Organic compounds of sulphur, selenium, and tellurium, vol 4

Con tents Chapter 1 Aliphatic Organo-sulphur Compounds, Compounds with Exocyclic Sulphur Functional Groups, and their Selenium and Tellurium Analogues By G, C.. Barrett 1 Textbooks an

A Specialist Periodical Report

Selenium, and Tellurium

Senior Reporter

D R Hogg, Deparfmenf of Chemistry, University of Aberdeen

Reporters

G C Barrett, Oxford Polytechnic

R J S Beer, Universify of Liverpool

E Block, University of Missouri, U.S.A

D C Dittmer, Syracuse University, New York, U.S.A

G L Dunn, Smith Kline and French Laboratories, Pennsylvania, U.S.A

T Durst, Universify of Ottawa, Ontario, Canada

U Eisner, Trent Polytechnic, Nottingham

J G Gleason, Smith Kline and French Laboratories, Pennsylvania, U.S.A

S Gronowitz, University of Lund, Sweden

M Haake, lnstifut fur Pharmazeutische Chemie, Marburg, West Germany

B Iddon, University of Salford

F Kurzer, Royal Free Hospitai School of Medicine, London

P A Lowe, University of Salford

P Metzner, Universith de Caen, France

G Prota, Universifa di Napoli, Italy

J Voss, Universifaf Hamburg, Wesf Germany

W Walter, Universitat Hamburg, West Germany

Burlington House, London, W I V OBN

ISBN : 0 85186 289 6

ISSN : 0305-9812

Library of Congress Catalog Card No 77-23818

Copyright @ 1977

The Chemical Society

All Rights Reserved

No part of this book may be reproduced or transmitted

in any form or by any means -graphic, electronic,

including photocopying, recording, taping or

information storage and retrieval systems - without

written permission from The Chemical Society

Organic formulae composed by Wright's Symbolset method

Preface

The general aims of this fourth Volume of ‘Organic Compounds of Sulphur,

Selenium, and Tellurium’ remain those set out in the Preface to Volume 1

Change of personnel has led to the division of the wide-ranging chapters on

thiocarbonyl compounds and on ylides into more manageable parts In keeping with more recent work, the short sections on sulphines and sulphenes have been confined to the chapter on thiocarbonyl compounds To avoid possible inconsistencies, the chemistry of sulphonyl, sulphinyl, and sulphenyl carbanions has been largely included in the chapter on ylides The order of the chapters has been revised so that the chemistry of acyclic sulphur compounds and sulphur- containing functional groups is covered before cyclic systems

In general, these Reports cover the period from April 1974 to March 1976

unless otherwise stated Due to necessary limitations of space, the topics have,

in parts, been treated more summarily than in previous Reports A review of the chemistry of thiepins and dithiins, omitted from Volume 3, has been included in this volume, but accounts of the chemistry of thiazepines and of heterocyclic compounds of quadricovalent sulphur have been held over to Volume 5

As was stated in earlier volumes, constructive criticism, comments, and advice

will be welcomed, particularly if they enable subsequent Reports to be orientated more exactly with the requirements of research workers

D R H

Con tents

Chapter 1 Aliphatic Organo-sulphur Compounds, Compounds with

Exocyclic Sulphur Functional Groups, and their Selenium and Tellurium Analogues

By G, C Barrett

1 Textbooks and Reviews

2 Spectroscopic and Other Physical Properties

General Conforinational Studies and Molecular Orbital

Ultraviolet Spectra

Infrared, Raman, and Microwave Spectra

Nuclear Magnetic Resonance Spectra

Mass Spectra

Photoelectron Spectra

Electron Diffraction

Dipole-moment and Kerr-effect Studies

Optical Rotatory Dispersion and Circular Dichroism Spectra Other Physical Properties

Addition Reactions of Thiols

Further Reactions of Thiols

Protection of Thiols in Synthesis

Generation of Thiyl Radicals and Thiolate-stabilized

Properties and Reactions of Saturated Sulphides

Preparation of Vinyl Sulphides

Properties of Vinyl and Ally1 Sulphides

vi Con tents

23

Rearrangements of Unsaturated Sulphides

Naturally Occurring Sulphides, and Sulphides Related

to Natural Products Thiocyclopropenium Salts

Elimination Reactions of Aliphatic Sulphoxides

Applications of Dimethyl Sulphoxide and Dimethyl

Sulphenamides and Related Compounds

10 Thiocyanates and Isothiocyanates

Con tents vii

11 Sulphinic Acids

Preparation

Properties and Reactions of Sulphinic Acids

Sulphinyl Halides

Sulp hina t e Esters

Sulphinamides and Related Compounds

13 Disulphides and Related Compounds

Preparation of Disulphides and Polysulphides

Properties of Disulphides and Polysulphides

viii Con tents

6 Sulphenyl Carbanions

Synthesis and Properties

Reactions

1,3-Dithianyl Anions Thioallyl and Kelated Anions Acyclic a-Thiocar bani ons, T h ioace t a1 A n io tis, and Trithioformate Anions

9 Organoselenium and Organotellurium Carbanions and Y l i h

11: Compounds with S=N Functional Groups

Sulphonylamines and Sulphurtri-imides

SS-Diorgano-sulphimides and Azasulphonium Salts

3 Tetra-co-ordinate Sulphur

SS-Diorgano-sulphoximides

SS-Diorgano-sulphodi-imides

4 Selenium Analogues

Chapter 3 Thiocarbonyl and Selenocarbonyl Compounds

I: Thioaldehydes, Thioketones, Thioketens, and their

Analytical Properties and Applications

Chemical React ions

Alkylation Addition to Multiple Bonds Oxidation

Hydrolysis and Related Reactions Cyclization

3 Thiosemicarbazides and Selenosemicarbazides

X Contents

5 Thiono- and Dithio-carboxylic Acids, their Derivatives, and

their Selenium Analogues

Synthesis of Dithiocarboxylic Acids

Synthesis of Thioacyl Halides

Synthesis of Thiono- and Dithio-esters

Alkylation of Thio- and Dithio-carboxylates Thiolysis and Thionation of Carboxylic Acid Derivatives Thioacylation of Alcohols and Thiols

Miscellaneous Physical Properties

3 Thiiran 1-Oxides (Episulphoxides)

4 Thiiran 1,l-Dioxides (Episulphones)

5 Thiiren Derivatives

6 Three-membered Rings containing Sulphur and One or Two

0 ther He teroa toms

Contents xi

11 Four-membered Rings containing One Sulphur Atom and One

or More Heteroatoms

Thiazetidines and Thiazetes

Sultines, Sultones, and Cyclic Sulphates (1,2-0xathietan 2-Oxides, 1,2-Oxathietan 2,2-Dioxides, and 1,3,2-Dioxa- thietan 2,2-Dioxides)

Properties and Reactions

3 Compounds with Two Sulphur Atoms in the Ring, and their Oxy-sulphur Analogues

Cycl ic Dis u 1 p h ides

1,3-Dithiolans and 1,3-Dithians

4 Compounds containing Three or More Sulphur Atoms

1,2,3- and 1,2,4-Trithiolans, 1,2,3- and 1,3,5-Trithians, 1,2,4,5Tetrathian, and Larger Rings containing Three

or More Sulphur Atoms Sulphur-containing Macrocyclic Rings

5 Compounds containing Sulphur and Oxygen

Sultines, Sultones, and Related Systems

1,3-Oxathiolans, 1,3-0xathians, 1 ,4Oxathians, and Related Cyclic Sulphites and Related Compounds

