Participation of 19-substituents in acid cleavage of steroidal 5α,6α-epoxides

1980 ◽  
Vol 45 (11) ◽  
pp. 3190-3198 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Methoxy Group ◽  
Acetoxy Group ◽  
Acid Cleavage ◽  
Aqueous Perchloric Acid ◽  
External Attack

Participation of the 19-methoxy and 19-acetoxy group in 5α,6α-epoxides IIIa and IVa on treatment with aqueous perchloric acid is investigated and compared with acid cleavage of previously studied 3β-acetoxy epoxides IIIb and IVb. The methoxy group in IIIa participates by a 5(O)n process. The participation is predominant on treatment with perchloric acid but is completely suppressed by the attack of an external nucleophile on treatment with hydrobromic acid. The acetoxy group in IVa participates by a 6(O)π,n process. Participation is predominant on treatment with perchloric acid and is only partially suppressed by a competitive external nucleophile attack on the action of hydrobromic acid. This behavior constitutes a difference to the 3β-acetoxy derivative IVb where hydrobromic acid completely suppresses the participation in favor of an external attack.

Participation of the methoxyl group in the cleavage of some 19-substituted steroid epoxides. A case of competition between internal and external nucleophile attack

1979 ◽  
Vol 44 (1) ◽  
pp. 226-233 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Methoxy Group ◽  
Methoxyl Group ◽  
Cyclic Ethers ◽  
Normal Reaction ◽  
Acid Cleavage ◽  
Aqueous Perchloric Acid ◽  
The Difference ◽  
Electrophilic Additions

Acid cleavage of two steroid epoxides III and IV, bearing a methoxy group in position 19, with aqueous perchloric acid or hydrobromic acid gives two types of products, i.e. diols or bromohydrins VI, VII, IX and X as products of the normal reaction course and cyclic ethers V and VIII formed by participation of the 19-methoxy group. Discussed is similarity of these reactions with electrophilic additions to the related 19-methoxy olefins I and II, the mechanism, and the difference in behavior of both epoxides III and IV. Also discussed is the dependence of product ratios on the nucleophility of the attacking species.

Participation of 19-substituents in electrophilic additions to 6,7-unsaturated 5α-cholestane and B-homo 5α-cholestane derivatives; A case of competition between the participation of an ambident neighboring group and external nucleophile attack

1980 ◽  
Vol 45 (2) ◽  
pp. 559-583 ◽  
Author(s):  
Pavel Kočovský ◽  
Ladislav Kohout ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Cyclic Ether ◽  
Cyclic Ethers ◽  
Neighboring Group ◽  
Acid Cleavage ◽  
Neighbouring Group Participation ◽  
Aqueous Perchloric Acid ◽  
The Difference ◽  
Electrophilic Additions

Hypobromous acid action upon the 6,7-unsaturated 19-substituted 5α-cholestans Va-Vc results in the formation of two types of products, the cyclic ethers IX as products of 5(O)n participation of the 19-substituent, and the bromohydrins X. All these compounds are formed from the 6α,7α-bromonium ions Va'-Vc'. Under the same conditions the B-homo-5α-cholestane derivatives VIIa-VIIc afforded solely the cyclic ethers XIV as products of 5(O)n participation of the 19-substituent in the cleavage of the bromonium ions VIIa'-VIIc'. Acid cleavage of the 6α,7α-epoxides VIb and VIc with aqueous perchloric acid or hydrobromic acid gave two types of products, i.e. the cyclic ethers XI and the diols XII or bromohydrines XIII. The cyclic ethers XI arise by 5(O)n participation of the 19-substituent. The B-homo-6α, 7α-epoxide VIIIc on cleavage with aqueous perchloric acid have solely the cyclic ether XVc and by treatment with hydrobromic acid VIIIc afforded the mixture of XVc, as the main product, and of the bromohydrin XVIc. Discussed is the similarity of the bromonium ion cleavage with the fission of the corresponding epoxides, the mechanism of these reactions and the difference in the behaviour of the isomeric olefins Ia-c, IIIa-c, Va-c and VIIa-c and epoxides IIb,c, IVb,c, VIb,c and VIIIb,c. The competition between ambident neighbouring group participation and external nucleophile attack is discussed as well as the dependence of the products ratio on the nucleophilicity of the attacking species.

Participation of 19-substituents in acid cleavage of steroidal 3α,4α- and 4α,5α-epoxides

1980 ◽  
Vol 45 (11) ◽  
pp. 3199-3209 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý
Keyword(s):  
Hydrobromic Acid ◽  
Acid Treatment ◽  
Cyclic Ether ◽  
Acetoxy Group ◽  
Limited Extent ◽  
Neighboring Group ◽  
Group Participation ◽  
Acid Cleavage ◽  
Neighboring Group Participation ◽  
External Attack

Participation of the 19-methoxy and 19-acetoxy group in 3α,4α- and 4α,5α-epoxides IIIc, IVb,c on treatment with aqueous perchloric or hydrobromic acid is investigated and compared with acid treatment of structurally similar 19-substituted 6α,7α- and 5α,6α-epoxides V and VI and with the behavior of analogous 3α,4α- and 4α,5α-bromonium ions. The 3α,4α-epoxides III react readily with 5(O)n participation. The reaction is practically quantitative on perchloric acid treatment. Under the same conditions, the 19-methoxy-4α,5α-epoxide IVb suffers mainly external attack leading to the diol XIb. The neighboring group participation is solely a 5(O)n process giving rise to the cyclic ether X. The 19-acetoxy-4α,5α-epoxide IVc reacts predominantly with participation of the ambident acetoxy group. This reaction is exclusively a 6(O)π,n process affording the diol XVI. External attack proceeds to a limited extent to give the isomeric diol XIc. In this respect the latter compounds react quite analogously to 5α,6α-epoxides VI and 4α,5α- and 5α,6α-bromonium ions bearing 19-acetoxyl.

