Chemistry of Heterocyclic Compounds. Volume 21. Multi-Sulfur and Sulfur and Oxygen Five - and Six-Membered Heterocycles. Part II

810 Pages·17.94 MB·english

by  Breslow D.S.

AND AND OXYGEN
MULTI-SULFUR SULFUR
AND
FIVE- SIX-MEMBEREDH ETEROCYCLES
In Two Pans
PART
TWO
Tbi8 is Part Two of tbe tiwntyjrst voltme in thc serk
THE CHEMISTRY OF HETEROCYCLIC
COMPOUNDS
CHEMISTRY
THE OF HETEROCYCLIC COMPOUNDS
A SERIES OF MONOGRAPHS
ARNOLD WEISSBERGER, Cmdting Editor
MULTI-SULFUR AND SULFUR
AND OXYGEN FIVE- AND
SIX-MEMBERED HETEROCYCLES
Part Two
David Breelow
S.
t\
Herman Skolnik
_ _ -~~
INTERSCIENCE
PUBLISHERS
a division of &
John Wiley Sons
- -
New London Sydney
York
First published 1966 by WUey &
John Sons, Ltd.
All Right8 Reserved
of Catalog Card 66-18380
Library Congress Number
CONTENTS
1. c@$ Ring Systems
a.
C20S2R ing Systems
3. Systems
C,S3 Ring
4. Ring Systems
C30S
5. Systems
C3S2 Ring
Part -0
6. Ring Systems
C202S2
7. Ring Systems
C2S4
8. C,02S Systems
Ring
9. Systems
C30S2R ing
10. Systems
C3S3R ing
11. Systems
C40S Ring
12. Systems
C,S, Ring
13. Rlng Systems Selenium and Tellurium
Containing
Subject Index
Index to Revised Index
Ring Numbers
CONTENTS OF PART TWO
. .
6. Ring Systems 611
C24S2
. .
611
I. C2O2SZ
.
A. 1,3, 2,4-Dioxadithiane , 611
. .
1. Preparation 611
.
2. Mechanism of Formation , 615
. .
3. Reactions 620
.
.
B. 1,3,2,4-Dioxadithiin 622
.
C,-C202S, 5H-Cyclopenta-l,3,2,4 -dioxaclithiin 622
II.
m. C1z,30,22S,42--dCizo0x,aSd2it1 h,h3, 2., 4-Dioxadithihd5,6-e]- . 622
.
.
N. 1,3,2,4 -Benzodioxadithiin 623
C,O$, -C,
. .
7. C8S4 Ringsystems 626
.
I. cs, , 626
. .
A. s-Tetrathiane 626
.
Spiro Derivatives 829
B.
1. S, 6,7,13,14-Tetrathiadispiro
fC4,.-2C.,4-.2Cj L-tetradecane . , 629
2. 7,8,15,16-Tetrathiadispiro
[C52.S24.5-.C2,]--hCe,x adecane . . 630
II. C,N,S-C2S4 2,3,.4 ,8-Tetrathia-6, '7-diazabicyclo .
13.2.11 octane 630
. .
8. C,O,SRingSystems 633
I. 1,3,2-Dioxathia . 633
Compounds
.
A. 633
CSO2S
. .
lY3,2-Dioxathiane 633
1.
. .
a. Sulfite Esters 633
.
(1) Preparation 633
.
(2) Structure and Physical 643
Properties
. .
(3) Reactions 645
vii
Contents of Part Two
.
Sulfate Esters 650
b.
.
(1) Preparation and Properties 650
.
(2) Reactions 65 3
c. Spiro Derivatives 65 6
2. 4H- 1,3,2-Dioxathiin 65 8
.
C,0-C302S 4H-Fur43,2-d]-l1 3,2-dioxathiin 658
B.
c. c302s-c,o
659
.
1. 8H-Pyrano(3, 2-d]-1,3, 2-dioxathiin 659
4H, .
2. 660
48,5H-Pyran44,3-d]-1,3,2-dioxathiin
D. c@~s-c6-c,N aphthdl, 8-de]-1,3,2-dioxathiin 660
c,o2s-c6-c,-c6 661
E.
1. Anthrdl, 9-de]-1,3,2-dioxathiin 66 1
4,10-Ethan0-4H-11aphtht$Z, 3-d]-1,3,2-
2. .
dioxathiin 662
3. Decahydro-5,9-methanobenzocycl&tene-
.
11 (W)-diol Cyclic Sulfite 66 2
4a,
F. Cyclic Sulfites of Steroids Related Com-
and
pounds , 662
1,3,4-Dimthia Compounds C,O,S-C, 2,4,1-
II.
Benzodioxathiin 667
IIl. 1,3, 5-Dioxathia .C ompounds C302S 1,3,5-
Dioxathiane 668
. .
9. C30E,RingSyetema 675
.
I. 1,2,6-Oxadithia Compounds 675
A. C3W2 1,2,6.-O xadithiane and 3H-1,2,6- .
oxadithiin 675
. .
1. 1,2,6-0xadithiane 675
.
3H-1,2,6-Oxadithiin 677
2.
B. c@8,-C,-c6 Naphwl, B-c~][ I, 2,610xadithiin 678
.
1,2,4-Oxadithia Compounds 679
