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Three Heterocyclic Rings Fused (6:6:6)
8.39 Three Heterocyclic Rings Fused (6:6:6) LUCJAN STREKOWSKI, SHOU-YUAN LIN, KOEN VAN AKEN and STEVEN E. PATTERSON Georgia State University, Atlanta, GA, USA 8.39.1
SURVEY OF SYSTEMS
1091
8.39.2
THEORETICAL METHODS
1092
8.39.3
EXPERIMENTAL STRUCTURAL METHODS
1092
8.39.3.1 X-ray Diffraction 8.39.3.2 Molecular Spectra 8.39.3.2.1 NMR spectroscopy 8.39.3.2.2 Electronic absorption and fluorescence spectroscopy 8.39.3.2.3 ESR spectroscopy
1092 1092 1092 1093 1093
8.39.4
THERMODYNAMIC ASPECTS
1093
8.39.5
REACTIVITY
1093
8.39.6
SYNTHESIS
1093
8.39.6.1 General Remarks 8.39.6.2 Hetero Analogues of Anthracene (Table 1) 8.39.6.2.1 Formation of the central ring 8.39.6.2.2 Formation of the terminal ring 8.39.6.2.3 Formation of two rings 8.39.6.2.4 Formation of three rings 8.39.6.2.5 Ring transformation 8.39.6.3 Hetero Analogues of Phenanthrene (Table 2) 8.39.6.3.1 Formation of the central ring 8.39.6.3.2 Formation of the terminal ring 8.39.6.3.3 Formation of two rings 8.39.6.3.4 Formation of three rings 8.39.6.3.5 Ring transformation 8.39.6.4 Hetero Analogues of Phenalene (Table 3) 8.39.6.4.1 Formation of one ring 8.39.6.4.2 Formation of two rings 8.39.6.4.3 Formation of three rings 8.39.6.4.4 Ring transformation 8.39.7
8.39.1
1093 1093 1093 1107 1107 1107 1107 1107 1107 1107 1107 1107 1108 1108 1108 1108 1108 1108
APPLICATIONS
1108
SURVEY OF SYSTEMS
This is the first attempt to review all fused heterocyclic systems (6:6:6) containing at least one ring junction heteroatom. There are three classes of these systems, namely heterocyclic analogues of anthracene, phenanthrene, and phenalene, which are surveyed in Tables 1-3 respectively. Please 1091
1092
Three Heterocyclic Rings Fused
(6:6:6)
consult Section 8.38.1 of the preceding chapter regarding the organization of the Tables and additional information concerning the tabulated material. The survey is an integral part of the sections that follow; brevity was necessary in order to review the large number of systems (6:6:6).
8.39.2
THEORETICAL METHODS
INDO/S CI computations have been conducted to predict sites of protonation and explain the absorption and emission spectra of a derivative of (15) <85MI 839-01, 86ZN(A)66l>. Semiempirical MNDO computations predict little charge delocalization in the pyrimidinediium system (38) and a similar dication derived from (39) <86CJC1711>. Htickel-McLachlan calculations have been used to explain the ability of a tetrazine (53) to form charge-transfer complexes and to help interpret PE and ESR spectra <87HCA1661, 94HCA86). The AMI Hamiltonian more accurately predicts a stable conformation of (72) than the MNDO method <89CB1989>. The electronic structure of azaphenalenes (152), (170)-(172), and (181)-(183) has been studied extensively by using HAM/3 semiempirical, STO-3G ab initio and other approximations <69JCS(A)1754, 80JA6068, 84JA2805, 84CCA991, 85JA3884, 86JA17,94JHC929). The HAM/3 computations predict the greatest HOMO and total electron density of (152) at positions 1, 3, 4, 6, 7, and 9 <85JA3884>. Neither the parent systems (40), (70), (73H75) (Table 1), (142), (151) (Table 2), (181), (198) (Table 3) nor their derivatives are known. These systems, however, have generated a considerable theoretical interest and have been examined by theoretical calculations. Numerous predictions have been made for presently unknown compounds. The features of interest are the aromaticity of boron-nitrogen heterocycles (40), (70), (75), (142), (151), (202) <67CJC2059,71CCC1248,84RRC613) and nitrogen heterocycles (164), (167), (173) <93J1C693, 94JHC929) and the potential conductivity or superconductivity of systems (73), (74), (184) (87IC3797,92JPC5184,93JPC4974).
8.39.3 EXPERIMENTAL STRUCTURAL METHODS 8.39.3.1
X-ray Diffraction
The conjugated systems (53) <86HCA1521>, (101) <91MI 839-01 >, (114) <91TL4473>, (171) <84MI 83907>, and (183) <82JA5497> are virtually planar in the solid state. The cation (84) is only approximately planar <71CC426), and a heterocyclic skeleton of the 2,2,3a,5,5,6a,8,8,9a-nonachloro substituted system (198) is not planar at all <72JCS(D)623, 73CJC520>. The molecular structures of noncyclically conjugated derivatives of (31) <90JOC467>, (39) <85JCS(P2)433>, (54) <9UA59io, 92JA6017), (139) (85CC311, 88TL1573), (144) <83JA2350>, and (187) <82TL2891, 83H(20)579, 83H(20)1891> have been solved. X-ray diffraction analysis has also been used to study the conformation of perhydro derivatives of (55) <78JCS(P2)818>, (67) <80JCS(P2)1733>, (69) <85AX(C)122, 87AX(C)170>, (152) <84JOC2217, 92TL1281), (191) <89HCA1125>, (192) <88JOM(34i)i09>, and (199) <84AG30i> in crystal.
8.39.3.2 8.39.3.2.1
Molecular Spectra NMR spectroscopy
The fully conjugated systems (6:6:6) of Table 2 are analogues of biaryls with a two-atom bridge linking positions. The integral application of 'H, 13C, and 15N NMR spectroscopy has been a highly successful approach in conformational studies of saturated compounds, such as derivatives of (39) <72TL1437>, (68) <84ZOR510>, (69) <89PS(41)235>, (72) <79JCS(P2)1133>, (82) <94T9909>, (98) <92T349>, (143) <81TL1711>, (189) <81TL2217, 91T1013), and (191) <80TL3635, 81TL4365).
Three Heterocyclic Rings Fused (6:6:6) 8.39.3.2.2
1093
Electronic absorption and fluorescence spectroscopy
Detailed spectroscopic and photophysical studies of the following systems or derivatives have been reported: (15) <83JOC2476, 87JCS(F2)1475,90ZN(A)999>, (25) <83CC183, 83JOC2481), (39) <82JPC2049>, (101) <89JCS(P2)1691>, (152) <86JA17>, and (183) <84JPC4324>.
8.39.3.2.3
ESR spectroscopy
Systems (53) <94HCA86>, (62) <91CB2781>, (152) <73JA6702>, and a 6,7-dihydroderivative of (139), diquat, <93JPC7800> are easily oxidized to stable cation radicals. The ESR spectrum of the unstable anion radical resulting from reduction of (152) has been obtained <73JA6702>.
8.39.4
THERMODYNAMIC ASPECTS
The concept of topological resonance energy was introduced to provide a relative measure of aromaticity <77JA1692>. In a newer approach, the absolute hardness, or HOMO-LUMO gap, as the measure of aromaticity is denned to be in the ionization potential of the species minus its electron affinity. The parameters of the absolute hardness and a related relative hardness for (152) are consistent with the high reactivity of this compound <89JA737l).
8.39.5
REACTIVITY
The reactions of heterocyclic compounds composed of fused systems (6:6:6), such as electrophilic and nucleophilic attack at a ring or a substituent and partial reduction, are often highly selective. Unfortunately, there are few unifying features among the reactivities of the three different classes of systems, and a detailed treatment of the reactivity is beyond the scope of this concise chapter. All references to the chemistry of a particular parent compound and derivatives are given in Tables 1-3.
8.39.6
SYNTHESIS
8.39.6.1
General Remarks
All synthesis references are printed in boldface in Tables 1-3. The many synthetic methods reported have been classified below into several general approaches according to a one-pot construction of one, two, and three fused rings, and ring transformation of a fused ring system substrate. The references listed in Tables 1-3 are not duplicated here if a particular ring system (6:6:6) has been constructed using one approach only. It should be noted that the particular approach according to this classification may involve different types of chemistry.