xii Contents

Syntheses of Thiophens from other Ring Systems

Ultraviolet and Infrared Spectra

Dipole Moments and Conformational Analyses

Electrochemical React ions

The Structure and Reactions of Hydroxy-, Mercapto-, and Amino-thiophens

Side-chain Reactivities

‘Benzylic’ Reactivity

Reactions of Thiophen Aldehydes and Ketones

Reactions of Cyano- and Carboxy-thiophens

Various Side-chain Reactions

Bi- and Poly-heterocycles

Macrocyclic Compounds containing Thiophen Rings

Reactions Leading to Destruction of the Thiophen Ring

Naturally Occurring Thiophens

Thiophens of Pharmacological Interest

3 Thienothiophens, their Benzo-derivatives, and Analogous Compounds

Synthesis

React ions

Physical Properties

Non-classical Thienothiophens and Related Systems

4 Benzothiophens and their Benzo-fused Systems

Synthesis of Benzothiophens by Ring-closure Reactions

Electrophilic Substitution

Metallation and Halogen-Metal Exchange

2- and 3-Hydroxybenzo[b]thiophens and Related Systems

Side-chain Reactions

Reaction at Sulphur

Pharmacologically Active Compounds

5 Thiophen Analogues of Polycyclic Aromatic Hydrocarbons

Thiophen Analogues of Anthracene and Phenanthrene

Thiophen Analogues of Helicenes

Thiophen Analogues of Indene

Thiophen-fused Tropylium Ions and Related Compounds

6 Thiophens Fused to Five-membered Aromatic Heterocyclic

7 Thiophens Fused to Six-membered Aromatic Heterocyclic Rings 29 1

Thiophen Analogues of Isoquinoline 292

8 Selenophens and Tellurophens

Monocyclic Selenophens

Physical Properties Reactions

5 Other Analogues of 6a-Thiathiophthens 304

Chapter 8 1,2- and 1,3-Dithioles

xiv

6 Dithiafulvene Derivatives

Contents

315

7 Tetrathiafulvalenes and Selenium-containing Analogues 316

Chapter 9 Thiopyrans and Related Compounds

4 4H-Thiopyrans and Related Compounds 322

7 Benzothiopyrans and Related Compounds 326

Chapter 10 Thiepins and Dithiins

1,4-Dithiins and Related Compounds

Benzo- and Dibenzo- I ,4-dithiins

Chapter 11 lsothiazoles and Related Compounds

From j5-Chlorovinylmethine-immonium and Bunte Salts 340

By B lddon and P A Lowe

Synthesis of Meso-ionic Thiazoles

3 Physical Properties of Thiazoles

4 Chemical Properties of Thiazoles

Electrophilic Substitution

Nucleophilic Substitution

Thiazolyl Radicals and their Reactions

Oxidation and Reduction

Ring Expansion to 1,4-Thiazines

9 Physical Properties of A%-Thiazolines

10 Chemical Properties of A4-Thiazolines

Contents

12 Physical Properties of Thiazolidines

13 Chemical Reactions of Thiazolidines

Ring-cleavage Reactions

Other Reactions

14 Rhodanines, Isorhodanines, and Thiorhodanines

15 Selenazoles

Chapter 13 Condensed Ring Systems Incorporating Thiazole

By B lddon and P A Lowe

Synthesis from Thiazoles

Synthesis from 3,5-Bis(arylimino)- 172,4-thiadiazolidines Synthesis from 1,4-Benzothiazines

Other Syntheses

(Dost's Bases) ; Structure o f Hugershoffs Bases

3 Physical Properties of Benzothiazoles

4 Chemical Properties of Benzothiazoles

Oxidation and Reduction

Reactions of Benzothiazoles with Singlet Oxygen

Nucleophilic Substitution

Reactions of Benzot hiazoles with Dimethyl Acetylene-

Organometallic Derivatives

Alkylation Reactions

Reactions of Benzothiazoliuni Salts

Reactions of Other Derivatives

dicarboxylate

5 Benzoselenazoles and Naphthoselenazoles

6 Structures Comprising Two Five-membered Rings

Thiazolo- [2,3-c]- and - [3,2-b]- [ 1,2,4] thiadiazoles

Thiazolo-[2,3-c]- and -[3,2-b]-[ 172,4]triazoles

7 Structures Comprising One Five-membered and One Six-

8 Structures comprising Two Five-membered Rings and One

[ 1,2,4]Triazolo- [3,2-b]- and - [3,4-b]- benzot hiazoles 407

Thiazolo-[2,3-f]- and -[3,2-e]-purines 409 Thiazolo-[3,2-a]- and -[3,4-~]-benzimidazoles 409

Thiazolo [4,5-a]phenot hiazines

Benzot hiazolo-[2,3-b]- and - [3,2-c]-quinazolines

Chapter 14 Thiadiazoles and Selenadiazoles

By Oxidation of a- Aryl hydrazono-thioamides

Meso-ionic 1,2,3-Thiadiazoles

Chemical Properties

Photolytic Reactions Thioketens from 1,2,3-ThiadiazoIes Biochemical Properties

1 ,2,3-Benzot hiad i azoles

From amidines Type C Syntheses From amidino-thiono-compounds

Chemical Properties

Alkylation Cycloaddi t ion Biological Activity

Chemical Properties

Alkylation Ring Fission Nucleophilic Substitution Reductive Removal of Mercapto-groups Dimerizat ion

Formation of Metal Complexes

Polymeric 1,3,4-Thiadiazoles Analytical

Biochemical Aspects Biological Activity

13 2,1,3-Benzothiadiazoles and Selenium Analogues

14 Condensed Ring Systems incorporating 1,2,5-Thiadiazole

1,2,3-Triazolo[4,5-c] [ 1,2,5]thiadiazoles and Selena-

Benzo- 1,4-thiazines and Related Compounds

Phenothiazines and Related Compounds

xxii Contents

Chapter 16 F-Lactam Antibiotics, other Sulphur-containing Natural

By J G Gieason and G L Dunn

3 Modification of the @-Lactam Ring System

5 Rearrangements of Penicillins and Cephalosporins 476

nuclear magnetic resonance

tristl, 1 ,1,2,2,3,3 ]heptafluoro-7,7-dimet hyl-4,6-octanedionato- tris[ ],I, 1,2,2,3,3,7,7,8,8,9,9,9]tetradecaAuoro-

optical rotatory dispersion circular dichroism

electron spin resonance

3,4dihydroxy-~-phenylalanine

gas-liquid chromatography N-bromosuccinimide

complete neglect of differential overlap

diazabicyclo-octane dicyclohexylcarbodi-i mide dimethoxyet hane

"-dime t hylformam ide

dimethyl sulphoxide tetramethylethylenediamine dimet h yl acetylenedicarbox ylat e

trifluoroacet ic acid hexamethylphosphoric triarnide tetrahydrofuran

p yridine Reference back to a preceding Volume of this series of

europium(r1i) 4,6-nonanedionato-europium(11~)

'Specialist Periodical Reports'

1

Aliphatic Organo-sulphur Compounds, Compounds

Selenium and Tellurium Analogues

~~

BY G C BARRETT

The literature covering compounds containing organosulphur functional groups

is reviewed in this chapter, which is split, as in previous Volumes, into sections dealing with the different classes of organosulphur compounds Preliminary sections list textbooks and reviews, and spectroscopic and other physical pro- perties, dealt with in an integrated manner Later chapters in this volume review the literature of organosulphur compounds containing thiocarbonyl functional groups, and compounds enclosing organosulphur functional groups as integral parts of cyclic systems

1 Textbooks and Reviews

Specialist textbook coverage is becoming less sparse in this area of organic chemistry; the plenary lectures and abstracts of papers presented at the VIth International Symposium on Organic Sulphur Chemistry have been published, and a number of specific topics have been reviewed in monograph form.2 Thorough coverage of organoselenium and organotellurium chemistry has been published

Recent developments in organosulphur chemistry have been broadly reviewedY5 and other more general reviews cover applications of electron spectroscopy and dynamic conformational analysis of organosulphur compound^.^

General comments on the problems of handling organotellurium compounds,

which are sensitive to oxygen in solution, are given in ref 138

‘Organic Sulphur Chemistry’, ed C J M Stirling, Butterworths, London, 1975

a (a) ‘Topics in Sulphur Chemistry’, ed A Senning, Vol 1, Thieme Verlag, Stuttgart, 1975;

(b) ‘The Chemistry of the Thiol Group’, ed S Patai, Wiley-Interscience, London and New York,

1974; (c) Y M Torchinskii, ‘Sulphydryl and Disulphide Groups of Proteins’, Plenum Press, London, 1974; ( d ) ‘Metabolic Pathways Vol 7 Metabolism of Sulphur Compounds’, ed

D M Greenberg, Academic Press, New York, 1975; (e) ‘Chemistry and Biochemistry of Thiocyanic Acid and its Derivatives’, ed A A Newman, Academic Press, New York, 1975;