Acid catalysed opening of 4,4-dimethyl-4a,5-epoxy-A-homocholestane derivatives

1982 ◽  
Vol 47 (9) ◽  
pp. 2530-2539
Author(s):  
Helena Velgová
Keyword(s):  
Carbon Atom ◽  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Point Of View ◽  
Conformational Effects ◽  
Aqueous Perchloric Acid

The acid catalysed cleavage of 4,4-dimethyl-4a,5-epoxy-A-homocholestane derivatives bearing an oxygen-containing substituent (OH, OCOCH3, OCH3) in the position 3 with hydrobromic acid or aqueous perchloric acid was investigated. It was found that 4a,5-epoxides of 4,4-dimethyl-A-homocholestane series are opened on the side of the more substituted carbon atom C(5), where a normal cleavage leads to the formation of 4a-hydroxy-5,6-unsaturated derivatives, while the participation of the substituent in the position 3 leads to 3,5-epoxides. In none of the investigated epoxides was an attack of an external nucleophile observed. The effect of the nature of the substituent in the position 3 on the ratio of the products of a normal cleavage and the participation of the 3-substituent is discussed from the point of view of conformational effects. The dependence of the products ratio on the nucleophilicity of the acid used is also discussed.

Participation of 19-ester groups in the cleavage of 2α,3α- and 5α,6α-steroid epoxides. A case of competition between participation and external nucleophile attack

1979 ◽  
Vol 44 (5) ◽  
pp. 1496-1509 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Ester Group ◽  
Carbonyl Oxygen ◽  
Cyclic Carbonate ◽  
Cyclic Ether ◽  
Normal Reaction ◽  
Neighboring Group ◽  
Ether Oxygen ◽  
The Difference

Acid cleavage of the acetoxy epoxide IIIa with aqueous perchloric acid or hydrobromic acid gave two types of products, i.e. the diol Va or the bromohydrin VIa, and the cyclic ether VIII. The latter compound arises by participation of ether oxygen of the ester group. On reaction with perchloric acid the epoxide IVa gave the diol XIIIa as a product of a normal reaction and the isomeric diol Xa as a product arising by intramolecular participation of the carbonyl oxygen of the 19-acetoxy group. Participation of the 19-ester group is confirmed by the formation of the cyclic carbonate XI when the 19-carbonate IVb is treated analogously. On reaction with hydrobromic acid, the epoxide IVa gave solely the bromohydrin XIVa as a product of the normal reaction course. Discussed is the similarity of these reactions with electrophilic additions to the related 19-acetoxy olefins I and II, the mechanism, the difference in behavior of both epoxides III and IV, the dependence of the product ratio on the nucleophility of the attacking species, and the competition between participation of an ambident neighboring group and an external nucleophile attack.

Mechanism of acid cleavage of some steroid epoxides. Competition between neighboring group participation and external nucleophile attack

1982 ◽  
Vol 47 (1) ◽  
pp. 124-129 ◽  
Author(s):  
Pavel Kočovský ◽  
František Tureček ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Cyclic Ether ◽  
Oxirane Ring ◽  
Neighboring Group ◽  
Group Participation ◽  
Acid Cleavage ◽  
Neighboring Group Participation

The mechanism of perchloric acid cleavage of epoxides I and II was established on the basis of experiments using H2 18O. The 2α,3α-epoxide I gave two products: the cyclic ether V (60%) arising by 5(O)n participation of the 19-acetoxyl and the diol VI (40%). The latter compound is formed by two mechanisms: 1) By direct cleavage of the oxirane ring with H2 18O as external nucleophile and 2) by 7(O)π,n participation via the ion III. Under the same conditions the 5α,6α-epoxide II yielded two diols: The diequatorial diol VIII (96%) arising by 6(O)π,n participation and the diaxial diol IX which is again formed by both direct cleavage of the oxirane ring with H2 18O and by 7(O)π,n participation via the intermediate ion X. The competition of several mechanisms is discussed.

15N N.M.R. Study of Some Palladium(II) Ammine Complexes

1988 ◽  
Vol 41 (9) ◽  
pp. 1425 ◽  
Author(s):  
TG Appleton ◽  
JR Hall ◽  
SF Ralph ◽  
CSM Thompson
Keyword(s):  
Perchloric Acid ◽  
Chemical Shifts ◽  
Free Ammonia ◽  
Silver Ion ◽  
Single Peak ◽  
Donor Atom ◽  
Ammine Complexes ◽  
Initial Product ◽  
Aqueous Perchloric Acid ◽  
Dimethylformamide Solution

Palladium(II) ammine complexes enriched in 15N give sharp singlets in their 15N n.m.r . spectra. The 15N chemical shifts depend primarily on the trans donor atom, in a qualitatively similar way to those for platinum(II) ammine complexes. A dimethylformamide solution of Pd(NH3)2Cl2 prepared in the usual way gave a single peak, consistent with the presence of only one isomer (trans). Reactions of increasing amounts of aqueous perchloric acid with Pd(NH3)42+ allowed peaks to be identified for Pd(NH3)3(H2O)2+, cis -Pd(NH3)2(H2O)22+ and Pd(NH3)(H2O)32+. The initial product of the reaction of trans-Pd(NH3)2Cl2 with silver ion is trans-Pd(NH3)2(H2O)22+, which rapidly disproportionates to Pd(NH3)3(H2O)2+ and Pd(NH3)(H2O)32+. With standing, subsequent reactions ultimately produce a solution containing predominantly cis -Pd(NH3)2(H2O)22+ in equilibrium with small amounts of the tri- and mono-ammine complexes, and free ammonia.

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