8.39.6.2 8.39.6.2.1
Hetero Analogues of Anthracene (Table 1) Formation of the central ring
The most widely used method involves an intermolecular cyclization of two one-ring components substituted with appropriate functional groups. This approach provides an efficient synthetic entry to (1), (6), (7) <78CB2297, 86ZC290, 91LA1215), (8), (9), (11) <86CB1070>, (12), (15) <81TL449, 83JHC575, 83JOC2476), (16) <72CB743, 86ZC290>, (20), (24), (25), (28), (30), (32), (34), (35), (39), (49), (51)-(56), (58), (62), (63), (65)-(68), and (71). An intramolecular cyclization of a substrate composed of two six-membered heterocycles and bridged by a one-atom unit has been applied to the synthesis of derivatives of (5), (15) <75JHC477,85JHC173,94JHC81), (17), (26), (27), (38), (43), (45), (46), and (69).
Table 1 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (2508) for the tricyclic skeleton. (References in bold refer to synthesis.) 10
\ / 7
l O a ^
6
T
10 11 .10a
1
;CTD
) \
-^ 3 4
7
Type i
io
r
11 /~-
5a " - ^ 4 a 5 4
6
4
6
Type ffl
Type II 1
12
6
J3 ' 5~\ / 4
10 ,,
12
1
6
4
7
5
4
Type VI
Type VII
13
6
5
4
Type IX Positions of ring heteroatoms
A One ring junction nitrogen atom A.I Two ring heteroatoms (1) II M.JV6 (2) II OX, N6
(3) A.2 Three ring (4) (5) (6)
III
02, MO
heteroatoms II NX,N3,N6 I NX,N5,NX0 III M , N5, MO
Ring identifier (Chem. Abstr.)
Type VIII
14 '
(8)
III
N2, N5, MO
2508.693
(9) (10)
II I II III I I
JV2, N6, NX 1
2508.674 2508.753 2508.149 2508.715 2508.754 2508.752
SX,N5, 08
6
4
I
Type XI Parent system
li/-Dipyrido[l,2-a:4',3'-rf|pyrimidine
Nl,N6, Ml
(12) (13) (14)
TypeX
2//-Pyrimido[4,5-6]quinolizine 2H-Pyrimido[l,2-g]naphthyridine l//-Dipyrido[l,2-a: 3',2'-rflpyrimidine 2//-Dipyrido[l ,2-a: 2',3'-
II
(H)
4
2//-Pyrido[l ,2-^]-l,6-naphthyridine 2i/,5//-Pyrano[2,3-6]quinolizine l//,3H-Pyrano[4,3-/>]quinolizine
(7)
NX, N5, 0 8 Ol,JV6,jVll O2, NS, MO Ol, W5, O8
7^ ^ 5 6
B
2508.86 2508.99 2508.855
2508.88 2508.759 2508.675 2508.144
5
7
N'
Type
5
Type IV
6
7
TypeV
Tricyclic system
5a
v. 2
9 R
5
N'
2//-Dipyrido[l,2-o: 3,4'-
References
57MI 839-01, 81CJC106 72LA(761)2S, 80M93, 83M48S 94H(38)81
70YZ127 89MIP890S809, 90JHC189 86ZC290 71JHC637, 71JOC2192, 78CB2297, 86ZC290, 91LA1215, 92JHC25 87JCS(P1)9O9, 87JHC1473, 87MI839-01,87MI839-02, 87T1157, 88MI 839-01, 93OMS(28)18 86ZC290 89LA1241 86CB1070, 90ZC98, 93MIP9323398 87JHC1557 89LA1241 89LA1241
A3 Four ring heteroatoms II (15)
N1,N3,N+6,NU
2508.146
Pyrido[l ,2-a]pyrimido[4,5-(flpyrimidin-6-ium
N\,N4,N5,N\0 N\,N5,N\0,Nll N\,04,NS,NIO Nl,N6,01,N\l N1,N5,NIO,SU N\,N6,S9,NU SI, N5, Si, Nil
2508.215 2508.631 2508.814 2508.698 2508.377 2508.145 2508.657
1 #-Pyrido[2,1 -A]pteridine 2//-Pyrido[2,3-t?]pyrimido[l,2-a]pyrimidine lff,77/-Pyrido[l',2': l,2]pyrimido[4,5-A][l,4]oxazine Pyrido[2',3': 4,5]pyrimido[l,2-6][l,2]oxazine 2H,6ff-Pyrido[3,2-e]pyrimido[2,1 -b][l ,3]thiazine Pyrido[2',3':4,5]pyrimido[2,l-c][l,4]thiazine 4',3': 4,5]pyrimido[2,1-6][1,3]thiazine
A.4 Five ring heteroatoms II (23) (24) II (25) II
N\,N2,N5,N6,NU N\,Ni,N5,N6,NU Nl,N3, N6, M, Nli
2508.736 2508.524 2508.406
2//-Pyridazino[3,4-e]pyrido[l ,2-b][ 1,2,4]triazine 2i/-Pyrido[l ,2-A]pyrimido[4,5-e][l ,2,4]triazine 2i/-Dipyrimido[l,6-a:4',5'-rf|pyrimidine
(26) (27) (28) (29) (30) (31)
N\, JV3, N6, N9, Nil N\,N4,N5,N6,N\0 N\,N3,N6,M,OU Nl, N3, N5, N\0, SU Nl, N3, S5, N6, Nil Nl,N3,N6,S9,Nll
2508.860 2508.216 2508.535 2508.625 2508.299 2508.147
2//-Pyrazino[l,2-a]pyrimido[4,5-rf)pyfiniidine 1 //-Pyrimido[2,1 -6]pteridine 2//,7//-Dipyrimido[6,l-A: 5',4'-e][l,3]oxazine 2i/,6W-Pyrido[3',2': 5,6][l,3]thiazino-[3,2-a]-l,3,5-triazine Pyrido[l ,2-i]pyrimido[4,5-e][l ,2,4]thiadiazine Pyrimido[4',5': 4,5]pyrimido[2,l-c][l,4]thiazine
(16) (17) (18) (19) (20) (21) (22)
(32) (33)
III I III II I II I
I III II I II II
11 III
A.5 Six ring hiHeroatoms (34) II (35) II (36) IV (37) IV
Nl,N3, N6, N10, S\\ Nl, N4, JV5, S6, AflO
2508.448 2508.450
2,l-6 : 5',4'-e][l,3]thiazine l//,7tf-[l,3]Triazino[2,3-%teridine
N\,N3,S5,N6,M,N\\ N\,m,S5,N6,N9,NU N\, S3, N5, N6, Ni, Nil P\,O2,N4,N5,N6,N\\
2508.301 2508.300 2508.148 2508.801
Pyridazino[l,6-6]pyrimido[4,5-e][l,2,4]thiadiazine Pyrazino[l,2-6]pyrimido[4,5-e][l,2,4]thiadiazine Pyrimido[4',5': 4,5]pyrimido[l ,2-d\[\ ,3,4]thiadiazine l//,3i/-Pyrido[2',3': 4,5]pyrimido[l ,2-c][l,3,5,2]oxadiazaphosphorine
2508.341
Dipyrido[l,2-c: 2',l'-:/]pyrimidinediium
B Two ring junction heteroatoms B.I Two ring heteroatoms (38) V JV+5, N+l
74USP3836533, 75JHC477, 81TL449, 83JHC575, 83JOC2476, 85JHC173, 85MI 839-01, 86JPC5820, 86ZN(A)661, 87JCS(F2)1475, 88JHC959, 90ZN(A)999, 94JHC81 72CB743, 86ZC290, 92MI839-01 85JHC193, 86MIP8606375, 93CCC1130 91IJC(B)839 87JHC175,91JHC2071 73JIC358 73CPB770 85M1 839-02
89CB1935, 90CB1415, 91CB1477, 92JAP(K)04015644 79DIS(B)5678 74CPB2086, 83CC183, 83JOC2481, 86JPC5820, 87ZN(A)485, 90ZN(A)999 94JHC81 86MIP8606375, 93CCC1130 80KGS992 85FES65 69GEP(O)1809013 66MI 839-01, 67CPB1178, 67CPB1183, 67JAP05000302, 67JAP42005665, 67JAP42009834, 67JAP42020070, 67JAP42025916, 68CPB1773, 68JAP43005397, 68JAP43010631, 68JAP43019553, 68JAP43019958, 68JAP43019959, 69JAP44030276, 72YZ27, 73CPB770, 74MI 839-01, 75MI839-01, 90JOC467 76IJC(B)759 77ACS(B)167, 78CB971, 93HCA431 69GEP(O)1809013 69GEP(O)1809013 70CPB1201, 70GEP(O)1954275, 72JAP47050120 89MI 839-01