(f) E Kiihle, ‘The Chemistry of the Sulphenic Acids’, Thieme Verlag, Stuttgart, 1973; (g) D

Martin and H G Hauthal, ‘Dimethyl Sulphoxide’, Van Nostrand, London, 1975

a K J Irgolic and M V Kudchadker, in ‘Selenium’, ed R A Zingaro and W C Cooper, Van Nostrand-Reinhold, New York, 1974, p 408

4 K J Irgolic, ‘Organic Chemistry of TelIurium’, Gordon & Breach, New York, 1974; K J Irgolic, J Organometallic Chem., 1975, 103, 91

P Neumann and F Voegtle, Chem.-Ztg., 1974,98, 138; 1975,99, 308

B J Lindberg, Internat J Sulfur Chem., Part C, 1972,7,33

C H Bushweller, Internat J Sulfur Chem., 1973,8, 103

1

2 Organic Compounds of Sulphur, Selenium, and Tellurium

Reviews of the following topics have appeared : alkynethiols and thioketens,8a

addition of SCI2 to unsaturated systems,8b pyridyl sulphides and selenides,80

1 -1ithiocyclopropyl phenyl sulphide and diphenylsulphonium cyclopropylide as alkylating agents,Rd sulphuranes,8e~ a-halogenosulphoxides and related com- pounds,8Q allylic sulphoxides and sulphides in organic synthesis,8h stereo- chemistry of sulphoxides,8i a-sulphinylcarbanions,sj aliphatic diazosulphones,sk base-induced rearrangements of sulphones,8z* sulphoximides,8n stereochemistry

of substitution reactions at insertion of SO, into Si-C 8 p and transition- metal-carbon 1,3-dipolar cycloaddition reactions of isothiocyanates,8g aromatic sulphenic acid derivatives,8r and sulphenarnide~.~~

2 Spectroscopic and Other Physical Properties

Like the preceding section, relatively little beyond a statement of the content of each paper is provided for most of the citations dealing with spectroscopic and other physical studies of organosulphur compounds in the following paragraphs However, all the references include interpretation of the data in terms of con- formation, bonding, or insight into reactivity; mere data compilations are excluded

Spectroscopic methods for the study of thiols, sulphides, and disulphides have been reviewed.$

General Conformational Studies and Molecular Orbital Calculations.-Factors favouring the increasing proportion of the trans,trans-rotamer through the series

divinyl sulphide, sulphoxide, and sulphone have been considered.1° The molecular

mechanics (or force-field) method has been extended to thiols and sulphides,ll leading to reasonable agreement between predicted conformations and those established by physical studies Conformational characteristics of sulphoxides suggest repulsion, rather than non-bonded attraction, between sulphoxide oxygen and nearby hydrogen afoms.l2 Attractive forces between sulphur and carbon atoms which have a lY4-relationship in aliphatic sulphides and disulphides are implied by M.O calculations of dihedral angle-energy re1ation~hips.l~

II ( a ) R Mayer and H Kroeber, 2 Chem., 1975, 15, 91 ; (b ) M Miihlstidt and D Martinetz,

Z Chem., 1974, 14,297; ( c ) H L Yale, in 'The Chemistry of Heterocyclic Compounds', Vol

14, Part 4, 1975, 189; ( d ) B M Trost, Accounts Chem Res., 1974, 7 , 85; ( e ) N E Hester,

Internat J Sulfur Chem., 1973,8, 119; (f) J C Martin and E F Perozzi, Science, 1976,191, 154; ( g ) C G Venier and H J Barager, Org Prep Proced Internat., 1974, 6, 79, Prepr., Dic Pet Chem., Amer Chem SOC., 1974, 19, 191; (h) D A Evans and G C Andrews, Accounts Chem Res., 1974,7, 147; ( i ) L Van Acker, Znd chim belge, 1974,39,125; ( j ) T Durst and R Viau, Zntra-Sci Chem Reports, 1973,7,63; (k) A L Fridman, Y S Andreichikov, V L Gein, and S S Novikov, Uspekhi Khim., 1975,44,2284; (1) J Skarzewski and Z Skrowaczewska, Wiad Chem., 1974,28, 155; (m) V N Drozd, Internat J Surfur Chem., 1973,8,443; (n) P D

Kennewell and J B Taylor, Chem SOC Rev., 1975, 4, 189; (0) D J Cram, J Day, D C

Garwood, D R Rayner, D M von Schrilz, T R Williams, A Nudelman, F G Yamagishi,

R E Booms, and M R Jones, Internnr J Sulfur Chem.,Part C, 1972,7, 103; ( p ) U Kunze and J D Koola, J Organometallic Chem., 1974,80, 281 ; (q) E van Loock, Znd chim belge,

1974, 39, 661 ; ( r ) E Vinkler and F Klivenyi, Internat J Surfur Chem., 1973, 8, 11 1 ; (s) F A

Davis, Internat J Sulfur Chem., 1973,8, 71

G Jung and M Ottnad, Chem.-Ztg., 1974,98, 147

l o A B Remizov, T G Mannafov, and F R Tantasheva, Zhur obshchei Khim., 1975, 45, 1402

l1 N L Allinger and M J Hickey, J Amer Chem SOC., 1975, 97, 5167

la N L Allinger and J Kao, Tetrahedron, 1976,32, 529

l8 H E van Wart, L L Shipman, and H A Scheraga, J Phys Chem., 1975,79, 1428, 1436

Aliphatic Organo-sulphur Compounds etc 3

Stabilization of an a-carbanion by divalent sulphur is the result of the polariza- bility of the sulphur atom rather than p,,-d, conjugation;l4# l6 and the same basis

is suggested for the enhanced acidity of an a-proton in aliphatic ~u1phides.l~ rr-Donating abilities for various heteroatoms towards an adjacent carbonium ion centre follow the series P > S 3 N > 0 > C1 > F,ls implying (in contrast to

current ideas) that a Period 3 element in the system X-CH2+ is a better electron

donor than the corresponding Period 2 element

Ultraviolet Spectra.-Int eraction between the chromop hores in p henylsulp honyl- guanidines through an empty d-orbital on S, and between the sulphone Ir-system and the guanidine chromophore, is indicated by U.V spectra,17 while related studies show the lack of homoconjugation (through-space conjugation) in aryl benzyl sulphides.l* U.V fluorescence and phosphorescence data indicate exciton interaction between the phenyl chromophores in diphenyl s~1phide.l~

Infrared, Raman, and Microwave Spectra.-Interpretation of i.r data in terms of hydrogen-bonding equilibria has been reported for thiols,20, 21 sulphides,22 and MeS02NMe2.23 A diminished H-bonding capacity is demonstrated for a sulphonamide compared with the corresponding ~ a r b o x a m i d e ~ ~

Aliphatic thiols have been subjected to ix., Raman,24 and microwave spectro- scopic 26 studies Methyl and ethynyl groups are gauche in ethyl vinyl sulphide,

as judged from microwave data.26 I.r./Raman studies of aliphatic sulphides 27

and disulphides 28 similarly include interpretation in terms of conformation or bonding Comparative i.r./Raman studies of dimethyl sulphide, sulphoxide, and sulphone 29 and the corresponding diphenyl series 30 have been described 1.r spectra of selenuranes 31 and sulphones 32 and sulphimides 33 have been inter-

A Streitweiser and J E Williams, J Amer Chem SOC., 1975,97, 191

F Bernardi, I G Csizmadia, A Mangini, H B Schlegel, M.-H Whangbo, and S Wolfe,

J Amer Chem SOC., 1975,97,2209

F Bernardi, I G Csizmadia, and N D Epiotis, Tetrahedron, 1975,31, 3085

A Rastelli, P G de Benedetti, A Albasini, and P G Pecorari, J.C.S Perkin ZZ, 1975, 522

V Mancini, 0 Piovesana, and S Santini, 2 Naturforsh., 1974,29b, 815

P G Russell, J Phys Chem., 1975,79, 1475

B Wladislaw, P R Olivato, and R Rittner, Rev Latinoamer Quim., 1974, 5, 206 (Chem

Abs., 1975, 82, 85 596)

