Chemischer InformationsdienstVolume 11, Issue 44 Physical Organic Chemistry ChemInform Abstract: CONFORMATIONAL STUDIES. PART 13. PROTON NMR AND X-RAY ANALYSES OF 2β-BROMO-3α-HYDROXY-5α-PREGNANE-11,20-DIONE, 3α-HYDROXY-2β-METHOXY-5α-PREGNANE-11,20-DIONE, AND 3α-HYDROXY-2α-METHYL-5α-PREGNANE-11,20-DIONE J. M. MIDGLEY, J. M. MIDGLEYSearch for more papers by this authorW. B. WHALLEY, W. B. WHALLEYSearch for more papers by this authorB. E. AYRES, B. E. AYRESSearch for more papers by this authorG. H. PHILLIPPS, G. H. PHILLIPPSSearch for more papers by this authorG. FERGUSON, G. FERGUSONSearch for more papers by this authorM. PARVEZ, M. PARVEZSearch for more papers by this author J. M. MIDGLEY, J. M. MIDGLEYSearch for more papers by this authorW. B. WHALLEY, W. B. WHALLEYSearch for more papers by this authorB. E. AYRES, B. E. AYRESSearch for more papers by this authorG. H. PHILLIPPS, G. H. PHILLIPPSSearch for more papers by this authorG. FERGUSON, G. FERGUSONSearch for more papers by this authorM. PARVEZ, M. PARVEZSearch for more papers by this author First published: November 4, 1980 https://doi.org/10.1002/chin.198044068AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume11, Issue44November 4, 1980 RelatedInformation

With the aim of finding a water-soluble intravenous general anaesthetic we have examined a range of steroids carrying a basic substituent at the 11-position. Compounds with 11β-dialkylaminoacyloxy-or 11α-dialkylamino-substituents formed water-soluble salts that showed the desired activity in mice. The 11β-esters can be prepared via the corresponding 11β-haloacetoxy compounds. The 11α-dialkyl-amines can be prepared by reduction of 11-oximes and subsequent alkylation. Structure-activity studies have involved modification of the solubilising group, variation of substituents on ring A and at the 17-position and introduction of double bonds. 11α-Dimethylamino-2β-ethoxy-3α-hydroxy-5α-pregnan-20-one (minaxolone) forms salts that are readily soluble in water at physiologically acceptable pH to give stable solutions of high anaesthetic potency.

Ring current intensities and proton chemical shifts have been calculated for a series of condensed aromatic hydrocarbons including biphenylenes. The calculations show that an induced paramagnetic ring current occurs in the 4-membered ring of each of the biphenylenes studied and this effect accounts for the observed spectra. PMR measurements on 1-mono-, 2-mono- and 2,3,6,7-tetra-deuteriated biphenylene prove that the chemical shifts of the 1- and 2-protons are at δCDCl3 6.60 and 6.70 respectively and not vice versa as assumed by previous authors.

AbstractAusgehend von dem Dichlorthiophen (Ia) werden nach üblichen Verfahren die Thiophene (Ib)‐(Ie) dargestellt.

3alpha-Hydroxy-5alpha-pregnane-11,20-dione-[21-14C] and 3alpha,21-dihydroxy-5alpha-pregnane-11,20-dione-[21-14C] 21-acetate were prepared from a common radio-labelled intermediate, 21-diazo-3alpha-hydroxy-5alpha-pregnane-11,20-dione-[21-14C] 3-nitrate, obtained by the reaction of 17beta-chlorocarbonyl-3alpha-hydroxy-5alpha-androstan-11-one 3-nitrate with diazomethane-[14C].

Starting from 2,5-dichlorothiophen many new 3,4-disubstituted thiophens have been made including the dialdehyde. Treatment of this with phosphorus pentabromide could be made to give 2,5-dichloro-3- dibromomethylthiophen-4-aldehyde, 2,5-dichloro- or 2-bromo-5-chloro-3,4-bisdibromomethylthiophen. the latter two compounds reacted with sodium iodide to give the corresponding cis - and trans -3,4-dibromo cyclobuteno[ c ]thiophen derivatives ( 18–21 ). Reaction of trans -3,4-dibromo-2,5-dichlorocyclobuteno[ c ]thiophen with N-bromosuccinimide resulted in fission of the 4-membered ring regenerating 2,5-dichloro-3,4-bisdibromomethylthiophen. When 2,5-dichloro-3,4-di-iodothiophen was treated with butyl-lithium followed by dimethylsulphate it gave 2,5- dichloro-3,4-dimethylthiophen together with a low yield of a red compound which is considered to be a dichloro dimethyl derivative ( 11 ) of bisthiophenindigo. Several unsuccessful approaches to the synthesis of dithiophen analogues of biphenylene are outlined. These included heating various 3,4-di-iodothiophens and 4,4′-di-iodo-3,3′-bithienyls with copper as well as the flash vacuum pyrolysis of the latter compounds, of thiophen-3,4-dicar☐ylic anhydrides and of 2,5-dichloro-3-iodothiophen-4-car☐ylic acid.