69JC250, 69MI 839-01, 70T3369, 73JOC1098, 74OMR(6)253, 76JCS(P2)418, 86CJC1711, 88SM371
re
3
3
Table 1 (continued) Trkyclic system
Type
(39)
VI
Positions of ring heteroatoms N5,NU
Ring identifier (Chem. Abstr.) 2508.342
(40)
2508.2
B.2 Three ring heteroatoms (41) VII N\,N6tNU
Dipyrido[l,2-a: l',2'-
Borino[l,2-rf]pyrido[l,2-a][l,4]azaborine
2508.87 2508.66 2508.350
Pyridazino[l,2-a]pyrido[2,3-rf|pyridazine Pyridazino[l,2-a]pyrido[3,4-rf]pyridazine 2//-Dipyrido[l,2-o:2',r-rf|[l,3,5] triazin-5-ium
N 5, N 7, Sel2
2508.849 2508.366 2508.474
11#-Pyrido[l',2':3,4]pyrimido[l,6-A][1,2] thiazine 2tf-Dipyrido[2,l-fc: )',2'-e][l,3,5] thiadiazinediium 2ff-Dipyrido[2,l-A: r,2'-e][l,3,5] selenadiazinediium
Nl,N4,N6, Nil Nl,N5,Nl,Nll NI,N6,N7,N12 N2, Nl, N6, Nl 1 N2, N5, NS, Nl 1
2508.205 2508.799 2508.343 2508.67 2508.601
Pyrazino[2,3-rf]pyridazino[l,2-a] pyridazine Pyrazino[l,2-a: 4,5-a']dipyrimidine Pyrazino[l,2-i: 4,5-A']dipyrimidine Dipyridazino[l,2-o:4',5'-
(42)
VII
7V2, JV6, JV11
(43)
V
r5,iV7,iVI2
(44) (45) (46)
IX V V
SI,NIO,N12
B.3 Four ring heteroatoms (47) VII (48) VI (49) VIII (50) VII VI (51)
Parent system
iV+5, AT+7, S I 2 +
+
(52) (53)
VIII VI
N2, N6, M, N12 N5,N6,Nll,Nl2
2508.522 2508.357
Dipyrido[l,2-ft:l',2'-e][l,2,4,5]tetrazine
(54) (55)
VI VIII
02, JV+5, 08, W+i; 05, JV6, O i l , JV12
2508.779 2508.365
Pyrazino[2,l-c:5,4-c']bis[l,4]oxazinediium 1#,7//-Dipyrido[l ,2-b: l',2'-e][l ,4,2,5] dioxadiazine
(56)
VI
52, JV5, S8, Nl I
2508.510
l#,6#-Pyrazino[2,l-c:5,4-c']bis[l,4]thiazine
2508.784
l//,7//-Bisphosphorino[l,2-i:r,2'-e][l,4,2,5]dithiadiphosphorine
References
67EGP55860, 70G421, 70JCS(D)482, 72CCC4060, 72TL1437, 73CCC1940, 73CCC1957, 74CPB157, 78JCR(S)224, 81 MI 83901, 82JPC2049, 84MI 839-01, 85JCS(P2)433, 85JOC2910, 86CJC1711 71CCC1248
70AQ561, 73JCS(P1)26 70AQ561 69MI 839-01, 73JOC1098, 74OMR(6)253, 82SM31, 86H(24)1893, 86JPC5820, 86S402, 86USP4594413, 88ZOB1685, 89ZOR1354 93SL551 67NAT381,68T2697 78ZN(B)118 70AQ561 90JCR(S)304 71JCS(C)526, 71RRC1107, 73MI 839-01 68JCS(C)2857, 75JHC95 84DIS(B)202, 85JMC1228, 89USP4871736, 93MIP9323075 80MI 839-01, 81RRC879, 94JHC1707 67CB2467, 73JOC4259, 75JPR561, 77ZOR948, 86HCA1521, 86HCA1531, 87HCA1661, 88JAP(K)63229455, 90HCA81, 94HCA86 89USP4871736, 91JA5910, 92JA6017 72LA(759)183, 78JCS(P2)818, 82M339, 92OS(70)265 79KGS1211, 87MI839-03
11
(57)
90HAC37
*. • • ^
c^ k^
1
B.4 Five ring heteroatoms IX (58) (59) VIII (60) VIII
N2,N5,m,N+Vj,Nl2 Nl, O4, N5, N+6, Nil Nl,SA,Ni, N+6,Nl2
2508.662 2508.692 2508.626
li/-Dipyrimido[l ,6-a:6', 1 '-d\[ 1,3,5]triazin-10-ium l#,8tf-Pyrido[l',2':l,6][l,2,4]triazino[3,4-6][l,3,4]oxadiazin-6-ium l//,8frPyrido[l',2':l,6][l,2,4]triazino[3,4-6][l,3,4]thiadiazin-6-ium
B.5 Six ring heteroatoms (61) V (62) VI (63) VIII (64) VIII (65) VI
Nl,N3,N5,NT, N9, Nil NI.N5, N6, NT, Nl\, N12 N2,N5,N6,M,Nll,Nl2 N2,O5,N6,M,Oll,Nl2 O2,NS,N6,OS,Nll,Nl2
2508.457 2508.443 2508.442 2508.425 2508.358
2i/,6i/-Pyrimido[l ,6-a:3,4-a']bis[l ,3,5]triazine Dipyrimido[l,2-A:l',2'-e][l,2,4,5]tetrazine Dipyrimido[l ,6-b: l',6'-e][l ,2,4,5]tetrazine l//,7//-Dipyrimido[l,6-6:l',6'-e][l,4,2,5]dioxadiazine l//,6.ff-Bis[l,4]oxazino[4,3-fc4',3'-e][l,2,4,5]tetrazine
2508.364
Bis[l,2,4]triazino[4,3-A:4',3'-e][l,2,4,5]tetrazine
C. Four ring junction heteroatoms C.I Four ring heteroatoms (67) X NS, NT, N12, N14
2508.370
6H, 13//-Dipyridazino[l ,2-a: 1 ',2'-a\l ,2,4,5]tetrazine
C.2 Six ring heteroatoms (68) X (69) X (70) XI
2508.596 2508.612 2508.4
l//,6H,8#,13//-Bis[l,3,4]oxadiazino[3,4-a:3',4'-(/][l,2,4,5]tetrazine 6ff,13//-Dipyridazino[l,2-a:l',2'-rf|[l,2,4,5,3,6]tetrazadiphosphorine 6i7,13/f-Bis[l,2]azaborino[l,2-a:2',l'-rf|[l,3,5]triazatribonne
2508.700
6//,13//-Bis[l,2,4,5]tetrazino[l,2-a:l\2'-d][l,2,4,5]tetrazine
85CI(L)797, 86H(24)1893, 86USP4594413 86JCR(S)460 84S697 77CR(C)25, 80EJM341 76RTC282, 89EGP272303, 91CB2781 76M1241, 90ZC133 75CB3387 65JA393
B.6 Eight ring nitrogen atoms (66)
VI
ATI, JV2, N5, N6, NT, NS, NU.N12
O2, JV5, NT, O9, N12, JV14 NS, P6, NT, ATI 2, P13, Afl4 NS, B6,NT,B12,N13,B14
C.3 Eight ring heteroatoms X N2, m, NS, NT, N9, NIO, (71) N12,N14 • (72) X 02, O3, NS, NT, O9, 010, N12,N14 C.4 Fourteen ring heteroatoms Ol,N2, N3, O4, N5, 06, (73) NT, O$,N9, NIO, Oil, N12, 0 1 3 , JV14 (74) SI, Ar2, AG, S4, NS, S6, NT, S8.A/9, AT10, S l l , AT12, S13, ATI4 ATI, B2, AR, B4, NS, B6, (75) XI
67CB2585, 87S1134
63JOC1144, 72JA3138, 74JA576, 74JCS(P2)948, TO1 76JA5748, 78LA1505, 79CB853, 80JCS(P2)91, ?? 80JCS(P2)1733, 87MI 839-04 g
84ZOR510 85AX(C)122, 87AX(C)170, 89PS(41)235 71CCC1248
60LA(635)73, 79JCS(P2)1133, 89CB1989
2508.371
l//,4//,6//,8H,ll//,13//-[l,2,4,5]Tetrazino[l,2-rf:4,5rf|bis[l,2,4,5]dioxadiazine
2508.820
Bis[l,4,2,3,5,6]dioxatetrazino[2,3-A:2',3'-e][l,4,2,3,5,6]dioxatetrazine
92JPC5184
2508.835
Bis[l,4,2,3,5,6]dithiatetrazino[2,3-ft:[l,4,2,3,5,6]dithiatetrazine
93JPC4974
2508.5
6i/,13//-Bis[l,3,5,2,4,6]triazatriborino[l,2-a:2',l'-rf|[l,3,5,2,4,6]triazatriborine
84RRC613
NT,B8,N9,BlO,Nll, B12,N13,B14 9 10 1 O 9a O 1Oa O H Si Si' S i ' "Si' (76) O 6
,Si, 5 5aa
O O 5
, 4a
2508.372
O 4
H
l,4,5,6,9,10-Hexaoxa-2,3,4a,5a,7,8a,9fl,10a-octasilaanthracene
I
88CB815
63MI 839-01
ON
Table 2 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (2404) for the tricyclic skeleton. (References in bold refer to synthesis.)
