Weygand/Hilgetag Preparative Organic Chemistry

Contents xvii
8.2. Formation of the carbon-sulfur bond by exchange 611
I. Replacement of hydrogen by sulfur groups 611
1. Introduction of the sulfonic acid group 611
a. Aliphatic sulfonation 611
b. Aromatic sulfonation by sulfuric acid or oleum 612
i, General 612
ii, Sulfonation and the influence of substituents in the benzene series .. 616
iii, Sulfonation and the influence of substituents in the naphthalene,
anthracene, and phenanthrene series 620
c. Sulfonation by sulfuric acid and oleum in the presence of catalysts 622
d. Sulfonation with sulfur trioxide and its addition compounds 623
e. Aromatic sulfonation by halosulfuric acids and other sulfonating agents 624
2. Introduction of the sulfonyl chloride group 626
3. Direct introduction of the sulfone and sulfoxide group 629
4. Direct introduction of the sulfinic acid group 631
5. Introductionofthioxo,thio,andmercapto groups: preparation ofsulforylides 632
II. Replacement of halogen by sulfur groups 634
1. Reaction of alkyl and aryl halides with salts and derivatives of hydrogen
sulfide 634
a. Preparation of thiols and disulfides 634
b. Preparation of sulfides and sulfonium salts 636
c. Preparation of thioketones, mercaptals, and mercaptols 640
2. Reaction of acyl halides with hydrogen sulfide and its derivatives 642
3. Reaction of alkyl halides with sulfites and sulfinic acids 642
4. Preparation of thiocyanic and isothiocyanic esters 645
III. Replacement of oxygen by sulfur groups 645
1. Reaction of alcohols with sulfur compounds 645
a. Reaction with hydrogen sulfide and its derivatives 645
b. Reaction with sodium hydrogen sulfite 646
2. Reaction of alkene oxides (oxiranes) with sulfur compounds 647
3. Reaction of carbonyl compounds with sulfur compounds 648
4. Reaction of carboxylic acid derivatives with sulfur compounds 652
5. Reaction of alkyl and dialkyl sulfates with sulfur compounds 653
IV. Replacement of nitrogen by sulfur 653
1. Replacement of the amino group by sulfur groups 653
2. Replacement of the imino group by sulfur groups 657
3. Replacement of tertiary-bonded nitrogen and of the ammonium group by
sulfur groups 557
4. Replacement of the nitro group by sulfur groups 659
V. Replacement of other elements by sulfur groups 659
1. Reactions of Grignard reagents 659
2. Reactions of other organometallic compounds 661
8.3. Preparation of organic sulfur compounds by alteration of sulfur groups 662
I. Reduction of sulfur groups 662
II. Oxidation of sulfur groups 665
1. Oxidation of thiols 665
2. Oxidation of disulfides 667
3. Oxidation of sulfides 667
4. Oxidative halogenation of sulfur compounds; sulfonyl chlorides 669
III. Cleavage of sulfur bonds 671
1. Cleavage of the C-S bond 671
2. Cleavage of the S-H bond 675
3. Cleavage of the S-S bond 676
4. Cleavage of the S-Cl bond 678
a. Cleavage of sulfonyl chlorides 678
b. Cleavage of sulfinyl and sulfenyl chlorides 681