Oxidation iodosobenzene diacetate

Under oxidative (iodosobenzene diacetate, h) and photolytic conditions some nonactivated amides from the alkaloid and steroid series form lactams via radical mechanisms. ... 

Iodosobenzene diacetate is used as a reagent for the preparation of glycol diacetates from olefins,9 for the oxidation of aromatic amines to corresponding azo compounds,10 for the ring acetylation of N-arylacetamides,11 for oxidation of some phenols to phenyl ethers,12 and as a coupling agent in the preparation of iodonium salts.13 Its hydrolysis to iodosobenzene constitutes the best synthesis of that compound.14... 

Peracetic acid, far oxidation of iodo-benzene to iodosobenzene diacetate, 43, 62... 

Oxidation of reserpine (109) with iodosobenzene diacetate in alcoholic medium (284) afforded in a single step the corresponding 7-alkoxyindolenine derivatives... 

IODOSOBENZENE, 43, 60 IODOSOBENZENE DIACETATE, 43, 62 hydrolysis to iodosobenzene, 43, 60 4-Iodosobiphenyl, 43, 61 4-Iodosobipbenyl diacetate, 43, 64 o-Iodosophenetole, 43, 61 o-Iodosophenetole diacetate, 43, 64 m-Iodosotoluene, 43, 61 o-Iodosotoluene, 43, 61 -Iodosotoluene, 43,61 jTodosotoluene diacetate, 43, 64 o-Iodosotoluene diacetate, 43, 64 p lodosotoluene diacetate, 43, 64 2-Iodoso-w-xylene, 43, 61 2-Iodoso- -xylene, 43, 61 4-Iodoso-m-xylene, 43, 61 2-Iodoso-wt-xylene diacetate, 43,64 4-Iodoso-m-xylene diacetate, 43,64 2-Iodoso- -xylene diacetate, 43, 64 N-Iodosuccinimide, 42, 73 Iodoxyarenes by oxidation of aryl iodides, 43, 66 IODOXYBENZENE, 43, 65... 

Iodosobenzene diacetate and iodine convert pentanol to 2-methyltetrahydrofuran by a similar mechanism. The secondary radical is most likely captured by iodine or oxidized to the carbocation prior to cyclization.271... 

Dinitro-2,2 -dichloroazobenzene. brn-red prisms (from solv naphtha), mp 274°(Ref 1) or red ndls (from benz), mp 265°(Ref 3), mp 275-76° (Ref 4) readily sol in benz mod sol in glac acet acid si sol in acet insol in ale was prepd by oxidization of 4-nitro-2-chloro-aniline with alk Na hypochlorite soln (Ref 1) and in 87% yield by oxidation of 4-nitro-2-chloroaniline with iodosobenzene diacetate at 35°(Ref 5)... 

Oxidation of a 1, 4,6-tetraketone (I).1 Oxidation of oxalyldiacetone (1) with iodosobenzene diacetate results in 2. Oxidation of 1 with lead tetraacetate gives dchydroacetic acid (3), previously obtained by dimerization of diketene. 

One of two products- can be obtained from the tetraketone (348), tautomeric with the furanone (349), depending on the oxidant (80TL1575). Lead(IV) acetate gives the 4-hydroxy-pyran-2-one (350), whereas the pyran-4-one results from the use of iodosobenzene diacetate (Scheme 109). 

Iodosobenzene diacetate [IBD, PhI(OAc)2] is able to oxidize benzylic alcohols to benzaldehydes when a solid mixture of iodosobenzene diacetate and the alcohol is irradiated with microwaves. Best results are obtained when iodosobenzene diacetate is supported on alumina.118 The use of polymer supported iodosobenzene diacetate (PSDIB) simplifies the work-up in the oxidation of benzylic alcohols to benzaldehydes.119 PSDIB can be employed in the presence of KBr and using water as solvent, resulting in the transformation of secondary alcohols into ketones and primary alcohols into carboxylic acids.117... 

Several other processes have been developed, however, to accomplish the oxidative decarboxylation of carboxylic acids oxidation by Pb(OAc)4, by iodosobenzene-diacetate, and by Ag(II) salt generated in situ in a catalytic cycle from a variety of peroxides (benzoyl peroxide, percarbonate, perborate) [2] other than the already mentioned peroxydisulfate. Representative examples are shown in Eqs (9)—(12) of Table 2. 