o oo
Type XII
Type XIII
Type XIV
8
Type XVIII
Type XVII Tricyclic system
Type
Positions of ring heteroatoms
A One ring junction nitrogen atom A.I Two ring heteroatoms (77) XIII JV1, Nl +
Ring identifier (Chem. Abstr.)
Parent system
2404.656
l//-Pyrido[l,2-A]-l,7-naphthyridine
(78)
XIV
N\,N U
2404.328
Pyrido[l,2-a][l,8]naphthyridin-ll-ium
(79) (80) (81) (82)
XIII XIV XIV XIII
N2,N7 N2, Nl 1 N3, N\ 1 N4,N7
2404.233 2404.692 2404.290 2404.234
1 tf-Pyrido[2,1 -a][2,7]naphthyridine 2//-Pyrido[l ,2-a][l ,7]naphthyridine 2//-Pyrido[l,2-a][l,6]naphthyridine l//-Pyrido[2,l-/][l,6]naphthyridine
(83)
XIII
04, Nl
2404.235
Nl, N2, N*l Nl,N2,Nll Nl, JV3, A'l 1 Nl, N5, A'l 1 Nl, N6, Nl 1
2404.274 2404.687 2404.532 2404.827 2404.330
Pyridazino[3,4-fl]quinolizin-7-ium 2//-Pyridazino[4,3-c]quinoIizine 2//-Pyrimido[5,4-6']quinolizine 2i7-Dipyrido[l ,2-a: 3',2'-e]pyrazine 2i/-Dipyrido[l,2-a: 3',2'-e]pyrimidine
Nl, N7,NU
2404.329
2//-Pyrimido[l ,2-a][l ,8]naphthyridine
2404.849
2i/-Pyrazino[l,2-a][l,8]naphthyridine
A.2 Three ring (84) (85) (86) (87)
heteroaloms XIII XIV XIV XIV XIV
(88) (89) (90)
XIV XIV
NS Nil
I? s
7
l//,6//-Pyrano[3,2-a]quinolizine
References
85EUP154142, 87EUP216247, 87USP4690928, 87USP4710504, 88JMC641 78H(9)1717, B-79MI 839-01, 80CPB220, 80FES1052, 81CPB2526, 84MI 839-02, 89UKZ839, 92S798, 93T2691 67ACSS80 86UKZ506 71USP3SS7100, 86MI 839-01, 86UKZ506 67ACS580, 67NAT381, 68AX(A)252, 70CPB124, 72MI 839-01, 81CJC106, 94T9909 72LA(761)25, 83M349
71CC426, 73AJC389 86MI 839-01 80CL817 91S982, 92JHC529 83M1197, 85EJM61, 86H(24)3075, 86JHC509, 87MIP554364 66G1443, 67G1262, 67G1274, 69G677, 71G129, 71JCS(C)2985, 72G2S3, 77JCS(P1)789, 90JHC881 92S798, 93H(36)1337
(91) (92) (93) (94) (95) (96) (97) (98) (99)
XIV XIV XIV XIV XV XIV XIV XIV XIV
2404.738 2404.844 2404.359 2404.639 2404.482 2404.850 2404.764 2404.832 2404.851
2//-Pyrimido[4,5-c]quinolizine 2//-Dipyrido[l,2-a: 3',4'-ejpyrazine 2//-Pyrimido[l ,2-a][l ,6]naphthyridine 2/f-Dipyrido[l,2-a: 2',3'-e]pyrazine 1 i/-Pyrimido[ 1,2-a][ 1,5]naphthyridine [l,4]Oxazino[4,3-«][l,8]naphthyridine Dipyrido[2,3-6: l',2'-rf)[l,4]oxazine 27/,5i/-Pyrano[3',2': 5,6]pyrido[t,2-
2404.718 2404.714
2//-Pyrido[2', 1': 2,3]pyrimido[4,5-c]pyridazine 2i/-Pyrido[2,1 -%teridine
Nl,S6,NT,Nll
2404.533 2404.275 2404.246 2404.689 2404.690 2404.691 2404.471 2404.564 2404.608 2404.484 2404.678 2404.553 2404.769 2404.717 2404.485 2404.716 2404.486 2404.751 2404.887 2404.546
2//-Pyrido[l,2-a]pyrimido[5,4-c]pyrimidine l//-Pyrido[l,2-a: 3,4-A']dipyrazine Pyrido[3,2-rf]pyrimido[l,2-/>]pyridazin-5-ium 2//-Pyrido[4,3-rf|pyrimido[l,2-/i]pyridazine 2//-Pyrido[3,4-rf|pyrimido[l,2-A]pyridazine 2i/-Pyrido[2,3-rf]pyrimido[1.2-A]pyridazine 2//-Pyrido[3,2-e]pyrimido[l,2-e]pyrimidine 2//-Pyrido[4,3-£]pyrimido[l,2-c]pyrimidine 2//-Pyrido[3',2': 5,6]pyrazino[l,2-a]pyrimidine 2//-Pyrazino[l,2-a]pyrido[3,2-e]pyrazine 2//-Pyrido[3,2-e]pyrimido[l,2-a]pyrimidine 1//-Pyrido[l ,6-b: 3,2-c']dipyridazine l//-Pyrido[l,2-e]pyrimido[5,4-e]pyrimidine 2//-Pyrido[4',3': 5,6]pyrazino[l,2-a]pyrimidine 2//-Pyrazino[l,2-a]pyrido[4,3-e]pyrazine 2//-Pyrido[3',4': 5,6]pyrazino[l,2-a]pyrimidine lff-Pyrazino[l,2-a]pyrido[2,3-e]pyrazine 2//,8//-Pyrazino[2,l-A]pyrido[2,3-rfl[l,3]oxazine Pyridazino[4',5': 5,6]pyrido[2,l-c][l,4]oxazine 2i/,8//-Pyrido[2,3-rf|pyrimido[2,1 -b][ 1,3]thiazine
Nl,N2,NS,N6,N& Nl,N2,NS,N6,Nll Nl,Ni,NS,NT,Nll Nl,N3,N6,NT,Nll Nl,NA,N5,NT,Nll Nl,N5,N6,NS, N10 Nl, N6,NT,NS,Nll N2, NA, NS, NS, Nl I N2, NA, NS, N9, Nl I
2404.247 2404.276 2404.607 2404.753 2404.828 2404.752 2404.679 2404.506 2404.355
2//-Pyrido[2',3', :4,5]pyridazino[6,l-c][l,2,4]triazine 2//-Pyrido[3',2':4,5]pyridazino[6,l-c][l,2,4]triazine 2H-Pyrimido[2,1 -/i]pteridine 1//-Dipyrimido[l,2-/): 4',5'-d]pyridazine 1 //-Pyrimido[ 1,2-c]pteridine 2//-Dipyrimido[l,2-6:5',4'-
Nl,NA,N6,ST,Nll
2404.447 2404.505 2404.393
2/f,8//-[l,3]thiazino[3,2-a]pteridine Pyrido[3',2',: 5,6][l,4]thiazino[3,4-c][l,2,4]triazine 2//,6a//,8//-[l,3]Oxazino[2,3-/;]pyrimido[4,5-rfl[l,3]oxazine
N2, NA, N\ 1 A3, NS, N\ 1 A 3 , NT, A'l 1
NA, NS, Nl 1 NA, NT, N\ 1 AT1.O8, JV11
N4, OS, Nl 1 Ol,N9, Nil Nl,SS,Nll
A.3 Four ring heteroaloms XIV (100) Nl, N2,N6, Nl 1 XIV (101) Nl,Ni,N5,Nll (102) (103) (104) (105) (106) (107) (108) (109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121)
XIV
XIII XII XII XII XII XII XII XIV XIV XIV XV
XIII XIV XIV XIV XV XIV XIV XIV
A.4 Five ring heteroatoms XII (122) XII (123) XIV (124) XIII (125) XIII (126) XII (127) XIV (128) XIV (129) XIV (130) (131) (132) (133)