F D Mamedov and M A Salimov, Izvest Akad Nauk Azerb S.S.R., Ser Fiz Tekh Mat Nuuk, 1973,104 (Chem Abs., 1974,80, 119 753)

B A Trofimov, N I Shergina, E I Kositsyna, E P Vyalykh, S V Amosova, N K Gusarova,

and M G Voronkov, Reakts spos org Soedinenii, 1973, 10, 747

M Jarra, M Saastamoinen, and P 0 1 Virtanen, Finn Chem Letters, 1974, 169

C S Hsu, Spectroscopy Letters, 1974,7,439; L D Neff and S C Kitching, J Phys Chem.,

1974,78, 1648; D Bhaumik, Indian J Phys., 1974,48,324; J N Som and D K Mukherjee,

J Mol Structure, 1975,26, 120

M Hayashi, H Imaishi, and K Kuwada, Bull Chem SOC Japan, 1974,47,2382; M Hayashi,

J Nakagawa, and K Kuwada, Chern Letters, 1975, 1267; A M Mirri, F Scappini, and H

Maeder, J Mol Spectroscopy, 1975,57,264; R E Schmidt and C R Quade, J Chem Phys.,

1975, 62, 3864; J H Griffiths and J E Boggs, J Mol Spectroscopy, 1975,56,257

A Bjorseth, J Mol Structure, 1974,23, 1

M Ohsaku, Bull Chem SOC Japan, 1975, 48, 707; Spectrochim Acta, 1975, 31A, 1271;

N Nogami, H Sugeta, and T Miyazawa, Bull Chem SOC Japan, 1975,48,2417,3573

H Sugeta, Spectrochim Acta, 1975, 31A, 1729; H E van Wart, F Cardinaux, and H A Scheraga, J Phys Chem., 1976,80,625

E I Gritsaev, S V Dozmorov, and Y G Slizhov, Zhur.fiz Khim., 1975,49, 3010

B Nagel, T Steiger, J Fruwert, and G Geiseler, Spectrochim Acta, 1975, 31A, 255

V Horn and R Paetzold, Spectrochim Acta, 1974, 30A, 1489

K Dathe and K DoerfFet, J prakt Chem., 1974,316,621 ; 317,757

J T Shah, Canad J Chem., 1975,53, 2381

4 Organic Cornpoundi of Sulphur, Selenium, and Tellurium

preted in terms of deformation modes of these functional groups 1.r spectro- scopic studies with a similar objective have been reported for isothiocyanato-

ethyl t h i o ~ y a n a t e , ~ ~ ~elenocyanates,~~ methanesulphenyl ~hloride,~' diaryltellurium d i h a l i d e ~ , ~ ~ N-alkyl sulphinamide~,~~ anilinesulphonic acids, their sodium salts, and deuteriated analogues,po bis(ary1) s ~ l p h o n i m i d e s , ~ ~ methane- sulphonyl and methanes~lphonarnide,~~

Nuclear Magnetic Resonance Spectra.-A broad study of 77Se n.m.r chemical shifts in selenides, diselenides, and selenocyanates has been published.44 13C

N.m.r data have been collected for 2-adamantanethi01,~~ alkyl vinyl s ~ l p h i d e s , ~ ~ and ring-substituted methyl phenyl sulphides, sulphoxides, and ~ u l p h o n e s ~ ~ Eu(fod), forms weak complexes with 2-adamantanethi01,~~ and with sulphides and d i ~ u l p h i d e s ~ ~ Larger shifts for sulphides and disulphides are induced by Eu(tfn),, in which the Lewis acidity of the lanthanide atom is enhanced by the larger degree of fluorination of the organic moiety.48 The chemical shift non- equivalence observed in isopropyl methanesulphinate is larger than that of the analogous sulphoxide, and is enhanced further by complex formation with benzene.49

2-Substituted 2-fluoroethyl phenyl sulphones, RCHF CH, S02Ph (R = SPh, SOPh, S02Ph, or Br), exist predominantly in the conformation in which the most

bulky groups are ~nti-periplanar.~~ N.m.r spectra give more reliable confor- mational information for did-pyridyl disulphide than that deduced from Kerr- effect data.51 Full details have now been published 52 on the empirical relationship between AAem and the relative orientation of a -CH2- group attached to 0, S,

SO, or SO, The chemical shifts of the CH, protons in para-substituted phenyl alkyl and phenylsulphonyl alkyl sulphones correlate well with Hammett substituent constants, indicating the transmission of electronic effects through the sulphone

Analogously, the MeSO, substituent is shown 54 to possess a lower

mesomeric electron-accepting power than a NO2 group when substituted in the

34 L Floch and S Kovac, Coll Czech Chem Comm., 1975,40,2845

86 A Bjorseth, Acta Chem Scund., 1974,28, 113

36 W J Franklin, R L Werner, and R A Ashby, Spectrochim Acta, 1974,30A, 387

37 F Winther, A Guamieri, and 0 F Nielsen, Spectrochim Acta, 1975, 31A, 689

38 N S Dance and W R McWhinnie, J.C.S Dalton, 1975,43

ss A Kolbe and E Wenschuh, J Mol Structure, 1975,20, 359

40 W H Evans, Spectrochim Acta, 1974, 3OA, 543

41 Y Tanaka and Y Tanaka, Chem and Pharm Bull (Jupun), 1974,22,2546

K Hanai, T Okuda, and K Machida, Spectrochim Acta, 1975, 31A, 1227

43 K Hanai, T Okuda, T Uno, and K Machida, Spectrochim Acra, 1975,31A, 1217

44 A Fredga, S Gronowitz, and A B Hornfeldt, Chem Scripta, 1975, 8, 15

4b H Duddeck and W Dietrich, Tetrahedron Letters, 1975, 2925

48 B A Trofimov, G A Kalabin, V M Bzhesovskii, N K Gusarova, D F Kushnarev, and

S V Amosova, Reukts spos org Soedinenii, 1974, 11, 367; G A Kalabin, B A Trofimov,

V M Bzhezovskii, D F Kushnasev, S V Amosova, N K Gusarova, and M L Alpert,

Izvest Akad Nauk S.S.S.R., Ser khim., 1975, 516

*' G W Buchanan, C Reyes-Zamora, and D E Clarke, Cunud J Chem., 1974,52,3895

T C Morrill, R A Clark, D Bilobran, and D S Youngs, Tetrahedron Letters, 1975, 397

4D R V Norton and I B Douglass, Org Magn Resonance, 1974,6,89

G Marchese, F Naso, D Santo, and 0 Sciacovelli, J.C.S Perkin ZZ, 1975, 1100

61 A Forchioni and G C Pappalardo, Spectrochim Acta, 1975,31A, 1367

62 R Davies and J Hudec, J.C.S Perkin I t , 1975, 1395

63 E V Konovalov, R G Dubenko, T Y Lavrenyuk, V M Neplynev, and P S Pelkis, Zhur org Khim., 1974,10,427

D D MacNicol, Tetrahedron Letters, 1975, 2599

Aliphatic Organo-sulphur Compounds etc 5

4-position of NN-dirnethyl-2-nitro-aniline N.m.r provides a particularly direct

technique for the study of the kinetics of proton exchange, exemplified in studies

of arenethiols in A c O H ~ ~

Both lH and l9F n.m.r data have been employed in the assignment of 2,5-

diAuoropheny1 methyl sulphide as the structure of the product of reaction between MeS- Naf and 1,2,5-trifl~orobenzene.~~

Mass Spectra.-Organosulphur compounds are well represented in mass spectro- metric studies, and the various sulphur functional groups promote individualistic rearrangement behaviour in certain molecular ions While mer~aptopyridines,~~ dialkyl sulphoxides,68 and dithioacetals and xanthates 69 undergo unspectacular fragmentation (although the formation of sulphenium ions in the latter classes 6g

is notable), rearrangements of (arylsulphony1)methyl arenesulphonates to a-disulphones with extrusion of HCHOYBo of aryl propargyl sulphones to the SO2-extrusion productYB1 of methyl- or benzyl-sulphonylmethyl methyl sulphones

to analogous Ramberg-Backlund rearrangement products,62 and 0 to S migra- tion in N-substituted sulphoximides under electron impact 63 illustrate more involved processes A further example,g4 the rearrangement of thiolsulphonates

to sulphenylsulphinates after electron loss, proceeds through an unprecedented [2,2,1]-bicyclic transition state