Alcohols with a hydrogen in the 8 position can be cychzed with lead tetraace-tate. ° The reaction is usually carried out at 80°C (most often in refluxing benzene), but can also be done at room temperature if the reaction mixture is irradiated with uv light. Tetrahydrofurans are formed in high yields. Little or no four- and six-membered cyclic ethers (oxetanes and tetrahydropyrans, respectively) are obtained even when y and s hydrogens are present. The reaction has also been carried out with a mixture of halogen (Br2 or I2) and a salt or oxide of silver or mercury (espe-cially HgO or AgOAc), with iodosobenzene diacetate and I2, and with ceric... 

DinitTO-3,3 -dichloTOazobenz ne, om prisms (from benz), mp 266.5-67.2° obtd by oxidizing 2-nitro-3-chloroaniline in dry benzene with iodosobenzene diacetate (Ref 5)... 

Potassium permanganate. Dimethyl sulfide-Chlorine. Dimethyl sulfoxide. Dimethyl sulfoxide-Chlorine. Dimethylsulf-oxide Sulfur trioxide. Dipyridine chro-mium(VI) oxide. Iodine. Iodine-Potassium iodide. Iodine tris(trifluoroacetate). Iodosobenzene diacetate. Isoamyl nitrite. Lead tetraacetate. Manganese dioxide. Mercuric acetate. Mercuric oxide. Osmium tetroxide—Potassium chlorate. Ozone. Periodic acid. Pertrifluoroacetic acid. Potassium ferrate. Potassium ferricyanide. Potassium nitrosodisulfonate. Ruthenium tetroxide. Selenium dioxide. Silver carbonate. Silver carbonate-Celite. Silver nitrate. Silver oxide. Silver(II) oxide. Sodium hypochlorite. Sulfur trioxide. Thalli-um(III) nitrate. Thallium sulfate. Thalli-um(III) trifluoroacetate. Triphenyl phosphite ozonide. Triphenylphosphine dibromide. Trityl fluoroborate. 

Several oxidants were tested in an epoxidation reaction in the presence of iminium salt catalysts to determine which offers the best profile in the absence of water [42]. These reactions were carried out at 0 °C with 1-phenylcyclohexene as substrate and (17) and /or (24) as catalysts (5-20 mol%), in dichloromethane as solvent. Most of the systems examined showed either high levels of background epoxidation (alkaline hydrogen peroxide, peracids, persulphates) or very low rates of reaction, even in the presence of 20 mol% of the catalysts (perselenates, percarbonates, perborates and iodosobenzene diacetate). Tetra-N-butylammo-nium Oxone, reported by Trost [43], was also unsuccessful as oxidant. 

Oxidative cyclization. The reaction of 2,2 -diaminodiphenylmethanes (1) with iodosobenzene diacetate in benzene at room temperature for several days affords dibenzo-[c,f]-[l,2]diazepines (2) in 30-60% yield.2 The reaction is not applicable to 2,2 -diaminobenzophenones. 

Two suitably positioned hydroxylamine groups undergo oxidative cyclization by low-temperature treatment with peracetic acid to give the 4-oxide, but when the diamino-sulphone was oxidized with iodosobenzene diacetate (review of uses [3714]), an azo group is formed to close the ring. 

The classical permanganate oxidation of a-pinene yields cis-pinonic acid (383). Now, using dicyclohexyl-18-crown-6 ether in benzene, the yield has been raised to 90%. In the conventional oxidation, the yield of the acid (383) is very low, but in the neutral part the interesting ether (384) has been found. This is quantitatively dehydrated by thionyl chloride to (385), which has led to the synthesis of ( - )-7-epichrysanlhenol (386), the structure of which was linked to chrysanthe-none by oxidation. It has been noted that with iodosobenzene diacetate and... 

Sulfones are valuable intermediates for the synthesis of chemically and biologically useful molecules. Traditionally, they are prepared by oxidation of sulfides with nitric acid, KMnO, MnO, NaClO, m-chloroperbenzoic acid, sodium metaperiodate, bromine, dinitrogen tetraoxide, oxaziri-dine, benzeneseleninic peracid, tert-butyl hydroperoxide, sulfinyl peroxy compounds, iodosobenzene diacetate and 4-methylmorpholine N-oxide/ osmium tetroxide. 

---