XIV XV XIV
Nl,N3,N6,NU Nl, NA, NT, NIQ Nl, N+S, Nb, NS Nl, NS, N6, N9 Nl, N5, N6, N10 Nl,N5, N6, Nil Nl, N5, NT, NS N\, NS, NT, N9 Nl,NS,NT,Nll Nl,NS,NS,Nll Nl,N6,NT,Nll Nl,NT,NS,Nll N2, NA, NS, NT N2, NS, NT, Nl 1 JV2, NS, NS, Nl 1 A3, NS, NT, Nil A3, N6, NT, Wl 1
Nl,O6,m,NU N2, A3, O8, A'l 1
A 3 , JV4, S6, NT, Nl 1
A'l, A3, O6,OT,NU
88MI 839-02 92JHC529 74JHC151 85IJC(B)182, 89MI 839-02, 94FES259 78PJC1395 92S798 90JAP(K)02096580 92T349 92S798
88CB2049 87T3955, 89JCS(P2)1691, 89MIP148975, 90CJC2164, 91JA1756, 91 MI 839-01, 91MI 839-02, 92MI839-02 80CL817, 85JHC173, 87KGS677 64MI 839-01 71JOC2457, 85MI839-03 85MI 839-03 85MI 839-03 85M1839-03 78JHC877 82EUP46446 83IJC(B)1233, 88EUP257508 79USP4138564 86JHC509, 87MIP554363 81JA7011 90MI839-01, 91TL4473, 93JOC6976 88EUP257508 79USP4138564 88EUP257508, 93BRP2257360, 93MI 839-01 79USP4138564 89MI 839-03 94H(37)171 81JHC495
70M303 70M303 83IJC(B)1233 89T4485 91CCC2288 89T4485 86JHC509, 90AF1349 82JMC161 74GEP(O)2330984,75B3338,81JMC1086,83B1005, 84MI 839-03, 87B522 77ACS(B)167 79URP638068, 93KGS559 75USP3860596
I I
Table 2 (continued) Tricydic system
Type
Positions of ring heteroatoms
Ring identifier (Chem. Abstr.)
Parent system
o o References
A.5 Six ring heteroatoms (134) XIII M,iV3, JV5, JV6, iV7, M l
2404.622
(135) (136)
2404.673 2404.504
li/-Dipyrimido[l,2-c: 4',5'-e][l,2,3]triazine 2i/-Pyrimido[2',l',: 2,3]pyrimido[5,4-rf][l,2,3]triazine Pyrimido[5',4': 5,6][l,4]thiazino[3,4-c][l,2,4]triazine
84JCS(P1)1475 86JCS(P1)711 93KGS559
2404.674
2//-Pyrimido[4,5-e][l ,2,4]triazino[4,3-c][l ,2,3]triazine
86JCS(P1)711
2404.864
2//-Pyridazino[3,4-
93MI839-02
2404.285
Dipyrido[l,2-a: 2', 1 '-c]pyrazinediium
XIV XIV
N2,N3,N4,N6,N7,NU N2,N4,S5,N7,NS,NU
A.6 Seven ring heteroatoms XII N\,N2,N5,N6,N7,N9, (137) Ml (138) XIV Nl,N2,N5,N6,N7,NlO, Ml B Two ring junction atoms B.I Two ring heteroatoms XVI N+5,N+% (139)
General chemistry: 67AJC1213, 68AJC2951, 68JCS(C)926, 68T4411, 68T5433, 68TL2599, 69CCC2037, 69E1247, 69JA3822,69JCS(C)610, 69T4781, 70JCS(D)494, 71JHC29, 72AX(B)1244, 72AX(B)3065, 72JCS(P1)138, 72JHC1165, 72JMR(8)207, 73JCS(P2)80, 74CPB157, 74JHC303, 76JA1711, 76ZN(B)115, 77AJC657, 77JCS(P2)445, 78JCS(F1)665, 78JPC1181, 82AJC1341, 82JCS(P1)125, 83JA2350, 84ANC1030, 84H(22)803, 84LA1731, 85BBA(810)385, 85JOC2910, 86CJC1711, 86CL2139, 86JC265, 86TAL745, 87CJC2425, 87JA2876, 87JOC521, 87MI 839-05, 88CL373, 88JA8232, 88JOC4745, 88TL1569, 89AG462, 89CB1023, 89GEP(O)3717071, 89JA5782, 90CL493, 90MI 839-02, 90URP1594175, 91BCJ1821, 91CPB956, 91EUP431547, 91JOC4678, 91MI 839-03, 91MI 839-04, 91SM1819, 92MI 839-03,92TL1771,93JC271,93JPC7800,94CC51,94JC217, 94MI 839-01 Applications: 67AJC1195, 67NAT381, 68NAT1067, 69NAT464, 70MI 839-01, 71MI 839-01, 72CI(L)195, 72MI 839-02, 72MI 83903, 73JA3411, 73LA324, 75GEP(O)2500409, 75MI 839-02, 75MI 839-03, 76JCS(F1)2416, 77CJC2601, 77MI 839-01, 78IC1827, 78JA579O, 78JPC2662, 79JCS(F1)1912, 79JEC283, 79M1 839-02, B-79MI 839-03, 80CPL(74)314, 80JMOC539, 80JPC2762, 80MI 839-02, 80MI 839-03, B80MI 839-04, 81JA4727, 81JA7270, 81JMOC261, 81JOC1255, 82IJ117, 82IJ147, 82JA2683, 82JA3618, 82JA7519, 82JEC211, 82MI 839-01, 82MI 839-02, 83CC1140,83IC1672,83JA5617,83JCS(F1)1135,83MI83901, 83NJC15, 84ANC866, 84JCS(F 1)2255, 84JCS(F 1)2693, 84JPC2009, 84JPC5845, 84MI 839-04, 84TL2867,
I? s ft
3
I (ft
O\
85AG584, 85CC311, 85CC314, 85IC451, 85ICA129, 85IC3399, 85JA2632, 85JA4647, 85JCS(P2)607, 85JMOC119, 85MI 839-04, 85MI 839-05, 85TL1681, 85TL1685, 86BCJ1709, 86JA3380, 87AG939, 87BCJ3663, 87CC1054, 87CC1058, 87CC1061, 87CC1066, 87GEP(O)3616923, 87ICA135, 87JAP(K)62062881, 87JAP(K)62201803, 87MI 839-06, 87MI 839-07, 87MI 839-08, 87TL6267, 88CC52, 88ICA55, 88JA6586, 88JA6673, 88MI 839-03, 88NKK569, 88PAC467, 88TL1573, 89B6057, 89CC1874, 89H(28)359, 89JA1128,89JPC294,89JPC7130,89MI839-04,89MI839-05,90B6102, 90BCJ2710, 90MI 839-03, 90MI 839-04, 91CE9, 91CE603, 91JCS(D)1691, 91JPC1348, 91JPC3780, 91JPC10694, 91MI 839-05, 91MI 839-06, 92JA1881, 92JA3784, 92JA9504, 93BCJ1764, 93CC522, 93JPC6492, 94ANC1817, 94BCJ847, 94HCA351, 94JC688, 94JCS(P1)995,94JCS(Pl)1009,94JPC3865,94MI839-02,94MI 839-03, 94MI 839-04, 94MI 839-05
N5,N+l2
2404.331 2404.333
2//-Dipyrido[l ,2-a: 1 ',2'-c]pyrimidin-5-ium Dipyrido[l ,2-b: 2', 1 '-y]pyridazinediium
(142)
2404.2
Borinof 1,2-6]pyrido[2,1-f\[ 1,2] azaborine
B.2 Four ring heteroatoms (143) XVI NI,N5,NZ,N12
2404.545
Pyrazinofl ,2-a: 4,3-a']dipyrimidine
(144)
XVI
N2, N5,NS, N\ 1
2404.548
Dipyrazino[ 1,2-a:2', 1 '-cjpyrazine