Detailed studies of mass spectrometric behaviour of aryl methyl and aryl chloromethyl ~ u l p h o n e s , ~ ~ chlorosulphonylmethyl methyl sulphones,Gs and a-diazosulphones 67 have been reported Broad studies of mass spectrometric behaviour of di- and tri-sulphides 64 and a-disulphones 64 are described in a key reference for this area A limited study of di-organotellurium dicarboxylates has been reported.68 The a-cleavage fragmentation path is followed by the molecular ion from methyl alkanesulphinates, resulting in parent ions of low abundance and the hydrocarbon ion as the base peak.sg

Modified mass spectrometric techniques are illustrated in chemical ionization studies of methanethiol 70 and in field desorption studies of sulphonic acids and esters .'l

V K Pogorelyi, V P Prokopenko, and I P Gragerov, Teor i eksp Khim., 1974,10, 399

G Haegele, J Richter, and M E Peach, 2 Naturforsch., 1974,29b, 619

A Maquestiau, Y van Haverbeke, C de Meyer, A R Katritzky, and J Frank, Bull SOC

chim belges, 1975, 84, 465

P Potzinger, H U Stracke, W Kuepper, and K Gollnick, Z Naturforsch., 1975,30a, 340

D Schumann, E Frese, K Praefcke, and W Knoefel, Org Mass Spectrometry, 1975,10,527

T Graafland, J B F N Engberts, and W D Weringa, Org Mass Spectrometry, 1975,10,33

D K Bates and B S Thyagarajan, Internat J Surfur Chem., 1973,8,57

R F Langler, W S Mantle, and M J Newman, Org Mass Spectrometry, 1975, 10, 1135;

W R Hardstaff and R F Langler, ibid., p 215

C P Whittle, C G MacDonald, and G F Katekar, Org Mass Spectrometry, 1974, 9,422

E Block, M D Bentley, F A Davis, I B Douglass, and J A Lacadie, J Org Chem., 1975, 40,2770

I Pratanata, L R Williams, and R N Williams, Org Mass Spectrometry, 1974, 8, 147; 9,

418

W R Hardstaff, R F Langler, and M J Newman, Org Mass Spectrometry, 1974,9, 1156

0 Luinenberg, J B F N Engberts, and W D Weringa, Org Mass Specfrometry, 1974, 9,

837

T J Adley, B C Pant, and R T Rye, Canad J Spectroscopy, 1975,20,71

W G Filby, R D Penzhorn, and L Stieglitz, Org Mass Spectrometry, 1974,8,409

B 0 Jonsson and J Lind, J.C.S Faraday II, 1974,70, 1399

H R SchuIten and D Kuemmler, 2 analyt Chem., 1976,278,13

6 Organic Compounds of Sulphur, Selenium, and Tellurium

Photoelectron Spectra.-The practitioners of this technique are now moving from the simplest representative compounds to bifunctional series, providing useful information on preferred conformations Studies of methanethiol 70 and dimercaptomethane 7 2 have been described, and suggest that the latter compound preferentially adopts a non-planar conformation in the gas phase 2,4-Dithia- pentane, MeSCH,SMe, has been shown to be planar.7e

Fundamental information on bonding is provided by photoelectron spectro- scopy of thioanisoles73 and other alkyl aryl ~ulphides.~* Two conformers are predominant for these compounds, RSPh, and the proportion of the conformer

with maximum p-n overlap decreases through the series R = H, Me, Et, Pri, or

But.74 Related studies for sulphoxides provide correlation diagrams for the effects of substituents R in RS(O)R, as well as information on preferred con-

f o r m a t i o n ~ ~ ~ An orienting survey of hexavalent sulphur functional groups, viz

alkyl, vinyI, and aryl sulphones, SS-dialkyl suIphimides, sulphuryl halides, sulphoximides, and sulphurdi-imides, is available.76

Electron Diffraction.-Bond-length and bond-angle data have become available for triflu~romethanethiol,~~ phenyl vinyl ~ u l p h i d e , ~ ~ dimethyl d i ~ u l p h i d e , ~ ~ ethyl methyl d i ~ u l p h i d e , ~ ~ dimethyl sulphurdi-imide,80 and benzenesulphonyl chloride.s1 Dipole-moment and Kerr-effect Studies.-Information on preferred conformations

is provided by these techniques, although only a relatively limited precision is possible in estimates of molecular geometry

Aromatic disulphides and diselenides adopt a conformation in which the torsion angle between the C-S-S- and -S-S-C’- planes lies between 70 and 90°.82 84 Related studies of aliphatic disulphides have also been under- taken.83 Comparisons of S, Se, and 0 analogues represented by ArXMe,sS

(Ar = Ph or meta-substituted phenyl) and aryl diarylmethyl sulphides 86 have been made, in terms of their conformational behaviour Studies of diary1 ditellurides ArTeTeAr and phenyl tellurobenzoates 87 PhCOTeR provide dipole-moment

data consistent with a non-planar Cs conformation and planar Z conformation,

7 2 C Guimon, M F Guimon, and G Mster-Guillouzo, Tetrahedron Letters, 1975, 1413

7 3 F Bernardi, G Distefano, A Mangini, S Pignataro, and G Spunta, J Electron Spectroscopy Related Phenomena, 1975,7,457

P S Dewar, E Ernstbrunner, J R Gilmore, M Godfrey, and J M Mellor, Tetrahedron,

1974,30,2455

i5 H Bock and B Solouki, Chem Ber., 1974,107,2299

7 6 B Solouki, H Bock, and R Appel, Chem Ber., 1975,108, 897

’’ C J Marsden, J Mol Structure, 1974, 21, 168

l n N M Zaripov and T G Mannafov, Zhur strukt Khim., 1974,21, 168

ia A Yokozeki and S H Bauer, J Phys Chem., 1976,80,618

J Kuyper, P H Isselmann, F C Mijlhoff, A Speltos, and G Renes, J Mol Structure, 1975,

29, 247

L A Sorokina, L M Kataeva, and A B Remizov, Zhur $2 Khim., 1974,48, 1559; S G

Vulfson, L A Sorokina, L M Kataeva, A N Vereshchagin, and E G Kataev, Dokludy

Akad Nauk S.S.S.R., 1974, 219, 1363; S G Vulfson, L A Sorokina, L M Kataeva, and

A N Vereshchagin, ibid., 216, 837

83 M J Aroney, S W Filipczuk, and D V Radford, J.C.S Perkin ZZ, 1975,695

8 4 G C Pappalardo and S Gruttadauria, Guzzettu, 1975, 105, 427

86 G Y Cheryukanova, G A Chmutova, and A N Vereshchagin, Zhur fiz Khim., 1975,49,

234

86 S Sorriso, G Reichenbach, S Santini, and A Ceccon, J.C.S Perkin ZZ, 1974, 1588

V Jehlicka, J L Piette, and 0 Exner, Coll Czech Chem Comm., 1974,39, 1577

81 J Brunvoll and J Hargittai, J Mol Structure, 1976,30, 361

Aliphatic Organo-sulphur Cornpoundr etc 7

respectively The series RXXR and RCOXR (X = 0, S, Se, or Te) adopt the non-planar and planar conformations respectively, and in this connection the Group VI atom exerts an insignificant effect Routine collection of data for diphenyl s u l p h ~ n e , ~ ~ dialkyl sulphoxides,88 substituted benzenesulphonamides,*B and aryl selenocyanates 90 has been undertaken The additional information available from dipole-moment data is illustrated in the last-mentioned study, which confirms the electron-withdrawing property of the -SeCN grouping as a

substituent on an aromatic ring system.Bo

Optical Rotatory Dispersion and Circular Dichroism Spectra.-The chirospectro- scopic properties of derivatives of optically active thiols have been ~urveyed.~' This provides a valuable background for the assignment of absolute configuration

to chiral thiols by 0.r.d and c.d methods, requiring the thiol to be converted into a sulphide, disulphide, A2-thiazoline, or S-acyl derivative, and exploiting the Cotton-effect behaviour of these classes of organosulphur compound.n1 Con- tinuing interest in the 0.r.d behaviour of chiral disulphides of natural origin, particularly L-cystine and its derivatives, is confirmed by detailed calculations of the Cotton-effect parameters associated with various conformations of the disul- phide chromophore in ~ - c y s t i n e ~ ~

