2- Iodobenzoic

The Dess-Martin periodinane ( DMP ) reagent, U,l-tris(acetyloxy)-l,l-dihydro-l,2-benziodoxol-3(l//)-one, has also been used in several complex syntheses for the oxidation of primary or secondary alcohols to aldehydes or ketones, respectively (e.g., M. Nakatsuka, 1990). It is prepared from 2-iodobenzoic add by oxidation with bromic add and acetylation (D.a Dess, 1983). 

The 2-iodobenzoate is introduced by acylation of the alcohol with the acid (DCC, DMAP, CH2CI2, 25°, 96% yield) it is removed by oxidation with CI2 (MeOH, H2O, Na2C03, pH > 7.5). ... 

Ullmann condensation of the sodium salt of p-chlorothiophe-nol (31) with 2-iodobenzoic (32) acid gives 33. Cyclization by means of sulfuric acid affords the thioxanthone, 34. Reaction with the Grignard reagent from 3-dimethylaminopropyl chloride affords the tertiary carbinol (35). Dehydration by means of acetic anhydride affords chlorprothixene as a mixture of geometric isomers, 36. (Subsequent work showed the Z isomer-chlorine and amine on the same side—to be the more potent compound.) Chlorprothixene is said to cause less sedation than the phenothiazines. ... 

Sandmeyer reaction provides access to 2-iodobenzo[h]selenophene (60MI1) the 4-iodo isomer is made from the lithium derivative (54J A5775). 

A two-component 2-halobenzoate 1,2-dioxygenase has been purified from Pseudomonas cepacia strain 2CBS that is able to metabolize 2-fluorobenzoate, 2-chlorobenzoate, 2-bromobenzoate, and 2-iodobenzoate to catechol by concomitant decarboxylation and loss of halide (Fetzner et al. 1992). The inducible 2-halobenzoate 1,2-dioxygenase consisted of... 

The nucleophilic displacement of the iodine moiety in 2-iodoben-zoates mediated by triphenyltin hydride and di-n-butyltin dichloride in aqueous solution has been demonstrated (Eq. 6.16).33 For example, 2-iodobenzoic acid reacts with a toluene solution of Ph3SnH/l,3-(N02)2 C6H4/aq. NaHC03 to give 89% yield of salicylic acid. 

Reaction of the sodium salt of 2 with 2-iodobenzoic acid results in formation of the corresponding bis-arylsulfide via nucleophilic aromatic substitution. 

A complementary approach to six-membered rings can be achieved with methyl 2-iodobenzoate or 2-iodobenzoyl chloride, as shown in Scheme 16 (Grigg et al. 2002). 

Methamidophos, see Acephate Methane, see Acetaldehyde, Benzoic acid, 7 Bromobenzoic acid. 3-Bromobenzoic acid. 4-Bromobenzoic acid. Bromoform, Carbatyl, Catechol, 2-Chlorobenzoic acid. 3-Chlorobenzoic acid. Chloroform, Dibromochloromethane, 2,5-Dichlorobenzoic acid. 1,2-Dichloroethane, Ethylamine, Ethyl bromide. Ethylene dibromide, Ethylenimine, Formic acid, Hydroqninone, 4 Hvdroxvbenzoic acid. Indole, 2-Iodobenzoic acid. 3 lodobenzoic acid. Methyl bromide, 4-Iodobenzoic acid. 2-Methylphenol, 4-Methylphenol, Phenol, Prorocatechuic acid. Svringic acid. Svringaldehvde. TCDD, Tetrachloroethylene, Toluene, Trichloroethylene, Vanillin. Vanillic acid. Vinyl chloride... 

Biological. Suflita et al. (1982) reported that 2-iodobenzoic acid degraded under anaerobic conditions by a stable methanogenic bacterial consortium enriched from sludge. The primary degradation pathway was dehalogenation forming iodides, methane, and carbon dioxide. 

In the cyclization of the (iodoaryl)diene, N-methyl-N-(l,5-hexadiene-3-yl)-2-iodobenzoic acid amide, the combined yield of the tricyclic products arising from a double intramolecular Heck reaction reached 52 % when the catalyst was prepared from [Pd(OAc)2] and 1,10-phenanthroline and the reaction was run in ethanol/water 1/1 (Scheme 6.4) [18,19]. Interestingly, in CH3CN the reaction did not proceed at all with this catalyst. It is also noteworthy, that Pd-phenanthroHne complexes are rarely used as catalysts in Heck-type reactions. 