(145) (146)
XVI XVII
N5,N6,JV7, S\,N5,SS,N12
2404.334 2404.488
Dipyrido[l ,2-d: T, 1 '-J\[\ ,2,3,4]tetrazine 2//,6//,9//,12a//-Pyrimido[2,l-6:4,3-//]bis[l,3]thiazine
B.3 Six ring nitrogen atoms (147) XVII N\,N3,N5,N8,NIO,N12 (148) XVI N2, N4, N5, NS, N9, N\ 1 (149) XVI 7V2,JV5, N6,Nl, NS, N\ 1
2404.453 2404.803 2404.469
2//,6//-Pyrimido[l ,2-a: 3,4-#']bis[l ,3,5]triazine Pyrazino[2,1 -/: 3,4-/]bis[l ,2,4]triazine Dipyrazino[l,2-d: 2 ,1'-_/] 1,2,3,4]tetrazine
B.4 Seven ring nitrogen atoms (150) XVII M , N2,N5, N6, NS,N9, N12
2404.813
(140) (141)
XVII XVIII
70LA(737)l, 71IJQ221, 76S201, 93BCJ1222 71GEP(O)2017343
i? 71CCC1248
81TL1711,84EUP113582,88MI839-04, 89MI839-05,90JCR(S)304, 92JCS(P1)561, 93JOC5753 81JMC1329, 83JA2350, 83MI 839-02, 85JMC1111, 92USP5130426, 93MIP9323075 73AG50, 74GEP(O)2327545, 78HCA1622, 94CB2073 79LA334 ON
,6//-Bis[l ,2,4]triazino[4,3-6:4',3'-d][l ,2,4]triazine
77CR(C)25, 80EJM341, 82MI 839-03 90TL7665, 92ZOR589 78HCA1622 91FES379
C Four ringjunction atoms C.I Six ring heteroatoms
(151)
2404.3
Bis[l,2]azaborino[l,2-a: r ^ ' -
71CCC1248
Table 3 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (1784) for the tricyclic skeleton. (References in bold refer to synthesis.)
8
8
8
Type XX
Type XIX
9a
N
Type XXI
3a
9b
9a
X
8
Type XXII Tricyclic system
Type
Positions of ring heteroatoms
A One ringjunction heteroatom A.I One ring heteroatom (152) XX N9b
(153) (154) (155)
XXI XXI XXI
S+9b P9b B9b
N
1784.152 1784.151 1784.1
8
X
6a
6a
Type XXIII
Type XXIV
Ring identifier (Chem. Abstr.)
1784.137
3a
N i
I 8
X
Parent system
Pyrido[2,1,6-de]quinolizine
96-Thioniaphenalene 96-Phosphaphenalene 9^-Boraphenalene
•3 References
General chemistry: 68YZ900, 69CC24, 69JCS(A)1754, 72BSB649, 72CC626, 72T3613, 72T3635, 72T3657, 72TL1767, 73JA6702, 73MI 839-02, 74AJC2025, 74TL409, 75CC565, 75T1541, 76CJC473, 76CJC1494, 76CJC1807, 76CPB2270, 76JCS(P1)341, 76TL2925, 77IJC(A)238, 77JA1692, 77JOC3210, 77JST(42)85, 77YGK739, 78AHC(22)321, 78JST(49)415, 79JA7032, 79TL1991, 80JA6068, 80TL1027, 80TL1093, 80TL1097, 81DIS(B)4524, 82H( 18)37, 84CCA991, 84JOC2217, 84JPC1376, 85JA3884, 85JOC4028, 86DIS(B)1919, 86JA17, 86MI 839-06, 87ZC28, 88DIS(B)1662, 89CPB1226, 89JA7371, 89PAC2117, 91CC1261, 92HAC19, 92SC3115, 92TL1281, 93EJM869, 94JHC929, 94T3139 Applications: 71C307, 71 El380, 72C74, 73MI 839-03, 74MI 839-02, 75E145, 78MI 839-01, 81KPS764, 86EUP172427, 91EUP451055, 91 MI 839-07, 92MI 839-04, 92MI 839-05, 93MI 839-03 72IZV2817, 73ZOR636, 74MI839-03 69USP3435076
Co Hi
ON
General chemistry: 67JA5478, 68LA(717)21, 69JA1226, 71JA7319, 73TL141, 74JOC861, 74LA54, 75CC565, 75DIS(B)1232, 76GEP(O)2608584, 76TL2925, 78CC805, 78JA3343, 78JOM(156)111, 78USP4082810, 79JMC401, 79JOC5604, 80JOM(188)1, 81T2359, 83OS(61)103, 84JOC2217, 85JOC520, 88ZOR742, 89CC1639, 93T8311 Applications: 81USP4251422 A.2 Two ring heteroatoms (156) XX
N\,N9b
1784.160
Pyrimido[2,1,6-de]quinolizine
(157) (158) (159)
XIX XIX XX
N2, Nba Ol,N6a 01, N9b
1784.113 1784.333 1784.138
1H,4#-Pyrido[3,2,1 -ij ][ 1,6]naphthyridine 4//-Pyrano[2,3,4-//]quinolizine 2H-[ 1,3]Oxazino[2,3,4-de]quinolizine
(160)
XIX
02, N6a
1784.114
l//,3//,4//-Pyrano[3,4,5-//]quinolizine
74CPB1424, 74CPB1939, 74YZ50, 75CPB2759, 75YZ1431, 76CPB2270, 78JST(49)415, 85JOC4028, 87H(26)2757, 88CPB4307, 89CPB1188, 89CPB1226, 92JAP(K)04338762 68KPS371, 73JA8427, 86CPB2018 91MIP9116894 72TL1767, 73MI 839-04, 74AJC2025, 76CJC473, 76CJC1494, 80M783, 88TL2229,93JA8851 58CPB222, 59CPB241
OS
A.3 Three ring heteroatoms
(161) (162)
XX XX
Nl,N3,N9b Nl,N4,N9b
1784.345 1784.167
[1,3,5]Triazino[2,1,6- dejquinolizine 1,4,96-Triazaphenalene
(163) (164) (165)
XX XX XX
Nl, N6, N9b Nl, m, N9b Nl, N9, N9b
1784.168 1784.365 1784.166
1,6,96-Triazaphenalene 1,8,96-Triazaphenalene 1,9,96-Triazaphenalene
1784.224
1//,5//-Pyrimido[5,6,1 -ij][l ,6]naphthyridine
1784.363
2,5,96-Triazaphenalene
(168)
1784.230
l/f,4//,7//-8-Oxa-2,3a-diazaphenalene
A.4 Four ring heteroatoms («9) XIX Nl, N2, N+6a, N9 (179) XX Nl,N3,N4,N9b
1784.280 1784.178
1H-1,2,9-Triaza-6a-azoniaphenatene 1,3,4,96-Tetraazaphenalene
(166)
(167)
XX
N2, N5, N9b 2
92DIS(B)6403 75YZ13, 77ACS(B)235, 78CPB680, 84CS170, 85CPB3034, 87H(26)2757, 87YZ344, 89CPB1188 75CPB1629, 85JOC4028, 87(26)H2757 93JIC693 74CPB2765, 75YZ13, 76ACS(B)466, 77JHC671, 78YZ623, 87H(26)2757, 89CPB1188
81CPB1193, 82KGS518, 83MI 839-03
93JIC693, 94JHC929
82KGS518
85MI839-03 77ACS(B)235, 85JA3884,92HAC19
>3
Table 3 (continued) Positions of ring heteroatoms
Ring identifier (Chem. Abstr.)
