RODD'S CHEMISTRY

OF CARBON COMPOUND S

A modern comprehensive treatis e

SECOND EDITIO N

Edited by

S . COFFE Y

M.Sc. (London), D .Sc. (Leyden), F .R.I .C .

formerly of

I.C.I . Dyestuffs Division, Blackley, Mancheste r

VOLUME II PART E

STEROID S

(continued from Vol . II Part D )

CUMULATIVE INDEX VOL . II PARTS A-E

PREFACE TO VOLUMES IID AND IIE IXOFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XII ILIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XI V

Chapter z8 : Steroid Saponins and Sapogenins

J . ELx s

1. The saponins I2. The sapogenins 6

a. The nucleus 7b. The side-chain 7

(i) Pseudosapogenins and cyclopseudosapogenins, 9 - (ii) Normal and iso-sapogenins : configuration at Co25), ri - (iii) Configuration of the sapogeninsand cyclopseudosapogenins at Co20) and C(22), 14 - (iv) Nomenclature, 18 --(v) Reactions of the sapogenin side-chain, 19 - (vi) Synthesis of thesapogenin side-chain, 21 - (vii) Biogenesis of the steroid sapogenins, 2 3

c. Individual sapogenins 2 9

(i) Sapogenins with normal side-chains, 29 - (ii) Sapogenins with modifie dside-chains ; kryptogenin and its congeners, 43 - (iii) Sapogenins bearinghydroxyl groups in Ring F, 46 - (iv) Sapogenins with Ring F unsaturated ,51 - (v) Aminospirostans, 5 2

Chapter 19 : The Biogenesis of Terpenes and Steroid s

T . W . GoonwI N

1 . Introduction 5 42 . Biosynthesis of isopentenyl pyrophosphate and dimethylallyl pyro -

phosphate 5 53 . Hemiterpenes 6 1

a. Classification 6 1

(i) Free hemiterpenes, 61 - (ii) Phenolic hemiterpenes, 62 - (iii) Alkaloid swith hemiterpene residues, 64 - (iv) Isopentenyl adenosine and relatedcompounds, 64

b. Biosynthesis of hemiterpenoids 6 54 . Monoterpenes 6 6

a . The basic precursor and classification 6 6

(i) Acyclic monoterpenes, 67 - (ii) Monocyclic monoterpenes, 68 [i . Cyclo-hexanes, 68 - 2 . Cyclopropanes, cyclopentanes and cycloheptanes, 68] -

(iii) Bicyclic monoterpenes, 69 - (iv) Tricyclic monoterpenes, 69 - (v) Phe-nolic monoterpenoids, 70 - (vi) Alkaloids with monoterpene residues, 7o -(vii) Atypical monoterpenes, 70

b. Biochemical studies on monoterpene biosynthesis 7 1c. Biogenetic considerations 7 6

(i) General, 76 - (ii) Oxidations, 76 - (iii) Aromatization, 77 - (iv) Cyclo-heptanes, 78 - (v) Furan rings, 78

5 . Sesquiterpenes 7 9a. The basic unit 7 9b. Classification 8 oc. Biosynthetic studies 8 1d. Biogenetic relationships 8 4

6 . Literpenes 8 5a . The basic unit and classification 8 5

(i) Monocyclic diterpenes, 86 - (ii) Bicyclic diterpenes, 86 - (iii) Tricyclicditerpencs, 86, - (iv) Tetracyclic diterpenes, 87 - (v) Diterpene derivatives ,8 7

h . Biosynthetic studies 8 87 . Sesterterpenes 9 28 . Triterpenes 9 3

a. The basic unit 9 3b. Biosynthesis of tetracyclic triterpenoids 94

(i) In animals, f4 - (ii) Synthesis in higher plants and micro-organisms ,103 - (iii) Mechanism of alkylation, lo8 - (iv) Formation of C(22) doublebond in plant sterols, 109 - (v) C(z1) Sterols in plants, r to [t . Pregnanederivatives, i lo - 2 . Cardenolides, 111] - (vi) C(I5) Sterols in plants, 112 -(vii) Spirostanols C (2) in plants, x 12 - (viii) I3nfaclicnolides, 113 - (ix) Eccly -soneS, 113 - (x) Compounds other than sterols with the cyclopentenophe-nantlirene nucleus, 11 5

c. Biosynthesis of pentacyclic triterpenes 116d. Degraded triterpenes 12 0

9 . Tetraterpenoids 12 0

a. Biosynthesis of tetraterpenoids Ito

(i) Formation of cyclic carotenoids, 126 - (ii) Insertion of oxygen, 126 -(iii) Degradation products of ft-carotene, 13 2

lo. Polyterpenoids 1 3 311. Terpenoid quinones 1 3 412. Regulation of terpenoid synthesis in seedlings 1 3 5

Cumulative Index Vols . IIA-E

13 9

VOLUMES IIA, B, C AND D

Vol. IIA Monocarbocyclic compounds Cg C 5

Vol . IIB Six- and higher-membered monocyclic compound s

Vol . IIC Polycarbocyclic compounds, excluding steroid s

Vol . IID Steroids (continued in Vol . IIE)