Oxidations with phenyliodoso acetate. VI. Oxidation of phenols containing electron-attracting substituents was written by Fox, A. R.;Pausacker, K. H.. And the article was included in Journal of the Chemical Society in 1957.Quality Control of 1-Iodo-4-(4-nitrophenoxy)benzene The following contents are mentioned in the article:
Some p-alkoxycarbonyl- or p-nitrophenols were oxidized with PhI(OAc)2 (I) in C6H6 solution; 4-alkoxycarbonyl- or 4-nitro-2-iododiphenyl ethers were formed. In AcOH p-O2NC6H4OH (II) gave a compound believed to be 2-hydroxy-5-nitrodiphenyliodonium acetate (III). III could readily be rearranged to 2-iodo-4-nitrodiphenyl ether (IV). II (5.4 g.) and 9.7 g. I in 300 ml. dry thiophene-free C6H6 set aside 48 hrs. at room temperature gave 2 g. brown amorphous precipitate; the filtrate chromatographed on silica gave 0.8 g. of a first band (compound A), needles, m. 61° (from MeOH), m.p. undepressed with authentic IV. The 2nd band yielded 0.6 g. compound B, yellow plates, m. 120° (from alc.); monoacetyl derivative, brown prisms, m. 126°; monomethyl ether, needles, m. 128° (from alc.). When only compound A was required, Al2O3 was used as an adsorbent, since compound B was strongly absorbed. With m-chlorophenyliodoso acetate (V) as oxidizing agent the products were (a) 2 g. C6H6-insoluble material, (b) 1 g. 3′(?)-chloro-2-iodo-4-nitrodiphenyl ether, needles, m. 64° (from MeOH), and 0.4 g. compound B. H2O2 (12 ml., 38%) and 53 ml. Ac2O stirred 4 hrs. at 40° and 10 g. m-ClC6H4I added gave 15 g. V, m. 154°. 2-Chloro-5-nitroacetanilide (3.5 g.) and 0.1 g. Cu added to a mixture of 5.3 g. PhOH and 3.6 g. KOH which had previously been heated to 140°, after 0.5 hr. heating at 150-60° the mixture poured into a solution of 5 g. NaOH in 50 ml. ice H2O, and the product isolated gave 2.5 g. 2-acetamido-4-nitrodiphenyl ether (VI), needles, m. 123°. Refluxing 2.2 g. VI with 20 ml. 20% HCl and basifying gave 2-amino-4-nitrodiphenyl ether (VII), m. 106°. VII diazotized and treated with KI gave 60% IV, identical with compound A. Compound A (0.58 g.) hydrogenated with 5 ml. Raney Ni and 0.3 g. KOH in 25 ml. alc. gave 20% 4-aminodiphenyl ether, m. 81°. o-IC6H4OH (1.8 g.) heated 0.5 hr. at 160° with p-FC6H4NO2 and 0.5 g. KOH gave 2-iodo-4′-nitrodiphenyl ether, m. 104°. Similarly prepared were 3-iodo-4′-nitrodiphenyl ether, yellow needles, m. 84° (from MeOH), and 4-iodo-4′-nitrodiphenyl ether, m. 64°. The latter liquefied on mixing. with compound A. Compound B (1.15 g.) hydrogenated in alc. with 5 g. Raney Ni and the crude amine (0.88 g.) diazotized in concentrated HCl, treated 48 hrs. at 2° with a 20-molar excess of 50% hypophosphorous acid, the mixture extracted with Et2O, and washed, gave m-methoxydiphenyl ether, b3 145°, which could not be crystallized o-Methoxydiphenyl ether m. 77°. m-MeOC6H4OH and p-ClC6H4NO2 gave 3-methoxy-4′-nitrodiphenyl ether, plates, m. 88° (from alc.). 3,4-Dinitrophenol (VIIa) (4.6 g.), 8.1 g. I, and 400 mg. C6H6 refluxed 9.25 hrs. and the solution chromatographed on Al2O3 gave 0.71 g. 2(?)