II. . .
C3oS2 1,2,4-Oxadithiane 679
viii
Contents of Part Two
.
1,3,4-oxadithia Compounds 679
III.
C,06,-C6 Naphth[ 1,2-e] [ 1,3,4]oxadithiin
-C,
and Spiro [naphthalene-1(W), 3'-naphtMl, 2-e] .
[ 1,3,4]oxadithiin] 679
.
N. 1,3,5dkadithia Compounds 680
.
.
C,OS, 1,3, fi-oxadithiane 680
. .
10. C3S3RingSystems 689
L 1,2,3-Trithia Compounds 1,.2 ,3-Trithiane and .
Related Spiro Derivatives 689
.
1,3,5-Trithia Compounds 692
II,
A. s-Trithiane 692
.
1. Preparation 692
2. Structure 716
.
3. Reactions 725
.
General Properties 725
a.
.
Complexes with Heavy Metal Salts 726
b.
.
c. Thermal Reactions 726
.
d. Halogenation' 7 29
.
e. Oxidation 733
.
f. Miscellaneous Reactions 751
.
Methylene Derivative 753
g.
.
4. Uses 756
C,S,-C@,-C,S, 2,4,6,8,9,10-HWthia-
B. adarnantane . 757
C. C,S,-C,NS-C,NS
. 4,6,1O-Trithia-l-azaadaman-
tane 762
.
11. C406FtingSystems , 774
.
I. o-Oxathia Compounds 774
. .
A. C,oS o-Oxathiane and o-oxathiin 774
. .
1. o-Oxathiane
. 774
a. Preparation 774
. .
Properties, Reactions, Uses 780
b. and
Contents of Part Two
783
.
3. 0-oxathiin 789
.
B. 5H-Cyclopentfc] [ 1,210xathiin 792
C,-C,OS
.
792
c. c4m-c,
.
1. l,%-Benzoxathiin 792
.
2. 2,l-Benzoxathiin 796
.
3. 2,3-Benzoxathiin 799
799
D. C4oS-C,-C6
1. W-NaphNl, 2-4-2, &oxathiin 799
.
2. 3H-Naphtql, 8-cd]-[lJ 2I-oxathiin 800
.
3. Dibenz[ ce]-[ 1, 21 -oxathiin 801
.
802
E. c,~-c6-c6-c6
1. Benzo[c]aaphth[2,l-e]-[ 1,2]-01mthiin 802
804
1ff-Peryldl,12-cd]-
F. c4oS-c6-c6-c6-. c6-c,
[1,2]-oxathiin 805
805
wt-Oxathia
IL Compounds .
805
A. C40Sn-oxathiane
.
810
B. C406-Ce
.
1. 3,l-Benzoxathian 810
.
2. 2-Oxa-4-thiabicycl~3.3. llnonane 814
C. C~OS.- C~OS-C2~,O6-SD iw-9, lO-dithiaadamm-
tane 8 14
D. C40S-C.4 0,-C,S, 2,10-Dioxa-6,9-dithiaadaman-
tane 816
p-Oxathia 816
III. Compounds.
.
p-Oxathiane and P-Oxathiin 816
A. C40S
.
1. p-Oxathiane 817
Preparation 817
a.
.
Properties and 825
b. . Uses
c. 9eactions 826
.
2. Substituted 828
P-Oxathianes
a. Preparation 828
.
Properties, Reactions and Uses 832
b.
X
Contents Part Two
of
.
3. p-Oxathiane 4-oxides 835
4. p-Oxathianium Compounds 838
.
5. p-Oxathiane-2,6-diones (Anhydride 840
Form)
.
6. Dihydro-$-Oxathiin 842
.
7. Spiro-p-Oxathianes 84 7
C203-C40S 6, 7, 8-Trioxa-3-thiabicyclo [3.2.1]
B.
octane 84 8
.
C. C,S-C4CH lloctane 850
3-Oxa-8-thiabicyclo(3.2.
.
D. C,0S-C5S 850
3-Oxa-9-thiabicycl~3.3.l]nonane
.
E. c4oS-c50 1
W-Pyrand2,3-b]-p.- oxathiin 85
F. 1,4-Benzoxathiin 85
C,oS-C, . 2
1. Preparation 852
.
Reactions 858
2.
G. c4~-c,o-c65 H-1,4-0Rathiin0[3, 2-12] [I]-
benz opyran 861
.
H. c,a-C,oS-c6 862 .
I
1. Benz$ 1,2-b :4 ,3-b' bis-l,4-oxathiin and
.
Benz 1,241: 4,5-b' bis-l,4-oxathiin 862
.
2. 4aii-Benzo[2,l-b: 2,3-b']bis-l, 863
4-oxathiin
1. c,a-C,-c, 864
.
1. Phenoxathiin 864
.
a. Phenoxathiin
864
(1) Preparation 864
Properties and Structure 865
(2) .
(3) Opening Reactions 866
Ring .
(4) 867
Uses
b. Phenoxathiin. 10-Monoxide and 10,lO-
Dioxide 868
.
c. Hydrocarbon-Substituted Phenaxathiins 870
.
(1) Alkylphenaxathifns 870
(2) Cycloalkylphenoxathiins 872
.
(3) Arylphenoxathiins 873
.
(4) Vinylphenoxathiins 8 73
.
(5) Miscellaneous Derivatives 874
xi