supplements to the 2nd edition (editor s. coffey) of rodd ...bredt's rule 2 5 c. bridged...
TRANSCRIPT
Supplements to the 2nd Edition (Editor S. Coffey) of
RODD'S CHEMISTRY O F
CARBON COMPOUND S
A modern comprehensive treatis e
Edited by
M. F. ANSELLPh .D ., D .Sc . (London), F.R .I .C.
Department of Chemistry, Queen Mary College ,University of London (Great Britain )
Supplement t oVOLUME II ALICYCLIC COMPOUND S
Part C :
Polycarbocyclic compounds, excluding steroid sParts D and E : Steroids
VOLUME IICDE
Alicyclic Compounds ; Polycarbocyclic Compounds ; Steroid s
Preface
vi iOfficial publications ; Scientific journals and periodicals
xvList of common abbreviations and symbols used
xv i
Chapter 9. Polycarbocyclic Compounds with Separate Ring-Systems ,and Spiro Compounds
by A . COX
1. Introduction
.
.
.
.
12. Compounds with rings joined directly or through a carbon chain
13. Spiro compounds ; spirans .
5a. Preparative methods .
5b. Properties
.
8
Chapter 10. Polycyclic Compounds. Fused or Condensed Cyclic System sby A . CO X
1. The bicyclo [ 1 .1 .0] butane group .
. '
92. The bicyclo [2 .1 .01 pentane group .
1 03. The bicyclo [ 3 .1 .0] hexane group .
1 24. The bicyclo [4 .1 .0] heptane group .
1 35. The bicyclo [5 .1 .01 octane group .
1 56. The bicyclo [6 .1 .01 nonane group .
1 57. The bicyclo [ 2 .2 .0] hexane group .
1 68. The bicyclo [ 3 .2 .01 heptane group .
1 89. The bicyclo[4 .2 .01 octane group .
1 910. The bicyclo [6 .2 .0] decane group .
2 011. The bicyclo [ 3 .3 .0] octane group .
2 112. The bicyclo[4.3 .01 nonane group .
2 113. The bicyclo [4.4 .01 decane group .
2 214. Highly condensed systems .
22
Chapter 11 . Polycarbocyclic Bridged Ring Compounds
by R . G . FOSTE R
1 .
Introduction .
2 3
a. General methods of synthesis
2 4
b. Bredt's rule
2 5
c. Bridged carbonium ions
2 6d. Molecular orbital theory
2 7
e. Nuclear magnetic resonance spectroscopy (n .m .r .)
2 7
f. Fluxional molecules
.
2 8
2 .
The bicyclo [ 1 .1 .1 l pentane group .
2 9
3 .
The bicyclo[2 .1 .11 hexane groups .
2 9
Preparation, 29 -
4 .
The bicycloheptanc group .
3 1
a. The bicyclo [ 3 .1 .1 ] heptane group
3 1
Preparation, 31 -
b. The bicyclo [2 .2 .11 heptane group
3 1
Mechanism and structure, 31 - Preparation, 32 -
5 . Polycyclic compounds derived from cyclopentadiene .
3 2
a . Oligomerisation products of cyclopentadiene
3 2
6 . The bi- and tri-cyclooctane group .
3 4
Mechanism and structure, 34 -
a. The bicyclo[2 .2 .21 octane group
3 5
Preparation, 35 -
b. The bicyclo [ 3 .2 .1 ] octane group
3 6
Mechanism and structure, 36 - Preparation, 37 -
c. The tricyclo[ 3 .3 .0 .0 2 ' 8 1 octane group
3 8Hydrocarbons, 39 -
7 .
The polycyclo [ 3 .3 .1 ] nonane group
3 9a. The bicyclo [ 3 .3 .1 ]nonane group
3 9Preparation, 39 -
b. The tricyclo [ 3 .3 .1 .0 2 ' 8 1 nonane group
4 1
Mechanism, structure and reactions, 41 - Preparation, 42 -
c. The tricyclo[ 3 .3 .1 .0 3 '1 nonane group
.
42
Hydrocarbons, 42 - Alcohols, 42 - Carbonyl compounds and car-
boxylic acids, 43 -
d. The tetracyclo[3 .3 .1 .0 2 ' 8 .04 ' 6 ] nonane, triasterane, group
4 3
Hydrocarbons, 43 - Carbonyl compounds, 43 -8 .