Other Physical Properties-Conformational information for thiols and sulphides can be obtained from enthalpy of formation data.B3 Proton-transfer of benzyl- mercaptan (protonation at sulphur with CF3S03H, and de-protonation by imidazole) has been studied.B4 Thermodynamic parameters for acidity constants

of substituted benzenethiol~,~~ and for hydrogen-bonding interactions between alkanols and di-n-octyl sulphide and the analogous ether and N-methylamine,Q6 reveal a dominant electronic influence of the or~ho-substituent,~~ and substantially higher hydrogen-bond acceptor ability for the aliphatic sulphide than is generally assumed.Qg

3 Thiols

Preparation.-Standard procedures developed in recent years have been used for the synthesis of 2-mercaptophenol from catech01,~~ and 3,5-dimethoxybenzene- thiol from 3,5-dimethoxyphenol g8 by way of the thionocarbamate-thiol-

carbamate rearrangement (ArOH f ArOCSNMe, -j ArSCONMe, -+ ArSH) Further development of 'sulphurated sodium borohydride' (NeBH,S,) as a

reagent for the preparation of thiols from benzyl halides, giving high yields of both a-toluenethiols and benzyl polys~lphides,~~ has been reported

ad D M Petkovic and M S Pavlovic, Z phys Chem (Frankfurt), 1974,88, 54

P RuosteSuo, Finn Chem Letters, 1975, 191

@ O G A Chmutova, L A Sorokina, L M Kataeva, and N S Podkovyrina, Z h u r 3 ~ Khim.,

1974.48, 282

C Toniolo, Zntermt J Sulfur Chem., 1973, 8, 89

@ e R W Strickland, J Webb, and F S Richardson, Biopolymers, 1974, 13, 1269

@3 J W H Kao and A Chung-Phillips, J Chem Phys., 1975,63,4152

#' J J Delpuech and D Nicole, J.C.S Perkin Zl, 1974, 1025

e6 P de Maria, A Fini, and F M Hall, J.C.S Perkin 11, 1974, 1443

s6 H L Liao and D E Martire, J Amer Chem Soc., 1974,96, 2058

R M Dodson and J B Hanson, J.C.S Chem Comm., 1975,926

H Wolfers, U Kraatz, and F Korte, Synthesis, 1975, 43

J.-R Brindle and J.-L Liard, Cunad J Chem., 1975, 53, 1480

8 Organic Compounds of Sulphur, Selenium, and Tellurium

While thiones give sulphides through thiophilic addition of alkyl- or aryl-

lithiurns (see also Chapter 3, p 131), di-t-butyl thioketone reacts through an

alternative reaction path loo (Scheme l), leading to hindered thiols /3-Phenylethyl

II v

-+

(1)

thiones, e.g (l), give cyclopropanethiols on irradiation with light of wavelength

longer than ca 460 nm.lol

Long-established methods for synthesis of thiols for which modified pro- cedures have been worked out include the use of Na,35SS0, for the synthesis of

35S-labelled thiols from alkyl bromides,loa the use of Na,S + S in D M F for

synthesis of dithiols from dihalides or disulphonates,lo3 and the analogous use of xanthates for the synthesis of optically active thiols from toluene-p-sulphonates under mild conditions.lo4 Modifications of known methods were also used

in the syntheses of glucopyranoside-6-thiols 105a and 1,3,4,6-tetrathio-~-iditol.~~~~

Related substitution processes have been illustrated in the recent literature, leading to 2,3-dimercaptopropanoic acid and the corresponding alcohol,106 and

0

l o o A Ohno, K Nakamura, and S Oka, Chem Letters, 1975, 983; A Ohno, K Nakamura,

M Uohama, S Oka, T Yamabe, and S Nagata, Bull Chem SOC Japan, 1975,48, 3718

lol A Couture, M Hoshino, and P de Mayo, J.C.S Chem Comm., 1976,131

loa G A Bagiyan, S A Grachev, I K Koroleva, and N V Soroka, Zhur org Khim., 1975,11,

l o 3 E L Eliel, V S Rao, S Smith, and R 0 Hutchins, J Org Chem., 1975, 40, 524

l o * E Beretta, M Cinquini, S Colonna, and R Fornasier, Synthesis, 1974,425

lo6 ( a ) D Trimnell, E I Stout, W M Doane, C R Russell, V Beringer, M Saul, and G van

Gessel, J Org Chem., 1975,40,1337; (b) G E McCasland, A B Zanlungo, and L J Durham,

ibid., 1976, 41, 1125

L N Owen and M B Rahman, J.C.S Perkin I, 1974, 2413

900

Aliphatic Organo -sub h ur Compounds e tc 9

to mono- and di-thiosquarate dianions (2) and (3) from diethoxy- or bis(alky1- amino)-precurs~rs,~~~ and to the dithiocyclobutenedithione dianion analogue.lo8

A novel synthesis of thiols from a-alkylamino-nitriles log by reaction with H2S

probably proceeds by way of the gem-dithiol:

R1R2CH(NHRS)CN -+ R1R2CHSH

Ring-opening reactions leading to thiols involve 6-nitrobenzothiazole with MeO-,llO, 810a 2-nitrothiophen with secondary amines,810b 2-alkylthiothiazolium salts with OH-,lll 2-aminothiazole and 2-aminothiazoline with [PtC1412- or [PdzC1,]2-,112 and mixtures of thiols (4)-(6) from penicillin derivatives by

reaction with mercury(@ acetate followed by treatment with H2S.11S More conventional ring-opening procedures involve the reactions of oxirans with xanthates 114 and of thiirans with RSH.l15 A route to 1-amino-2-methylpropane- 2-thiol has been re-worked, so as to provide authentic material.lla

Ethane-1 ,Zdiselenol, HSeCH,CH,SeH, is accessible through reduction of the corresponding di-selenocyanate with H3P02.117

Heterocyclic Thio1s.-Representative synthetic methods described in the recent literature cover the synthesis of tetrachloropyridine-2-thiol from pentachloro-

pyridine N-oxide and thiourea,l18 the synthesis of 2-phenylthiazole-5-thiols from the S-acetyl compounds,110 and syntheses of 4-phenyl-l,2-dithiolan-3-

lo' D Coucouvanis, F J Hollander, R West, and D Eggerding, J Amer Chem SOC., 1974,96,

3006

lo8 G Seitz, K Mann, R Schmiedel, and R Matusch, Chem.-Ztg., 1975, 99, 90

loB R Crossley and A C W Curran, J.C.S Perkin I, 1974, 2327

G Bartoli, F Ciminale, and P E Tedesco, J.C.S Perkin 11, 1975, 1472

ll1 Y Gelernt and P Sykes, J.C.S Perkin I , 1974,2610

112 J Dehand and J Jordanov, J.C.S Chem Comm., 1975,743

119 R J Stoodley and N S Watson, J.C.S Perkin I , 1975,883

114 M E Ali, N G Kardouche, and L N Owen, J.C.S Perkin I, 1975, 748

115 A V Fokin, A F Kolomiets, L S Rudnitskaya, and V I Shevchenko, Zzvest Akad Nauk S.S.S.R., Ser khim., 1975, 660

J L Corbin and D E Work, J Org Chem., 1976, 41, 489

117 M V Lakshmikantham, M P Cava, and A F Garito, J.C.S Chem Comm., 1975,383

118 B Iddon, H Suschitzky, A W Thompson, and E Ager, J.C.S Perkin I, 1974,2300

llB G C Barrett and R Walker, Tetrahedron, 1976,32, 583

2

10 Organic Compounds of Sulphur, Selenium, and Tellurium

NH

0 OH 0' OH

Me s-s

thione-5-thi01,'~~ and of the pyrrole-3-thiols 121 (7), totally unexpectedly, by

thiation reactions involving S,

(6H)-1,3,4-Thiadiazines rearrange to pyrazole-4-thiols with LiPri,N in THF at

- 110 OC.laa

The thiol tautomeric form predominates for pyra~ole-5-thiols,l~~ and for

2-phenylthiazole-5-thiols,lle in contrast to the behaviour of their oxygen analogues

