Supplements to the 2nd Edition (Editor S. Coffey) of

RODD'S CHEMISTRY O F

CARBON COMPOUND S

A modern comprehensive treatise

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 A : Monocarböcyclic compounds to and including five ring atom sPart B: Six- and higher-membered monocyclic compounds

VOLUME II A B

Alicyclic Compounds ; Monocarbocyclic Compounds to and including Five Rings Atoms ;

Six- and Higher-Membered Monocyclic Compounds .

Preface

vi i

Official publications ; Scientific Journals and periodicals

xiv

List of common abbreviations and symbols used

x v

Chapter 1 . Introductio nby MARTIN F . ANSEL L

1 .

Pericyclic reactions .

.

.

1

a. Generalised Woodward-Hoffmann rule for pericyclic reaction .

6

b. Theoretical basis of Woodward-Hoffmann rules .

7

2 . Stereochemistry and conformational analysis

8

Chapter 2 . The Cyclopropane Groupby P . H . BOYL E

1 . Preparative methods

9

a. Methods based on 1,3-cyclisation

9

b. Methods based on ring contraction .

1 2

c. Methods based on carbene addition .

.

1 4

(i) Halocarbenes, 14 - (ii) Other carbenoid reactions, 16 -

2 . Saturated hydrocarbons

.

1 8

3 . Unsaturated hydrocarbons .

2 0

4 . Halogen derivatives of cyclopropane

2 7

5 . Organometallic compounds derived from cyclopropanes

3 0

6 . Alcohols derived from cyclopropanes

3 1

7 . Sulphur derivatives of cyclopropanes

3 3

8 . Nitrocyclopropanes .

3 4

9 . Amines and related compounds derived from cyclopropanes .

3 4

10 . Aldehydes and ketones derived from cyclopropanes

3 6

11 . Cyclopropane- and cyclopropene-carboxylic acids

4 3

12 . Cyclopropyl and cyclopropenyl carbanions

44

13 . Cyclopropyl radicals

_

4 5

14 . Natural products containing a cyclopropyl ring .

46

Chapter 3 . The Cyclobutane Groupby IAN FLEMIN G

1 . Occurrence, formation and general properties .

49

a. Syntheses and preparative methods

49b. General properties of cyclobutanes .

5 7

2 . Natural products containing a cyclobutane ring

_

5 9

Chapter 4 . The Cyclopentane Group

by P . W . HICKMOTT

1 . Synthesis and spatial geometry of cyclopentane compounds .

6 1

a. Preparative methods .

6 1

(i) Ring-contraction, 61 - (ii) Ring-expansion, 64 - (iii) Miscellaneou s

cyclizations, 65 -

b. Conformational analysis

6 6

2 . Hydrocarbons

6 8

a. Saturated hydrocarbons

6 8

b. Mono-unsaturated hydrocarbons

6 8

(i) Cyclopentenes, 68 - (ii) Hydrocarbons with unsaturated side chains ,

70 - (iii) Cyclopentyne, 72 -

c. Poly-unsaturated hydrocarbons

7 2

(i) Cyclopentadiene, 72 - (ii) Alkyl- and aryl-cyclopentadienes, 73 -

(iii) Cyclopentadienyl ions and radicals, 74 - (iv) Fulvenes and ful-

valenes, 77 -

3 . Metal cyclopentadienyls ; metallocenes

8 1

a. Synthesis

8 2

b. Chemical properties

8 4

(i) Electrophilic substitution, 84 - (ii) Nucleophilic addition and sub-

stitution, 86 - (iii) Reduction and oxidation, 88 - (iv) Ligand

exchange and insertion, 89 - (v) Stability and reactions of the a-

metallocenyl carbonium ion, 94 - (vi) Bridged ferrocenes, ferroceno-

phanes, 96 - (vii) Bi- and poly-ferrocenes, 98 - (viii) Di- and poly -

nuclear complexes, 99 - (ix) Carboranes, 101 -

c. Physical properties and structure of cyclopentadienyl metal compounds

102

(i) Structure and fluxional behaviour, 102 - (ii) Stereochemistry, 10 6

- (iii) Spectroscopic properties, 107 -

d. Orbital symmetry considerations

10 7

4.

Halogen derivatives .

