Action Of Sodium Iodide Research Articles

Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes

In the oxidative system (t-BuOCl+NaI) trifluoromethanesulfonamide is regio- and stereoselectively added to only one double bond of cyclopentadiene and 1,3-cyclohexadiene giving rise to 1,1,1-trifluoro-N-(5-iodocyclopent-2-en-1-yl)methanesulfonamide 7 and trans-N,N′-cyclohex-3-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 8. The structure of 7 and 8 was determined by X-ray, NMR, and MS. With 1,4-cyclohexadiene, addition to both double bonds occurs with the formation of N,N′-(4-chloro-5-iodocyclohexan-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide) 9. Under the action of sodium iodide in acetone, the latter product undergoes halogenophilic attack with the reduction of the CHI group and elimination of HCl to give trans-N,N′-cyclohex-4-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 10, whose structure was also determined by X-ray analysis. 1,3,5-Cycloheptatriene under these conditions is oxidized to benzaldehyde and does not react with trifluoromethanesulfonamide.

Synthesis of monomercurated N-protected pyrroles and the use of these compounds as pyrrolyl group transfer reagents to ruthenium and osmium. Crystal structures of (2-C 4H 3NC[O]CH 3)HgCl, (2-C 4H 3NC[O]CH 3) 2 Hg and

N-Acetylpyrrole and N-phenylsulfonylpyrrole are each selectively mercurated in the 2-position on treatment with mercuric chloride. The resulting organomercuric chlorides are symmetrized to the corresponding diorganomercury derivatives (2-C 4H 3NC[O]CH 3) 2Hg ( 2) and (2-C 4H 3NSO[O]Ph) 2Hg ( 4) by the action of sodium iodide. The crystal structures of (2-C 4H 3NC[O]CH 3HgCl ( 1) and (2-C 4H 3NC[O]CH 3) 2Hg ( 2) have been determined. The acetyl oxygen atom interacts weakly with the mercury centre in both cases, but more strongly in 1 than 2. Treatment of the hydrido complexes MHCl(CO)(PPh 3) 3 (M  Ru, Os) with the diorganomercurial 2 or 4 affords in good yield the 2-pyrrolyl complexes ▪ CH 3)Cl(CO)(PPh 3) 2 or ▪, respectively. In each case the pyrrolyl group is coordinated in a bidentate fashion through C-2 and an oxygen atom of the N-substituent. The chloride ion in ▪ ▪( 7) is labile, and upon treatment with AgSbF 6 and CO, the cationic complex ▪ ▪ is formed. Treatment of 7 with AgSbF 6 and sodium dimethyldithiocarbamate gives the neutral monophosphine complex ▪ ( 10), the crystal structure of which has been determined.

ChemInform Abstract: A CONVENIENT SYNTHESIS OF 1‐(2′,3′‐DIDEOXY‐β‐D‐ERYTHRO‐HEX‐2′‐ENOPYRANOSYL)URACIL

AbstractDas Glucopyranosyluracil (I) reagiert mit Benzaldehyd zu dem Benzyliden‐Derivat (IIa), dessen Mesylat (IIb) in das Anhydronucleosid (III) übergefihrt wird.

A Convenient Synthesis of 1-(2′,3′-Dideoxy-β-d-erythro-hex-2′-enopyranosyl)uracil

Abstract 2,2′-Anhydro-l-(4′,6′-O-benzylidene-3′-O-methylsulfonyl-β-d-mannopyranosyl)urasil, prepared smoothly from β-d-glucopyranosyluracil in three steps, was converted into the corresponding unsaturated nucleoside in a good yield by the action of sodium iodide. The unsaturated nucleoside was then debenzylidenated with acid to afford the title compound.

Synthesis of a (2,3-dideoxyglyc-2-enopyranosyl)thymine and a (2,3-dideoxyglycopyranosyl)thymine via a 2,2′-anhydro-nucleoside

2,2′-Anhydro-1-(4,6-O-benzylidene-3-O-methylsulphonyl-β-D-mannopyranosyl)thymine (5), prepared quantitatively from the 2′,3′-bismethanesulphonate (3), was converted into the corresponding unsaturated nucleoside (8) in 56% yield by the action of sodium iodide in boiling NN-dimethylformamide. Debenzylidenation of (8) with acid gave a free unsaturated nucleoside (12) in 91% yield. Reduction of (12) over palladium–carbon gave the (2,3-dideoxyhexopyranosyl)thymine (14). A mechanism for the formation of unsaturated nucleoside is described.

A synthesis of 3′,4 [formula omitted]dideoxykanamycin B

3′,4′-Dideoxykanamycin B, the kanamycin B derivative that is active against resistant bacteria, was prepared from kanamycin B via N-tosylation, 3′,4′- O-sulphonylation, 3′,4′-unsaturation, and hydrogenation. The unsaturated intermediate was obtained from the 3′,4′-di- O-sulphonyl derivatives by the action of sodium iodide in N, N-dimethylformamide; if zinc dust was added in this reaction, aziridine derivatives were formed, Removal of the tosyl group was successfully performed by using sodium in ammonia-ethylamine.

Synthesis of 1-N-[(S)-4-Amino-2-hydroxybutyryl]-3′,4′-dideoxyneamine

Abstract The titled compound (5) has been prepared from 3′,4′-dideoxyneamine or ribostamycin via 1,6-cyclic carbamate intermediates (2 and 12). 3′,4′-Dideoxygenation, which is the key step in the synthesis from ribostamycin, was accomplished by the hydrogenation of 3′,4′-unsaturated derivative which was prepared from the corresponding 3′,4′-di-O-mesyl derivative by the action of sodium iodide and zinc dust in DMF. The title compound was found to have an improved antibacterial spectrum broader than 3′,4′-dideoxyneamine.