The bicyclo [ 3 .2 .2] nonane group .
44
Preparation, 44 -
9 . The bicyclo [4.2 .1 1 nonane group .
44Preparation, 44 -
10 . The bicyclo[4 .2 .21 decane group .
46
Mechanism and structure, 46 - Preparation, 4 6
11 . The tricyclodecane group
47
a .
The tricyclo[ 3 .3 .2 .0 2 ' 8 ] decane group
4 7
Hydrocarbons and halogenated derivatives, 47 - Carbonyl compound s
and carboxylic acids, 47 --
b. The tricyclol3 .3 .1 .1 3 '] decane, adamantane, group
4 7Mechanism and structure, 47 - Preparation, 48 - Homoadamantane ,51 - Diamantane, 51 -
c. The tricyclo[4.4 .0 .03 ' 8 1 decane, twistane, group .
5 112 . The bicyclo[3 .3 .3] undecane group
5 2
Chapter 12 . Bicyclic Monoterpenoids
by R . T . BROWN
1. Introduction
.
5 32. The thujane group .
5 33. The carane group
.
5 84. The pinane group _
6 55. The norbornane group
7 6a. Camphene and related compounds .
7 6b. Bornane (camphane) derivatives
8 1c. Fenchane derivatives .
9 1
Chapter 13 . The Sesquiterpenoid s
by R . RAMAG E
1. Introduction .
9 52 .
Acyclic types
9 6(i) Hydrocarbons, 96 - (ii) Oxygenated derivatives, 96 --
3. Monocyclic types
9 74 . Cyclopentylcyclohexanes .
9 9(i) Hydrocarbons, 99 - (ii) Oxygenated derivatives, 99 -
5 .
Bicyclo[4 .1 .0]heptanes
.
.
100(i) Hydrocarbons, 100 - (ii) Oxygenated derivatives, 101 -
G .
Bicyclo[4 .4 .0] decanes
.
.
.
10 1(i) Hydrocarbons, 101 - (ii) Oxygenated derivatives, 103 -
7 .
Bicyclo[4 .3 .0] nonanes
10 58 .
Bicyclo [ 5 .3 .0] decanes
.
10 6(i) Hydrocarbons, 106 - (ii) Oxygenated derivatives, 106 -
9 .
Spiro compounds
.
.
.
.
106(i) Hydrocarbons, 106 - (ii) Oxygenated derivatives, 107 -
10 .
Polycyclic systems .
.
.
10 8(i) Hydrocarbons, 108 - (ii) Oxygenated derivatives, 110 -
11 .
Macrocyclic sesquiterpenes .
11 1(i) Hydrocarbons, 111 - (ii) Oxygenated derivatives, 113 -
Chapter 14 . Diterpenoids, Sesterterpenoids and Triterpenoids
by J . D . CONNOLLY and K . H . OVERTO N
1. Introduction .
11 52. Diterpenoids .
11 5a .
Bicyclic diterpenoids .
11 5(i) Unrearranged labdanes, 115 - (ii) Rearranged labdanes, 116 -
b. Tricyclic diterpenoids .
.
-
.
1 1 8
(i) Rearranged pimaranes, 118 - (ii) The abietane group, 119 -c. Tetracyclic diterpenoids
12 1
(i) The kaurane group, 121 - (ii) The atisirane group, 122 -
d. The cembrane group .
12 3e. Eremolactone .
12 4
3. Sesterterpenoids
12 5
4. Triterpenoids
12 7
(a) The fusidanes, 127 - (b) Group A, 129 - (c) Group B, 132 -
5. Laboratory synthesis
13 4
a. Diterpenoids
13 4
b. Triterpenoids .
136
Chapter 15, Steroids : Sterols and Bile Acids
by A . B . TURNE R
1 .
Introduction
_
14 32 . Geometry of the steroid nucleus .
14 3
3 .
Structure in relation to physical properties
144
4 .
Principal chemical reactions
146
(i) Colour reactions, 146 - (ii) The 3,5-cyclosteroid rearrangement an d
related reactions, 146 - (iii) Backbone rearrangements and related
reactions, 148 - (iv) Side-chain oxidation, 150 - (v) Epoxidation o fO 5 -stenols and related compounds, 152 - (vi) Reactions of 7-dchydro-
sterols, 153 - (vii) Stanols, 153 - (viii) Stanones, 153 - (ix) Remot eoxidation, 154 -
5 .