Thiols as Nuc1eophiles.-Citations describing nucleophilic substitution reactions and related processes are grouped together here, and nucleophilic addition reactions are discussed in the following section Some of the routes leading to sulphides (see Preparation of Sulphides, p 16) will be relevant reading for those seeking all references in this Chapter describing the nucleophilic reactions of

thiols

Studies of aromatic substitution reactions with thiolates have been described for halogenobenzofurans,124 polyfluorobenzenes (an interesting generalization

is that all but two fluorine substituents can be replaced by reaction with

125 benzenediazonium salts (with AgSCF3),126 aryl iodides (with CuSCF3),la7 and 3,4,5-trichloropyridine-2,Bdicarbonitrile (all three Cl sub- stituents are replaced by alkyl- or aryl-thiolates).128 Kinetic studies of substitu- tion reactions of thiolates with chlorobenzenes,12g ha loge no nitro benzene^,^^^ and 2-fluoropyridines 131 have been described An example of reversible addition (8) + (9) (X = H or D), characterized by n.m.r., provides a near analogy to the formation of Meisenheimer c o m p I e ~ e s ~ ~ ~

Photostimulated reactions of thiolates with iodobenzenes in liquid NH3, leading

to sulphides in good yields, proceed through RS- + ArI -+ R%kr -+ Re +

l R 0 J P Brown and M Thompson, J.C.S Perkin I , 1974, 863

lZ1 I R Gelling and M Porter, Tetrahedron Letters, 1975, 3089

l r P R R Schmidt and H Huth, Terrahedron Letters, 1975, 33

J J Bergman and B M Lynch, J Heterocyclic Chem., 1974, 11, 135

l P 4 L Di Nunno, S Florio, and P E Todesco, Tetrahedron, 1974, 30, 863

lZ5 M E Peach and A M Smith, J Fluorine Chem., 1974, 4, 341, 399

126 N V Kondratenko and V P Sambur, Ukrain khim Zhur., 1975,41,516 (Chem Abs., 1975,

83, 58 321)

lS7 L M Yagupolskii, N V Kondratenko, and V P Sambur, Synthesis, 1975, 721

1 3 8 C T Goralski and T E Evans, J Org Chem., 1975,40, 799

li9 K V Solodova, N V Kozhevnikova, and S M Shein, Zhur org Khim., 1974, 10, 214

130 G Guanti, C Dell'Erba, S Thea, and G Leandri, J.C.S Perkin 11, 1975, 389

131 R A Abramovitch and A J Newman, J Org Chem., 1974, 39, 3692

194 C A Veracini and F Pietra, J.C.S Chem Comm., 1974, 623

Aliphatic Organo-sulphur Compounds etc 1 1

ArS- -+ mixed sulphides, indicating the operation of an aromatic Smi

reaction.133

Conditions have been worked out for the synthesis of methyl polyfluor-lkyl sulphides lS4 and 2-bromo-1 ,l-difluoroethyl phenyl sulphide 136 by halogen- substitution reactions involving sodium thiolates p-Nitrothiophenol reacts with 1,2-dichlorohexafluorocyclopentene to give the 1,2-bis(p-nitrophenylthio)-

ana10gue.l~~ Aryl alkyl tellurides PhTeR lS7 and bis(phenyltel1uro)methane

PhTeCH,TePh188 can be obtained from PhTeLi and an alkyl halide, or di- iodomethane, respectively

The nucleophilicity of thiols towards an spa ester carbon atom has previously

been little studied.lSO A detailed report has appeared showing that rates of reac- tion of substituted arenethiols with p-nitrophenyl acetate can be correlated with

pK, values of the thiols, after substantial solvent effects have been taken into account; this is a key reference for this area.lS0

SN2-Type processes are involved in the ring-opening reactions of oxirans, under mild conditions (by thiols, adsorbed on and in the ring- closure of a penicillin-derived enethi01ate.l~'

Addition Reactions of Thiok-Base-catalysed (i.e ionic) addition of thiols RlSH

to acetals R2CH=CXCH(OEt), gives R1SCR2=CHCH(OEt)a,142 while addition

of PhCHaSH to isopropenyl ketones gives PhCH,SCH,CMeCOR in partly resolved form when Ca or Ba (- )-amyl oxides are used as 2-Phenyl- thiazole-5-thiols behave as typical heteroaromatic thiols in addition reactions,llg while their oxygen analogues undergo cycloaddition reactions with the same unsaturated systems This is a result of the respective dominance of the keto- tautomeric and meso-ionic forms

Radical-addition processes have been studied using vinylphosphines (radical addition at either C or P),lr14 a l l y l h y d r a ~ i n e , ~ ~ ~ cw-methylstyrene~,~~~ and methyl oleate (C-9 and C-10 adducts are formed in nearly equal amounts).14'

lS3 P J Bunnett and X Creary, J Org Chem., 1974,39,3173; 1975,40,3740

134 B Haley, R N Haszeldine, B Hewitson, and A E Tipping, J.C.S Perkin I, 1976, 525

lS6 V A Korinko, Y A Serguchev, and L M Yagupolskii, Zhur org Khim., 1975,11, 1268

136 R F Stockel, Canad J Chem., 1975,53,2302

lJ7 K J Irgolic, P J Busse, R A Grigsby, and M R Smith, J Organometallic Chem., 1975,88,

175

lJ8 D Seebach and A K Beck, Chem Ber., 1975,108,314

G Guanti, C Dell'Erba, F Pero, and G Leandri, J.C.S Perkin 11, 1975, 212

140 G H Posner, D Z Rogers, C M Kinzig, and G M Gurria, Tetrahedron Letters, 1975,3597

I4l A G W Baxter and R J Stoodley, J.C.S Chem Comm., 1975, 251

142 N A Keiko, L G Stepanova, G I Kirillova, I D Kalikhman, and M G Voronkov, Izuest

Akad Nauk S.S.S.R., Ser khim., 1975,2274

143 K Yamaguchi and Y Minoura, Chem and Ind., 1975,478

144 D H Brown, R J Cross, and D Millington, J.C.S Dalton, 1976, 334

G Y Gadzhiev and V A Budagov, Azerb khim Zhur., 1975, 53

u6 D F Church and G J Gleicher, J Org Chem., 1975,40, 536

A Sugii, K Harada, and K Kitahara, Chem and Pharm Bull (Japan),

12 Organic Compounds of Sulphur, Selenium, and Tellurium

A detailed study of the free-radical addition of alkanethiols to (a1kylthio)- vinylacetylenes 148 and their Se and Te analogues reveals interesting differences conferred by the presence of the different heteroatoms While MeSC=CCH= CH2 gives MeSC=CCH,CH,SEt, MeSCECCHMeSEt, and MeSCH= C(SEt)- CH,CH,SEt with ethanethiol, the Se analogue gives MeSeCH=C(SEt)CH,- CH,SEt (40%), MeSeC(SEt)=CHCH=CH, (ca 20%), MeSeC=CCH,CH,SEt (25%), and MeSeCH=C=CHCH,SEt (1 1%); the Te analogue, in contrast, suffers oxidation by the t-butyl peroxide used to create the thiyl radicals, or C-Te bond cleavage in the absence of

The other studies of thiol addition to alkynes in the recent literature involve the ionic mechanism, the major interest being the stereoisomer ratios of the resulting vinyl s ~ l p h i d e s ~ ~ * ~ 150 An interesting study 15* of the addition of 2 equivalents of PhCH2SH to acetylenedicarboxylic acid in alkaline solution includes an assessment of factors allowing control of the proportions of the

resulting racemic and rneso-l,2-bis(benzylthio)succinic acids

Addition of C6F5SH to various unsaturated systems151 and the kinetics of addition of propanethiol to benzylideneanilines in non-aqueous solvents 162

provide examples of related reactions

Further Reactions of Thio1s.-Treatment of PhCHzSLi with B P L i at - 5 "C gives the species (Ph?H-S-)2Li+, which is equally well named the thiobenz- aldehyde dianion or the dianion of the thi01.l~~ The carbanion centre is involved

in the reaction of the dianion with electrophiles; e.g benzaldehyde gives

PhCH(SH)CH(OH)Ph

1 ,2-Anionic rearrangement from sulphur to carbon under the influence of ButLi

is observed with benzylthiotrimethylsilane, PhCH,SSiMe, + PhCH(SH)SiMe3.154

A form of anchimeric assistance is involved in the elimination of HCl from 3-chlorobutanethiols ( Two papers 156~ deal with differently based