108

5 . Nitro and amino derivatives

11 1

6 . Alcohols of the cyclopentane and cyclopentene series .

11 2

a. Secondary and tertiary cyclopentanols

11 2

b. Cyclopentanediols

-

11 3

c. Unsaturated cyclopentanols

11 4

d. Cyclopentanepentols

11 4

7 .

Aldehydes

_

11 5

8 . Ketones

11 7

a.

Ring ketones

11 7

(i) Saturated monoketones, 117 - (ii), Unsaturated monoketones, 118 -

9 . Hydroxyketones and polyketones of the cyclopentene series .

12 3

a. Hydroxycyclopentenones ; cyclopentenolones

.

12 3

(i) Pyrethrins, rethrolones, and rethrones, 123 - (ii) "Anhydroacetone-

benzils" , 125 -

b. Ring-polyketones

12 6

(i) 1,2-Diketones, 126 - (ii) 1,3-Diketones, 126 -

c. Poly- and exo-cyclic ketones .

12 8

10 . Carboxylic acids, amides and esters

13 0

a. Saturated monocarboxylic acids

13 0

b. Unsaturated monocarboxylic acids and derivatives

13 0

c. Polycarboxylic acids .

13 2

d. Keto-acids

13 3

e. Prostaglandins .

13 5

Chapter 5 . The Cyclohexane Groupby A. J . BELLAM Y

1 . Formation and properties .

14 3

a . Methods of formation .

14 3

(i) Cyclohexenes, 150 - (ii) Alkylidene- and alkenyl-cyclohexanes, 15 3- (iii) Cyclohexadienes, 154 - (iv) Alkylidene- and alkenyl-cyclo-

b . hexenes, 156 -

14 5

2 . Hydrocarbons

14 9

a. Saturated hydrocarbons: Cyclohexanes

14 9

b. Unsaturated hydrocarbons .

.

15 0

(i) Cyclohexenes, 150 - (ii) Alkylidene- and alkenyl-cyclohexanes, 15 3- (iii) Cyclohexadienes, 154 - (iv) Alkylidene- and alkenyl-cyclo-hexenes, 156 -

3 . Halogeno derivatives of the hydrocarbons

15 6

4 . Alcohols and their derivatives

15 7

a. Alcohols

15 7

(i) Monohydric alcohols, 157 - (ii) Dihydric and trihydric alcohols ,

158 - (iii) Polyhydric alcohols (tetrols, pentols, and hexols), 159 -

b. Epoxycyclohexanes .

16 0

c. Peroxides

16 1

5 . Nitro- and amino-cyclohexanes

16 1

a. Nitro compounds

16 1

b. Amines .

16 1

6 . Alicyclic aldehydes

16 2

7 . Alicyclic ketones

16 3

a. Saturated ring ketones

1b 3

(i) Cyclohexanones, 163 - (ii) Cyclohexanediones, 166 -

b. Unsaturated ring ketones

.

.

16 7

c. Exocyclic unsaturated ring ketones .

17 0

d. Exocyclic ketones

17 0

8 . Carboxylic acids

17 1

(i) Cyclohexanecarboxylic acids, 171 - (ii) Unsaturated carboxylic

acids, 172 - (iii) Exocyclic carboxylic acids, 172 - (iv) Hydroxycar-

boxylic acids, 172 - (v) Aminocarboxylic acids, 173 -

Chapter 6. The Acyclic and Mono cyclic Mono terpenoids

by S . H . HARPE R

1. Introduction

17 52. Acyclic monoterpenoids

17 5

3. Monocyclic monoterpenoids

17 9a. Tetramethylcyclohexane derivatives

17 9

b. p-Menthane derivatives

18 2

C . o-Menthane derivatives

18 3d. Cyclopentane derivatives

18 4

e. Other monocyclic monoterpenoids

18 9

Chapter 7. The Carotenoid Group

by J . B . DAVI S

1 .

