Structure and stereochemistry of the benzilic acid rearrangement product of 3.alpha.,17.beta.-diacetoxy-11-hydroxy-5.beta.-androst-9-(11)en-12-one

1967 ◽  
Vol 32 (11) ◽  
pp. 3626-3635 ◽  
Author(s):  
Paul Kurath
Keyword(s):  
Rearrangement Product ◽  
Benzilic Acid

Reaction of 1,4-dibromohexafluoro-2-butene with O- and N-nucleophiles

1988 ◽  
Vol 53 (3) ◽  
pp. 619-625 ◽  
Author(s):  
Ivan Hemer ◽  
Věra Moravcová ◽  
Václav Dědek
Keyword(s):  
Kinetic Study ◽  
Sodium Methoxide ◽  
Allylic Rearrangement ◽  
Rearrangement Product

Reaction of 1,4-dibromohexafluoro-2-butene (I) with sodium methoxide, ethoxide or isopropoxide in the corresponding alcohols proceeds with allylic rearrangement under formation of 3-alkoxy-4-bromohexafluoro-1-butenes II-IV. A kinetic study has proven the SN2’ mechanism for reaction of I with potassium phenoxide leading to 4-bromo-3-phenoxyhexafluoro-1-butene (V). Also the reaction of I with ammonia, affording 3-amino-4-bromo-2,4,4-trifluoro-2-butenenitrile (IX), is compatible with the allylic rearrangement by SN2’ mechanism. On the contrary, reaction of I with diethylamine gave no rearrangement product and, after hydrolysis, afforded N,N-diethyl-4-bromo-2,3,3,4,4-pentafluorobutanamide (XVI) and N,N-diethyl-4-bromo-2,3,4,4-tetrafluoro-2-butenamide (XVII) in the ratio 85:15.

An Approach to the Carbocyclic Skeleton of Shinjudilactone Using a Benzilic Acid Rearrangement1,2

1988 ◽  
Vol 18 (1) ◽  
pp. 13-20 ◽  
Author(s):  
Norma K. Dunlap ◽  
Raymond S. Gross ◽  
David S. Watt
Keyword(s):  
Benzilic Acid ◽  
Carbocyclic Skeleton

Stereoselective Synthesis of (±)-Ireland Alcohol Using Titanium-Mediated [2,3]Wittig Rearrangement Product as a Starting Material

1992 ◽  
Vol 65 (7) ◽  
pp. 1841-1848 ◽  
Author(s):  
Satoru Ikegami ◽  
Hiroaki Okamura ◽  
Satoru Kuroda ◽  
Tsutomu Katsuki ◽  
Masaru Yamaguchi
Keyword(s):  
Stereoselective Synthesis ◽  
Starting Material ◽  
Rearrangement Product ◽  
Wittig Rearrangement

Syn-Anti Isomerization in Testosterone 17-Enanthate 3-Benzilic Acid Hydrazone

1979 ◽  
Vol 68 (6) ◽  
pp. 736-739 ◽  
Author(s):  
R. Roman ◽  
C.H. Yates ◽  
J.F. Millar
Keyword(s):  
Benzilic Acid

scholarly journals C18FATTY ACIDS. IV. A REARRANGEMENT OF THE BENZILIC ACID TYPE IN THE ALIPHATIC SERIES

1922 ◽  
Vol 44 (5) ◽  
pp. 1136-1141 ◽  
Author(s):  
Ben H. Nicolet ◽  
Alfred E. Jurist
Keyword(s):  
Acid Type ◽  
Benzilic Acid

scholarly journals The chemical behavior of terminally tert-butylated polyolefins

2015 ◽  
Vol 11 ◽  
pp. 1246-1258
Author(s):  
Dagmar Klein ◽  
Henning Hopf ◽  
Peter G Jones ◽  
Ina Dix ◽  
Ralf Hänel
Keyword(s):  
Catalytic Hydrogenation ◽  
Spectroscopic Data ◽  
Model Compound ◽  
Saturated Hydrocarbon ◽  
Complex Mixture ◽  
Diels Alder ◽  
Equivalent Amount ◽  
Chemical Behavior ◽  
Rearrangement Product ◽  
Olefinic Carbon

The chemical behavior of various oligoenes 2 has been studied. The catalytic hydrogenation of diene 3 yielded monoene 4. Triene 7 was hydrogenated to diene 8, monoene 9 and saturated hydrocarbon 10. Bromine addition to 3 and 7 yielded the dibromides 17 and 18, respectively, i.e., the oligoene system has been attacked at its terminal olefinic carbon atoms. Analogously, the higher vinylogs 19 and 20 yielded the 1,8- and 1,10-bromine adduts 23 and 24, respectively, when less than 1 equivalent of bromine was employed. Treatment of tetraene 19 with excess bromine provided tetrabromide 25. In epoxidation reactions, both with meta-chloroperbenzoic acid (MCPBA) and dimethyldioxirane (DMDO) two model oligoenes were studied: triene 7 and tetraene 19. Whereas 7 furnished the rearrangement product 31 with MCPBA, it yielded the symmetrical epoxide 32 with DMDO. Analogously, 19 was converted to mono-epoxide 33 with MCPBA and to 34 with DMDO. Diels–Alder addition of 7 with N-phenyltriazolinedione (PTAD) did not take place. Extension of the conjugated π-system to the next higher vinylog, 19, caused NPTD-addition to the symmetrical adduct 37 in good yield. Comparable results were observed on adding NPTD (equivalent amount) to pentaene 20 and hexaene 21. Using 36 in excess provided the 2:1-adduct 40 from 21 and led to a complex mixture of adducts from heptaene 22. With tetracyanoethylene (TCNE) as the dienophile, tetraolefin 19 yielded the symmetrical adduct 43, although the reaction temperature had to be increased. Pentaene 20 and hexaene 21 led to corresponding results, adducts 44 and 45 being produced in acceptable yields. With nonaene 42 and TCNE the 2:1-adduct 48 was generated according to its spectroscopic data. Exploratory photochemical studies were carried out with tetraene 19 as the model compound. On irradiation this reacted with oxygen to the stable endo-peroxide 52.

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