(1 1)

14* S I Radchenko, I G Sulirnov, and A A Petrov, Zhur org Khim., 1974,10, 2456

14@ M T Omar and M N Basyouni, Bull Chem SOC Japan, 1974,47,2325; L V Tirnokhina,

A S Nakhrnanovich, 1 D Kalikhman, and M G Voronkov, Zhur org Khim., 1974, 10, 2468; I L Mikhelashvili and E N Prilezhaeva, ibid., p 2524; I L Mikhelashvili-Fioliya,

V S Bogdanov, N D Chuvylkin, and E N Prilezhaeva, Izvest Akad Nauk S.S.S.R., Ser khim., 1975, 890; H A Selling, Tetrahedron, 1975,31,2387

160 E Larsson, Bull Soc chim belges, 1975, 84,697

Ibl T S Leong and M E Peach, J Fluorine Chern., 1975, 6 , 145

Ira Y Ogata and A Kawasaki, J.C.S Perkin ZI, 1975, 134

lbs D Seebach and K H Geiss, Angew Chem., 1974, 86, 202

lS4 A Wright and R West, J Amer Chem SOC., 1974, 96, 3222

C A Grob, B Schmitz, A Sutter, and A H Weber, Tetrahedron Letters, 1975,3551

l6* A D U Hardy, D D MacNicol, J J McKendrick, and D R Wilson, Tetrahedron Lerrers,

1975,471 1

H Maarse and M C Ten Noever De Brauw, Chem and Ind., 1974,36

Aliphatic Organo-sulphur Compounds etc 13

physical properties of thiols; one describes CCI, clathrate formation by the sulphur analogue (1 1) of Dianin's Commercial t-dodecanethiol has a catty odour, which is detectable over several miles, and which has now been shown 16' to be due to the presence of an impurity, PrfC(SH)Me2

Protection of Thiols in Synthesis.-Commonly used protecting groups for cysteine (5'-trityl, S-diarylmethyl, S-acetamidomethyl) are cleanly removed by 2-nitro- benzenesulphenyl chloride in A C O H ~ ~ ~

Generation of Thiyl Radicals and Thiolate-stabilized Radicals.-Oxidation of thiols

by Ti"'-H,O, or CeIV species gives products resulting from successively formed

thiyl (RS=), sulphinyl (RSO-), and sulphonyl (RS02*) ~adica1s.l~~ A new outlook

is provided by reassignment of e.s.r spectra, previously interpreted in terms of thiyl radicals, to RS-LSR, a*-radicals, structurally similar to disulphide anion radicals R S ~ ~ R l s o ~ 161 Low-temperature radiolysis of thiols, sulphides, and disulphides definitely involves the formation of thiyl radicals as the initial

162 this was shown by spin-trapping with ButNO.lsl Radiolysis of RSH

at 77 K gives thiyl radicals,ls2 and R2S gives RS- and R* through an electron- capture process during radiolysis.ls2

A long-lived alkylselenolate radical R,MSeCBut, is formed 163 by the reaction

of di-t-butyl selenoketone with organometalloid species R,M* (M is an element

of Group IV, V, or VI)

Thiols in Biochemistry.-As in previous volumes of these Reports, no attempt is made at comprehensive coverage in this section However, there are relatively few topic areas linking to the general title of this section, and it is possible to indicate these with a few key references

A review of cysteine proteinasesls4 gives a perspective to one role of SH groups in proteins The estimation of the reactivity of this functional group in proteins, as a function of the local charge distribution, is feasible using 5,Y-

di t hio- bis(2-nitro-N- t rime t hyl benzylammonium iodide) and the N-2'-hydroxy- ethylbenzamide as positively charged and neutral analogues, respectively, of Ellman's reagent.ls5 Modified procedures for the determination of SH groups

in proteins have been reported, employing 9-vinylacridine,lBs W(7-dimethyl-

amino-4-methyl-3-coumarinyl)maleimide and its 6-coumarinyl analogue,lS7 and p-hydroxymercuribenzoate lss as reagents Estimation of disulphide groups

in peptides and proteins employs a similar approach after first cleaving the disulphide

lb8 A Fontana, J.C.S Chem Comm., 1975,976

lb9 B C Gilbert, H A H Laue, R 0 C Norman, and R C Sealy, J.C.S Perkin II, 1975,

892

160 M C R Symons, J.C.S PerkinII, 1974, 1618

J A Wargon and F Williams, J.C.S Chem Comm., 1975, 947

162 D Nelson and M C R Symons, Chem Plzys Letters, 1975, 36, 340

J C Scaiano and K U Ingold, J.C.S Chem Comm., 1976,205

164 G Lowe, Tetrahedron, 1976,32,291

16b G Legler, Biochim Biophys Acta, 1975,405, 136

166 Y Nara and K Tuzimura, Agric and Biol Chem (Japan), 1975,39, 7

le7 M Machida, N Ushijima, M I Machida, and Y Kanaoka, Chem and Pharm Bull (Japan),

1975,23,1385

J B Carlsen, Analyt Biochem., 1975, 64, 53

14 Organic Compounds of Sulphur, Selenium, and Tellurium

Studies of addition of thiolates to flavans1es-171 showing that addition to a 4a- or 5-position of an isoalloxazine ring may be implicated in flavin catalysis of

thiol-disulphide oxidation, are sufficiently broad to include dithiols I7O and arenesulphinic acids.171

mercaptoethanol was the most effective for the catalysis of the conversion of oleic acid f trans-9-octadecenoic acid The

compound (12; n = 1) was more effective than homologues (n = 0, 2, or 3) in

Cysteine and cytosine undergo acetone-sensitized photoreaction in water, to give 5,6-dihydrouracil and 5-S-cysteinylura~il.~~~

Thiol-acids and Thiol-esters.-Most of the references in the recent literature dealing with these classes of compound from the point of view of new chemistry concern thiol-esters, and apart from a study of the formation of diacyl sulphide using

DCCI 176 and reaction with arene oxides [(13) -+ (14)],177 the current literature on

thiol-acids concerns mainly welt-established reactions e.g.17* homolytic addition

of AcSH to methylenecyclohexanes

Agathosma oils, previously shown to be rich in organosulphur compounds,

contain S-prenyl thioisobutyrate, Me,C=CHCH,SC(0)CHMe,.17B

Novel synthetic routes to thiol-esters use carboxylic acids and thiols with diethyl phosphorocyanidate or diphenyl phosphorazidate, and Et,N in DMF,laO

16* I Yokoe and T C Bruice, J Amer Chem SOC., 1975,97,450

1 7 0 E L Loechler and T C Hollocher, J Amer Chem SOC., 1975,97, 3235

l i l B R Brown and M R Shaw, J.C.S Perkin Z, 1974,2036

l i 2 W G Niehaus, Bio-org Chem., 1974, 3, 302

173 J Schoenleber and P Lochon, Compt rend., 1974, 278, C, 1381

l i 4 D M E Reuben and T C Bruice, J Amer Chem Soc., 1976,98, 114

l i 5 N C Yang, R Okazaki, and F.-T Lu, J.C.S Chem Comm., 1974,462

l i 6 M Mikolajczyk, P Kielbasinski, and H M Schiebel, J.C.S Perkin Z, 1976, 564

l i 7 A M Jeffrey, H J C Yeh, D M Jerina, R M De Marinis, C H Foster, D E Piccolo, and

G A Berchtold, J Amer Chem SOC., 1974,96, 6929

178 J C Richer and C Lamarre, Canad J Chem., 1975,53,3005

1 7 D D E A Rivett, Tetrahedron Letters, 1974, 1253

S Yamada, Y Yokoyama, and T Shioiri, J Org Chem., 1974,39, 3302