Ultraviolet irradiation produces cytotoxic synergy and increased DNA interstrand crosslinking with cis- and trans-diamminedichloroplatinum(II)

Reactions of cyanide with the dimethylplatinum (IV) complexes, [PtMe2(OH) (H20)1.5 n, [PtMe2Br2]n and fac-PtMe2Br(H2O)3+, have been studied, principally by 1H, 13C and 195Pt n.m.r. Cyanide rapidly displaces the ligands trans to the methyl groups. Subsequent reactions cis to the methyl groups occur more slowly with heating, or, for bromo complexes, on ultraviolet irradiation. These substitution reactions compete with reductive elimination of groups from the platinum(IV) compounds to produce platinum(II) products. All attempts to prepare solutions of fac-PtMe2(CN)(H2O)3+ were unsuccessful. Oxidative addition of ICN to cis-PtMe2( py )2 ( py = pyridine) gave PtMe2I(CN)( py )2, from which a solution of fac-PtMe2(CN)( MeOH )3+ in methanol could be obtained. Addition of water or aqueous acid to this solution gave a very insoluble precipitate of [PtMe2(CN)(OH)n. The cis and trans influences on Jpt -C and δC of the cyanide ligands have been evaluated.

Download Full-text

PERFLUOROALKYL ARSENICALS: PART IX. SOME REACTIONS OF COMPOUNDS CONTAINING As–As BONDS

Canadian Journal of Chemistry ◽

10.1139/v64-174 ◽

1964 ◽

Vol 42 (5) ◽

pp. 1123-1129 ◽

Cited By ~ 21

Author(s):

W. R. Cullen ◽

N. K. Hota

Keyword(s):

Ultraviolet Irradiation ◽

Major Product ◽

Mild Conditions ◽

Cis And Trans

Arsenobenzene reacts with CF3I to give C6H5As(CF3)2, C6H5As(CF3)I, and C6H5AsI2. C6H5As(CF3)I and AgCl yield C6H5As(CF3)Cl. The compounds CF2=CFX react with (CH3)2As—As(CH3)2 under mild conditions to give 1:1 adducts (CH3)As—CF2CFX—As(CH3)2 (X = CF3, Br). Some (CH3)2As—CF=CF2 is produced when X = Br and is the major product when X = I. When X = F a 1:4 adduct (CH3)2As—(CF2CF2)4—As(CH3)2 is probably formed on ultraviolet irradiation. (CH3)2As—As(CH3)2 reacts with CF3C≡CCF3 to give cis and trans (CH3)2AsC(CF3)=C(CF3)As(CH3)2 and with [Formula: see text] to give (CH3)2AsF and [Formula: see text].

Download Full-text

PHOTOCHEMICAL TRANSFORMATIONS OF SOME 4′-AMINO-2-STYRYLPYRIDINES AND THEIR SALTS

Canadian Journal of Chemistry ◽

10.1139/v65-183 ◽

1965 ◽

Vol 43 (5) ◽

pp. 1345-1356 ◽

Cited By ~ 10

Author(s):

J. L. R. Williams ◽

J. M. Carlson ◽

R. E. Adel ◽

G. A. Reynolds

Keyword(s):

Aqueous Solutions ◽

Trans Isomer ◽

Ultraviolet Irradiation ◽

Water Soluble ◽

Trans Isomers ◽

Photochemical Behavior ◽

Photochemical Transformations ◽

Cis And Trans Isomers ◽

Cis And Trans

The photochemical behavior of 4′-amino-, 4′-dimethylamino-, 4′-diethylamino-, and 4′-di-n-propylamino-substituted trans-2-styrylpyridine were studied. Ultraviolet irradiation of aqueous solutions of the bishydrochlorides and methiodide–hydrochlorides for moderate periods of time produced mixtures of the corresponding cis and trans isomers. Long irradiation times produced the corresponding dimers in all cases except that of trans-4′-di-n-propyl-amino-2-styrylpyridine. The cis isomers of the free bases and methiodides were isolated from the cis–trans mixtures. The trans-methiodides are not photochemically labile. The spectra of each pair of isomers were determined in water and in 50% methanol–water, with the exception of the 4′-di-n-propylamino derivative, which is not sufficiently water soluble. In addition, the spectra of the corresponding methiodides, hydrochlorides, bishydrochlorides, and methiodide–hydrochlorides were determined. The basic strengths of the nitrogens in the cis–trans isomer pairs of the free bases and methiodides have been determined spectroscopically in water and in 50% methanol-water.

Download Full-text