Parent system
Tricyclic system
Type
(171)
XX
N\,N3,N6,N9b
1784.139
1,3,6,96-Tetraazaphenalene
(172)
XX
Nl,N4,N7,N9b
1784.141
1,4,7,96-Tetraazaphenalene
(173) (174) (175) (176)
XX XX XX XX
N2, N5, m, N9b 01, N4, Nl, N9b si, N4, N9, N9b 01, 04, 01, N9b
1784.364 1784.142 1784.346 1784.144
2,5,8,96-Tetraazaphenalene 2H-1 -Oxa-4,7,96-triazaphenalene 2H-1 -Thia-4,9,96-triazaphenalene 2H,5H,SH-1,4,7-Trioxa-96-azaphenalene
Nl, N3, N4, N6, N9b,
1784.143
1,3,4,6,96-Pentaazaphenalene
Nl, N3, N4, Nl, N9b, Nl, N3, N5, Nl, N9b, Nl, N3, N6, Nl, N9b
1784.157 1784.181 1784.140
1,3,4,7,96-Pentaazaphenalene 1,3,5,7,96-Pentaazaphenalene 1,3,6,7,96-Pentaazaphenalene
A.5 Five ring heteroatoms (177) XX
(178) (179) (180)
XX XX XX
A.6 Six ring heteroatoms (181) XX (182)
XX
Nl,N3,N4,N6,Nl,N9b
1784.163
1,3,4,6,7,96-Hexaazaphenalene
Nl, N3, N4, N6,NS, N9b
1784.182
1,3,4,6,8,96-Hexaazaphenalene
1784.145
1,3,4,6,7,9,96-Heptaazaphenalene
A.7 Seven ring heteroatoms (183) XX Nl,N3, N4, N6,Nl, N9, N9b
References 72ACS596, 72ACS611, 72ACS624, 73ACS2095, 73ACS3259, 73ACS3264, 74CPB1424, 75CPB1629, 75ACS(B)867, 76JHC1029, 77ACS(B)239, 81 MI 839-02, 82JHC357, 84MI 83902, 85JCS(P2)153, 85JA3884, 85JOC4028, 86JHC381, 87CL675, 87JHC321, 88CPB4307, 88JHC1837, 90JHC1591, 91JHC987, 92HAC19, 93JIC693, 94JHC929 General chemistry: 68JCS(B)760, 69USP3444166, 70M1037, 79JCS(P2)143, 81CAR(89)237, 84CS170, 86JA17, 94JHC929 Applications: 68USP3397167, 69GEP(O)1914955, 74P2519, 74KPS752, 74USP3794609, 84EUP113582 93JIC693, 94JHC929 70M1037, 74P2519 92PS(72)145 76CB650, 77JEC193, 77MI 839-02, 89EGP265428, 91JOC452 72CC1070, 74JHC627, 76JHC127, 77JHC341, 78AX(B)1667, 81JHC75, 82JHC357, 83JHC1095, 84AX(C)2108, 84JA4374, 84JHC429, 85JA3884, 85JCS(P2)153, 85JHC255, 87CL675, 88JHC1837, 89MI 839-06, 92HAC19, 93JIC693, 94JHC929 73ACS2421, 93JIC693, 94JHC929 77JHC679, 93JIC693, 94JHC929 72ACS635, 73ACS359, 93JIC693, 94JHC929 74JHC627, 75MI 839-04, 81JOC1457, 85JA3884, 92HAC19, 93JIC693, 94JHC929 77JHC679, 92HAC19
General chemistry: 71ZOR972, 72ZOB419, 76JC63, 76ZOB1423, 76ZOB1653, 77CR(C)913, 77ZOB1763, 79ZAK385, 80MI 839-04, 80MI 83905, 80URP707917, 80USP4205167, 81MI 839-03, 81MI 839-04, 81MI 839-05, 81ZOB2377, 82JA5497, 82NKK662, 83MI 839-04, 83MI 839-05, 84DIS(B)197, 84JA2805, 84JAP(K)59031861, 84JAP(K)59033353, 84JPC4324, 84MI 83905, 84PJC3, 84PJC13, 85EUP137652, 85JA3884, 86MI 839-02, 86MI839-03, 86MI 839-04, 86MI839-05, 86URP1237668, 87URP1294806,
Si's OS
••
ON
(184)
XXI
(185)
XXI
Sbl, Sb3, Sb4, Sb6, Sbl, Sb9, Sb9b Sil, SB, Si4,5/6, Sil, Si9, SBb
1784.283
1,3,4,6,7,9,96-Heptastilbaphenalene
1784.154
1,3,4,6,7,9,96-Heptasilaphenalene
88USP4775696, 88EUP286478, 89JAP(K)01018907, 89MI 839-07, 89MI839-08, 89URP1490122, 90GEP(O)3908815, 90IZV113, 90JAP(K)02274761, 90URP1539654, 91MI 839-08, 91URP1685939, 92HAC19, 92M1839-06, 92URP1747448, 92URP1775402, 92USP5120821, 93JIC693, 93MI 839-04, 94JHC929 Applications: 79URP697603, 80URP712097, 80URP773139, 81URP817043, 81URP833576, 81URP887612, 84GEP(O)3231540, 84JAP(K)59041360, 84JAP(K)59045352, 85MI 839-06, 86URP902450, 86USP4619735, 89URP770027, 89USP4822825, 89USP4824869, 90MIP1038845, 91EGP296967, 91JAP(K)03202458, 92JAP(K)04239558, 92MI 839-07, 92MI 839-08, 92URP1775428, 93JAP(K)05339417, 94MI 839-06 87IC3797 58AG701, 59ZAAC(299)232, 59ZAAC(299)316, 59ZAAC(302)60
B Two ring junction atoms B.I Two ring heteroatoms
So
(186)
1784.2
3a-Azonia-9A-boraphenalene
B.2 Three ring heteroatoms (187) XXII N2, N+3a, N6a
1784.233
1
(188)
1784.366
4//,9i/-l-Oxa-6a,9a-diazaphenalene
B.3 Four ring heteroatoms (189) XXII N\,N3a,N6a,N9
1784.133
1 H,AHJH-\ ,3a,6a,9-Tetraazaphenalene
81TL1711, 81TL2217, 91T1013
(190)
1784.222
1tf,5/f-Pyrimido[ 1,2,3-(flpteridin-4-ium
81H(15)437
tf,4//-2,6a-Diaza-3a-azoniaphenalene
68TL2707, 71CCC1248
82BEP892120, 82TL2891, 83H(20)579, 83H(20)1891, 85H(23)1093, 85H(23)1167, 85H(23)2549, 88MI839-05
94JAP(K)06148845
I
i
Table 3 (continued) Tricyctic system
Positions of ring heteroaloms
Type
Ring identifier (Chem. Ahstr.)