-iodo-4,5-dinitrodiphenyl ether (VIIb), yellow crystals, m. 115° (from cyclohexane). The oxidation of 3.8 g. Me p-hydroxybenzoate with 1 and 2 moles I in C6H6 at room temperature gave 1.9 g. and 3.1 g., resp., 2(?)-iodo-4-methoxycarbonyldiphenyl ether (VIII), m. 63° (from MeOH). Similarly, the oxidation of Et p-hydroxybenzoate (4.2 g.) gave 1.6 g. and 3.1 g., resp. of 4-ethoxy-2(?)-iododiphenyl ether (IX), b1.3 215°. When IX or VIII was hydrolyzed with aqueous alc. NaOH, 70% 4-carboxy-2(?)-iododiphenyl ether (X) was obtained as needles, m. 160° (from MeOH). 2,6-Dichloro-4-nitrophenol (8.8 g.) and 16.1 g. I in 1 l. C6H6 kept 50 days at 45° and the solution chromatographed on Al2O3, gave a red band of 3.55 g. 2,6-dichloro-1,4-benzoquinone, orange needles, m. 123° (from ligroine). II (4.4 g.) and 12 g. I in 50 ml. AcOH set aside 36 hrs. gave 10 g. crude product; the residue refluxed 2 hrs. in C6H6, and chromatographed on Al2O3 yielded 0.6 g. compound A. The combined precipitates (compound C) washed with Et2O, m. 156°. When compound C was heated several hrs. at 164° it gave 95% compound A. Similarly, when 0.55 g. compound C refluxed 2 hrs. with alc., AcOH, or C6H6 was converted to compound A in yields of 83, 87, and 92%, resp. Compound C (1.8 g.) refluxed 2 hrs. with 50 ml. 2N NaOH gave 0.5 g. compound A and 0.7 g. intractable brown tar. Compound C (5 g.) refluxed 0.5 hr. with 60 ml. 10% HCl gave 4.7 g. product, m. 210°. Compound C suspended in dioxane and left 10 days with excess Et2O and CH2N2 gave 88% compound A. 3-Methoxy-4-nitrophenol (0.56 g.) oxidized with 1.12 g. I in 50 ml. AcOH gave 0.93 g. 2(?)-iodo-5-methoxy-4-nitrodiphenyl ether, needles, m. 103° (from MeOH). p-Ethoxycarbonylphenol (1 g.) similarly oxidized 13 hrs. gave 4-ethoxycarbonyl-2(?)-iododiphenyl ether, which on hydrolysis gave X. VIIa (2 g.), 3.64 g. I, and 50 ml. AcOH heated 5 hrs. at 78° gave 3.41 g. VIIb. Solutions of 1.3 g. II and 2.4 g. I in C6H6 saturated with 100 ml. and 150 ml. C6H6, resp., set aside 15 hrs. and the product chromatographed gave 0.4 g. compound A. Finely powdered I (40 g.) stirred 0.5 hr. in 100 g. BzOH and 800 ml. Et2O until solution was effected, the solution stirred a further 2 hrs., and the solids collected gave 51 g. PhI(OBz)2, m. 161°. The mechanisms of the above reactions were discussed. This study involved multiple reactions and reactants, such as 1-Iodo-4-(4-nitrophenoxy)benzene (cas: 21969-05-1Quality Control of 1-Iodo-4-(4-nitrophenoxy)benzene).
1-Iodo-4-(4-nitrophenoxy)benzene (cas: 21969-05-1) belongs to iodide derivatives. The indole subunit is an almost ubiquitous component of biologically active natural products, and its study has been the focus of research for decades. More than 200 indole derivatives have already been marketed as drugs or are under advanced stages of clinical trials.Quality Control of 1-Iodo-4-(4-nitrophenoxy)benzene
Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com