Basic constitution, classification, and nomenclature

19 2

2 . Occurrence, function and isolation

19 5

3 . Structure and synthesis

19 9

4 . Properties of carotenoids

20 1

a. General properties ; cis-trans isomerism

20 1b. Physical properties

20 3

(i) Visible and ultraviolet absorption spectra, 203 - (ii) Infrare d

spectra, 204 - (iii) Nuclear magnetic resonance, 204 - (iv) Mas s

spectrometry, 208 - (v) Optical rotatory dispersion (o .r.d .) and

circular dichroism (c .d), 210 - (vi) Resonance-enhanced Raman (r .e .r . )

spectroscopy, 212 -

C .

Chemical properties

21 3

(i) Oxidative cleavage at the central double bond of p-carotene (an d

ring-substituted 0-carotenes) to give retinal (and substituted retinals) ,

213 - (ii) Reaction with N-bromosuccinimide (NBS), 213 - (iii)

Reaction with titanium tetrachloride, 213 - (iv) Reactions of caro-

tenoids containing allylic hydroxyl (or alkoxyl) groups, 215 -

5 . Carotenoid hydrocarbons

21 7

6 . The vitamins A and related compounds

22 5

a. Vitamin A 1 : retinol

22 5

(i) The conversion of carotenoids into retinol, 225 - (ii) Synthesis o f

retinol (vitamin A) and related compounds, 227 -

b. Vitamin A 2 : 3,4-dehydroretinol

22 8C .

Retinal and 3,4-dehydroretinal, and the visual process

22 8

The visual process, 229 - (A) Properties of rhodopsin : The nature o f

the retinal-opsin link, 232 - (B) The position of the absorption maxi -

mum in rhodopsin and prelumirhodopsin, etc ., 235 - (C) The nature

of the opsin part of the rhodopsin molecule, 238 - The bleaching

process in vivo ; the final step in the bleaching process; the retinal cycle ,

240 - The visual process in other species, 241 -

d. Kitol

24 1

e. Properties of the vitamins A and related compounds

242

(i) Physical properties, 242 - (ii) Chemical properties, 242 -

7 . Carotenoid compounds containing oxygen ("xanthophylls")

24 5

a. Carotenoid epoxides : general properties

24 5

b. Cyclic hydroxycarotenoids and their oxides, and the hydrocarbo n

oxides

.

24 9

c. Acyclic hydroxy-, methoxy-, and methoxy oxo-carotenoids

26 3

d. Aldehydo-, keto-, and hydroxyketo-carotenoids .

26 6

(i) Aldehydes and hydroxyaldehydes, 266 - (ii) Keto- and hydroxy-

keto-carotenoids, 270 -

e. Carotenoid carboxylic acids .

28 4

f. Allenic carotenoids

288

g. Acetylenic carotenoids

300

h. C 50 (and C45 ) carotenoids

309

i. Carotenoids with partially oxidised methyl groups

320

j. Nor-carotenoids : C3 8 and allied compounds

327

k. Aryl carotenoids

. .

330

I .

Carotenoids of uncertain constitution

33 2

8 . The biosynthesis of carotenoids

33 5

a. Biosynthesis of hydrocarbons

33 5

(i) General, 335 - (ii) The conversion of mevalonic acid into phytoen e

and lycopene, 337 - (iii) The cyclisation step, 350 -

b. Biosynthesis of xanthophylls .

35 5

(i) The insertion of oxygen functions, 355 - (ii) Me 2 C(OH)•CH 2 ••• - >

Me 2 C(OMe)•CH 2 •••, 357 - (iii) Miscellaneous postulated pathways ,

357 -

Chapter 8 . The Cycloheptane, Cyclo-octane and Macro cyclic Group s

by S . H_ GRAHA M

1 . Cycloheptane group .

35 9

a. Hydrocarbons .

35 9

b. Alcohols

36 1

c. Ketones .

36 1

d. Carboxylic acids

36 1

2 . Tropylium salts, tropone

36 1

a. Tropylium salts

36 2

b. Tropone

36 2

c. Tropolones

36 3

d. Rearrangements of tropones .

364

e. Photochemistry of tropolones

36 5

f. Thia analogues of tropolone .

'36 6

3 . Macrocyclic compounds

36 6

a. Hydrocarbons .

36 6

(i) Cyclic olefins, 367 - (ii) Annulenes, 371 -

b. Functionally substituted macrocycles

37 7

4 . The nonadrides

38 3

5 . Conformations of larger rings

38 5

6 . Catenanes and very large rings

389

Index

391