Halomethyl-metal compounds : LIX. An Improved preparation of phenyl(fluorodichloromethyl)mercury, a useful fluorochlorocarbene precursor

An improved procedure for the preparation of phenyl(fluorodichloromethyl)mercury involving the reaction of phenylmercuric chloride with sodium methoxide and fluorodichloromethane in THF/methanol at −40° is described. This procedure gives PhHgCCl 2F in high yield and generally of about 85% purity. Reactions of the PhHgCCl 2F thus prepared with olefins [cyclohexene, cyclooctene, allyltrimethylsilane, vinyltriethylsilane, Me 2CCHCl, Me 2CC(Br)Me, CH 2C(Me)CH 2Cl and norbornene] gave the expected cyclopropanes in high yield. This mercury reagent added CClF to the CN bond of PhNCCl 2, giving 1-phenyl-2-fluoro-2,3,3-trichloroaziridine and to the CS bond of thiobenzophenone. The thiirane formed was, however, unstable to the reaction and work-up conditions and only its desulfurization product, Ph 2CCClF, could be isolated. Fluorochlorocarbene transfer from this mercurial also could be induced by the action of sodium iodide in DME. Evidence is presented which shows that PhHgCCl 2F is more reactive in CClF transfer than indicated in a previous report.

Synthesis of derivatives of cyclobuteno[c]thiophen

cis- and trans-3,4-Dibromocyclobuteno[c]thiophen derivatives have been made by the action of sodium iodide on 2,5-dihalogeno-3,4-bisdibromomethylthiophens.

The synthesis and reactions of unsaturated sugars : Part II. Introduction of endocyclic double bonds into pentoses and hexoses

The action of sodium iodide in acetone on methyl 4- O-benzyl-3-deoxy-3-iodo-2- O-tosyl-β- l-xylopyranoside ( 1) is described. At room temperature, methyl 4- O-benzyl-2,3-dideoxy-β- l- glycero-pent-2-enoside ( 2) and methyl 2- O-benzyl-3,4-dideoxy-β- l- glycero-pent-e-enoside ( 2a) were formed. At lower temperatures (0–5°), the action of sodium iodide in acetone on 1 produces only the expected 2,3-alkene 2, and a mechanism, based on conformational analysis, is suggested to account for this fact. The action of sodium iodide in acetone on methyl 4- O-benzyl-3-deoxy-3-iodo-2- O-tosyl-6- O-trityl-α- d-glucopyranoside [ 12, made from the iodohydrin 9 obtained by the action of methylmagnesium iodide on methyl 2,3-anhydro-4- O-benzyl-6- O-trityl-α- d-allopyranoside ( 8)] is also described. The structure of the iodohydrin 9 was established by mild, acid hydrolysis, followed by sequential hydrogenolysis, to yield methyl 3-deoxy-α- d- ribo-hexopyranoside. Treatment of 12 with sodium iodide in refluxing acetone yielded a crystalline alkene, which has an n.m.r. spectrum consistent with the structure of methyl 4- O-benzyl-2,3-dideoxy-6- O-trityl-α- d- erythro-hex-2-enoside ( 13). This structure was further confirmed by cis hydroxylation of 13 with neutral potassium permanganate, followed by catalytic hydrogenolysis, to give methyl α- d-mannopyranoside.

Ring opening of aziridin-1-yl-quinones

Certain aziridin-1-yl-quinones are converted by the action of sodium iodide and aluminium halides into 2-halogenoethylamino-quinones. The behaviour of the latter on catalytic reduction has been studied. The reaction of 3,6-diaziridin-1-yl-p-xyloquinone with concentrated sulphuric acid is reported.

Additions and Corrections - Halomethyl-Metal Compounds. XII. The Action of Sodium Iodide on Phenyl(trihalomethyl)mercury Compounds. A New Method of Dihalocarbene Generation.

Additions and Corrections - Halomethyl-Metal Compounds. XII. The Action of Sodium Iodide on Phenyl(trihalomethyl)mercury Compounds. A New Method of Dihalocarbene Generation.

Halomethyl-Metal Compounds. XII.1 The Action of Sodium Iodide on Phenyl(trihalomethyl)mercury Compounds. A New Method of Dihalocarbene Generation

Halomethyl-Metal Compounds. XII.¹ The Action of Sodium Iodide on Phenyl(trihalomethyl)mercury Compounds. A New Method of Dihalocarbene Generation

A SYNTHESIS OF 5,6-DIDEOXY-D-XYLOHEXOSE(5-DEOXY-5-C-METHYL-D-XYLOSE)

A synthesis of 5,6-dideoxy-D-xylohexose (I) from D-glucose is described. The action of sodium iodide in acetone on some toluene-p-sulphonyl esters of sugar derivatives is detailed.

Synthesis of organoarsenic compounds of the types ArAr?AsX and ArAr?Ar?As via double diazonium salts

1. A general method was developed for the synthesis of mixed organoarsenic compounds of the type ArAr'AsX. In consists in the action of sodium iodide on a mixture of an aryldichloroarsine and a double diazonium ferric or zinc chloride (ArN2Cl · FeCl3 or (ArN2Cl)2 · ZnCl2) in an acetone medium in the cold. Yields of 40–60% were obtained. 2. A method was developed for the synthesis in 50–80 yield of triarylarsines of the type ArAr'Ar"As. It consists in reaction of mixed diarylchloroarsines ArAr'AsCl with double diazonium zinc or ferric chlorides in the cold in an acetone medium in presence of iron powder.