction Procedure (Scheme 4.9) In an oven-dried, 10 mL round-bottomed flask equipped with a magnetic stirrer was added amide (0.5 mmol), 2-iodoaniline (0.5 mmol), Cul (20 mol%), K2CO3 (1.25 mmol) in anhydrous DMSO (1.5 mL). The reaction mixture was then stirred at 135 °C under a nitrogen atmosphere. After completion of the reaction, as determined by TLC, the reaction mixture was allowed to cool to room temperature. The crude reaction mixture was then purified by column chromatography without work-up using hexane-ethyl acetate as the eluent to yield the compound. 

C 1 1H1 i,N202, 3-Methyl-N-ethyl-isonitrosoacetanilide, 40B, 11 5 Cl 1H1 6BFi,N03, (2 -(2-Formyl-4-nitroanilino)ethyl)dimethylammonium tetrafluoroborate, 43B, 135 Ci2H7lNi,06, N-Picryl-p-iodoaniline, 12, 395 C12H7N5, 4-Ethyl-2,3,5,6-tetracyanoaniline, 4IB, 121 Ci2H8Na06, 2,4,6-Trinitrodiphenylamine, 39B, 71... 

All the chemicals were commercially obtained and used without further purification. PET bottles of Spritzer (Malaysia) mineral water were shredded into flakes. Sodium hydroxide AR (Chem.AR), Ethylene glycol (Aldrich Chem. Co.) and sulphuric acid (MaUinckrodt Chem. Co.) were used as purchased. Aniline, p-iodoaniline, p-bromoaniUne and p-chloroaniline were purchased from (Aldrich Chem. Co.). 2,5-dihydroxybenzaldehyde, absolute ethanol, methanol, 1-butanol, dimethyl-sulfoxide (DMSO), ethyl methyl ketone and diethyl ether (Fluka Chem. Co.). 

---