Individual sterols and related compounds
15 6a.
The cholesterol series .
15 6(i) Cholesterol and its derivatives, 156 - (ii) Methyl derivatives, 157 -
(iii) Epicholesterol, 157 - (iv) Cholestadienols, 158 - (v) Hydroxy-
cholesterols, 158 - (vi) Oxocholesterols, 160 -- (vii) Cholestanols, 16 0
- (viii) Phosphorous- and sulphur-containing steroids, 160 - (ix) Chol-
estanediols, 161 - (x) Oxidocholestanes, 161 - (xi) Cholestenes, 16 1
- (xii) Cholestenones, 162 - (xiii) Cholestenediones, 163 -
b. Ergosterol and related compounds .
16 4
(i) Ergosterol, 164 - (ii) Irradiation products of ergosterol, 167 -
c. Other sterols
.
16 8
(i) Sterols of algae, 168 - (ii) Phytosterols, 168 - (iii) Sterols fro m
marine invertebrates, 170 - (iv) Sterols from miscellaneous sources ,173 -
d. Miscellaneous structural type
17 36 .
Bile acids
17 6Additions
17 8
Chapter 16 . Steroids : Sex hormones; Adrenocortical hormone s
by P . G . MARSHAL L
1 . Sex hormones and related compounds
17 9
a . Oestrogens
179
b. The gestogens .
.
.
.
18 2
Stereoisomers of progesterone, 186 - Progestational activity an d
structure, 186 - Gestogenic 19-nor-steroids, 186 -
c. The androgens .
.
.
.
18 7Dehydroepiandrosterone, 187 - Testosterone, 188 - Physiologica lproperties of testosterone etc ., 188 -
d,
Homosteroids .
.
.
.
18 9e .
Synthesis of adrenocortical steroids .
19 0Dehydro derivatives of cortisone, etc ., 190 -
2 . Adrenocortical hormones .
19 0d. Aldosterone
19 03 . Cyclosteroids
19 14 . Dimeric steroid hormones .
19 15 . Halogenated steroids
19 1a. Oestrogens
19 1(i) Halogenation in ring A, 191 - (ii) Halogenation in ring D, 192 - -
b- Androgens
_
192(i) Halogenation in ring B, 192 - (ii) Halogenation in ring D, 192 -
c . Gestogens
-
192Halogenation in rings A and B, 192 -
6 . Other substituted steroids 19 3b .
Pregnane series -
-
19 3
Chapter 17. Steroids: Cardiotonic glycosides and aglycons ; Toad poisons, p . 19 5by P . G . MARSHAL L
Digoxin derivatives, 199 - Digitoxigenin and derivatives, 199 -Canatigenin (A 4-analogue of digitoxigenin), 200 - Uzarigenin an drelated compounds, 201 - Digitalis glycosides and aglycons, 202 -Digitoxigenone, 202 - Toad poisons, etc ., 20 2
Chapter 18 . Steroid Saponins and Sapogenins
by J . ELKS
1. The saponins .
20 52 . The sapogenins
_
20 7
Sources and isolation, 207 - Biogenesis, 210 - Physical properties ,2111 - New sapogenins, 211 - Aminospirostans, 223 - Reactions o fthe sapogenin side-chain, 225 -
Chapter 19 . Biogenesis of Terpenes and Sterol sby T . W . GOODWI N
1. Introduction .
.
.
23 72. Biosynthesis of mevalonate (MVA)
23 73. Hemiterpenes
23 8
4. Monoterpenes
24 15. Sesquiterpenes
24 76. Diterpenes
252
8 .
Triterpenes 25 9(i) General, 259 - (ii) Demethylation reactions, 265 - (iii) Alkylatio nat C(24), 268 -- (iv) Insertion of double bonds, 271 - (v) Spirostanols ,
273 - (vi) Cardenolides, 275 - (vii) Bufatenolides, 276 - (viii )
Ecdysones, 277 --
9 . The tetraterpenoids : the carotenoids
27 9
(i) Prephytoene, 279 - (ii) Desaturation of phytoene, 279 - (iii )
Cyclisation of lycopene, 282 - (iv) Xanthophyll formation, 284 - (v )
C4 5 and C 50 carotenoids, 285 - (vi) Biosynthesis in photosyntheti c
bacteria, 287 -
10. Terpenoid quinones .
_
28 9
Index
291