The third-generation dendrimer palladium complex (31, containing 24 PdC groups) was applied in the Stille coupling of methyl-2-iodobenzoate with 2-(tributyl-stannyl)thiophene in DMF (Scheme 10 lmol% catalyst). In contrast to what was observed with the monomer (PPh3)2PdCl2, no palladium metal formation was... 

A facUe synthesis of 3,4-disubstituted isocoumarins and their benzologues is based on the Pd-catalysed annulation of internal alkynes by 2-iodobenzoate esters (Scheme 27). Tri- and tetra- substituted pyran-2-ones are also available by this route <99JOC8770>. 3-Substituted isocoumarins result from the Pd-catalysed 6-endo-dig cyclisation of 2-ethynylbenzoic acids. The 5-exo-dig products, phthalides, are also formed when there is a terminal bulky group on the alkyne moiety <99S1145>. 

Oxone was added to a suspension of 2-iodobenzoic acid in water (200 mL) and the mixture was heated at 70°C for 3 h. The mixture was cooled to 0 C, then filtered and washed with water (4 x 75 mL) and acetone (2 x 75 mL) to alford IBX, which was then dried under vacuum and stored in a foil-shielded flask. 

The coupling of 2-iodobenzoic acid and phenylacetylene under Sonogashira coupling conditions was found to give a mixture of an isocoumarin derivative and a phthalide (4.40.), The proper choice of the catalyst system led to the preferential formation of the latter compound.53 The process might also be diverted towards the formation of the isocoumarin derivative by isolation of the intermediate o-cthynyl-benzoic acid and its subjection to carefully selected cyclization conditions54... 

A. 1 -Hydroxy-1,2-benziodoxol-3(1 H)-one 1-oxide (1). A 2-L, three-necked, round-bottomed flask, fitted with a mechanical stirrer, condenser, and an immersion thermometer is charged with 80.0 g (0.48 mol) of potassium bromate (KB1O3) and 750 mL of 2.0 M sulfuric acid (Notes 1-3). The resulting clear solution is heated to 60°C in an oil bath and 80.0 g of finely powdered 2-iodobenzoic acid (0.323 mol) is added in... 

Use of higher concentration sulfuric acid ( 2.0 M) than traditionally employed is crucial to allow complete conversion of the 2-iodobenzoic acid to 1.2 In the submitters hands, use of lower concentrations ( 0.5 M) of sulfuric acid at 60°C led to exclusive formation of 1-hydroxy-1,2-benziodoxol-3(1 H)-one. When lower concentrations of sulfuric acid are employed, higher temperatures are required to effect oxidation, as judged by the initiation of bromine evolution. One of the factors leading to the lack of reproducibility in the preparation of 2 results from incomplete conversion to 1. 

Addition of the 2-iodobenzoic acid to the bromate-aqueous acid mixture results in an easily controlled, smooth reaction and an easily stirred reaction mixture. The stirring rate should be regulated such that splashing is minimized and solids do not accumulate on the walls or roof of the reaction vessel. Any solids which adhere to the sides or roof of the reaction vessel above the level of the liquid should be washed back into the reaction mixture with the minimum amount of 2M sulfuric acid. Addition... 

Iodination of benzo[6 jthiophene in benzene in the presence of mercury(II) oxide gives exclusively 3-iodobenzo[6 jthiophene, and 2-iodobenzo[6 jthiophene is formed exclusively by reaction of iodine on the 2-lithio derivative (Section 3.14.3.9). 2,3-... 

The closely related o-iodylbenzoic acid (IBX) and Dess-Martin oxidations have proved to be effective methods for the synthesis of peptide aldehydes (Table 7, Scheme 6) 9 38 39] 2-Iodobenzoic acid is oxidized by potassium bromate to form 2-iodylbenzoic acid (IBX), which can be used directly for IBX oxidation. IBX can be further treated with acetic anhydride and TosOH at 100 °C for 40 minutes to form the more stable Dess-Martin periodinane reagent 45 46]... 

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