Parent system
o References
C Three ring junction atoms C.I Three ring nitrogen atoms
(191)
1784.193
l//,4//,7//-6a,9a-Diaza-3fl-azoniaphenalene
1784.134
l//-2,3-a,5,6a,8,9a-Hexasilaphenalene
1784.175 1784.210
1 //,4//,7//-3a,6«,9«-Triaza-9/j-phosphaphenalene m,4W,7//-3a,6a,9a-Triaza-9A-boraphenalene
1784.165 1784.5
1 H,4H,TH-2,3a,6a,9a-Tetraaza-1,3-diphospha-9/>-boraphenalene 1 //,4//,7//-2,3a.6a,9a-Tetraaza-1,3-disila-9i-boraphenalene
1784.4
l//,4//,7//-2,3a,6a,9«-Tetraaza-l,3,9/>-triboraphenalene
1784.149
3a//,6a//,9a//-l,3,4,6,7,9,9A-Heptaaza-2,3a,5,6a,8,9ahexaphosphaphenalene
1784.136
1 H,4H,TH-1,3,4,6,7,9,96-Heptaaza-2,3«,5,6a,8,9flhexaboraphenalene
1784.153
l//,4//,7//-2,3«,5,6a,8,9a-Hexaaza-9A-stiba-l,3,4,6,7,9hexasilaphenalene
1784.155
Tricyclo[7.3.1.05ll]heptasilazane
1784.3
l//,4//,7i/-2,3a,5,6a,8,9a-Hexaaza-l,3,4,6,7,9,9Aheptaboraphenalene
78USP4085106, 80JA6363, 80JA6364, 80JA6365, 80TL3635, 81TL4365, 87AG1216, 87CC886, 87MI 839-09, 87T1903, 88MI 839-06, 89HCA1125, 89POL2333, 90DIS(B)1260, 91TL7755, 92CC507. 93AG640
C.2 Six ring silicon atoms
(192)
H
72ZAAC(390)157, 88JOM(341)109
.5
Si.
• Si 6a
H
D Four ring junction atoms DA Four ring heteroatoms (193) XXIII N3a, N6a, N9a, P9b (194) XXIII Nia, N6a, N9a, B9b D.2 Seven ring heteroatoms (195) XXIII P\,N2,Pi,Nia,Nba,N9a,B9b (196) XXIII Si\,N2, SB, N3a, N6a, N9a, Bf)b (197) XXIII B\,N2,B3,N3a,Nba,N9a, B9b D.3 Thirteen ring heteroatoms XXIV (198) N\,P2, N3, P3a, NA, Pi, N6, P6a, NT, Pi, N9, P9a, N9b XXIV (199) N\,B2,N3,B3a,N4,B5, N6, B6a, NT, B8, N9, B9a, N9b XXIII (200) Sil,N2,SB,Nia,Si4,N5, Si6, Nba, SiT, NS, Si9, N9a, Sb9b XXIII (201) Sil, N2, SB, Nia, S/4, A"5, Si6, Nba, SiT, N$, Si9, N9a, S»b (202) XXIII B\,N2,Bl,N3a,B4, N5, B6, Nba, BT, N8, B9, N9a, B9b
76USP3996276, 77USP4038312, 78TL4331, 81JA2054 80JA5790, 81JCS(D)511, 81JA6133, 89JCS(P1)2O79, 91IC4524
t
74CB3806 70CB2234, 75CB3109
a.
65IC886
O\
71JCS(D)357, 72JCS(D)623, 73CJC520 67CJC2059, 84AG301 72MI 839-04 71 MI 839-02, 79JAP(K)54093100, 84MI 839-06 67CJC2059
Three Heterocyclic Rings Fused (6:6:6) 8.39.6.2.2
1107
Formation of the terminal ring
This approach involves the construction of a third ring on a suitably substituted fused bicyclic substrate: (2)-(4), (7) <71JOC2192, 92JHC25), (11) <90ZC98>, (16) <92MI 839-01), (18), (22), (23) (89CB1935,90CB1415), (29), (33) <78CB97i>, (37), (41), (42), (47), (50), (59), (60), and (61).
8.39.6.2.3
Formation of two rings
Intramolecular and intermolecular tandem cyclizations of a suitably substituted six-membered heterocycle, which result in a simultaneous formation of two rings fused to the substrate ring, have been reported for (5) <89MlP8905809>, (10), (13), (14), (19), (21), (31) <73CPB770>, (33) <93HCA43i>, (44), and (51) <85JMC1228>.
8.39.6.2.4
Formation of three rings
Derivatives of systems (64), (72), and (76) have been synthesized by one-pot cyclization of acyclic substrates.
8.39.6.2.5
Ring transformation
The synthesis of derivatives of (23) <90CBl4l5>, (36), (48), and (57) involves a one-step ring transformation of a heterocyclic substrate.
8.39.6.3 8.39.6.3.1
Hetero Analogues of Phenanthrene (Table 2) Formation of the central ring
The vast majority of systems in this class has been constructed by cyclization of an unfused heterobiaryl or a substrate composed of two six-membered heterocycles and linked by a two-atom bridge: (78)-(82), (84)-(87), (90M92), (97), (102), (108), (109), (111), (112), (116), (118), (120), (126), (128), (140), (141), and (143). An intermolecular condensation of two appropriately functionalized six-membered heterocyclic substrates provides a facile synthetic entry to (88) <83M1197,86H(24)3075>, (100), (101) <92MI 839-02), (110), (114) (91TL4473, 93JOC6976), (115), (117), (121), (124), (139) <85JOC29io>, (145), (146), (148), and (149).
8.39.6.3.2
Formation of the terminal ring
The cyclization of a substituted fused bicyclic substrate has been used in the preparation of derivatives of (77), (83), (88) <86JHC509>, (93M95), (104)~(107), (114) <90Mi 839-oi>, (122), (123), (125), (127), (129)-(131), (134), (135), (137), and (138).
8.39.6.3.3
Formation of two rings
This approach involves mainly cyclization of substituents at a six-membered heterocycle which becomes the central ring in the product. Derivatives of the following systems have been prepared: (89), (96), (99), (119), (132), (133), (136), (144), (147), and (150).
8.39.6.3.4
Formation of three rings
One-pot cyclization of acyclic substrates provides a facile synthetic entry to substituted derivatives of(103)and(113).
1108
Three Heterocyclic Rings Fused
8.39.6.3.5
(6:6:6)
Ring transformation
Substituted derivatives of (98) and (101) <87T3955, 9UA1756, 91MI 839-02> have been obtained by ring transformations of heterocyclic substrates.
8.39.6.4
Hetero Analogues of Phenalene (Table 3)
8.39.6.4.1
Formation of one ring
Intramolecular cyclizations of ^en-substituted fused bicyclic substrates (6:6) and intermolecular cyclizations that involve the peri positions of unsubstituted systems (6:6) have been applied to the synthesis of the following parent compounds or derivatives: (152) <69CC24,91CC1261), (156)-(158), (160)-(162), (165) <74CPB2765>, (166), (168), (170), (183) <82JA5497, 84JA2805), (186), (187), (190), (191) <92CC507>, and (195)-(197).
8.39.6.4.2
Formation of two rings
A double cyclization of a substituted six-membered heterocyclic substrate provides a synthetic entry to derivatives of (152) <94T3139>, (153), (159), (165) <76ACS(B)466,77JHC67l>, (169), (171), (175), (177)-(182), and (192).
8.39.6.4.3
Formation of three rings
One-pot cyclization of acyclic substrates provides a facile synthetic entry to derivatives of (152) <75CC565,92SC3115), (172), (174), (176), (183) <86Mi 839-05>, (185), (189), and (198)-(201).
8.39.6.4.4
Ring transformation
The synthesis of derivatives of parent compounds (152) <80TLi093> and (163) involves a one-step ring transformation of a heterocyclic substrate. Derivatives of (153)-(155), (191) (80JA6365,80TL3635, 81TL4365), (193), and (194) have been obtained by reactions of macrocyclic compounds.
8.39.7
APPLICATIONS
Diverse applications have been found and many potential uses have been suggested for the parent compounds or derivatives of the three classes of fused heterocyclic systems (6:6:6). A detailed list of reports that deal with these topics can be found in Tables 1-3. When a particular system contains many references the publications describing mostly applications or potential applications are collected separately from the general chemistry references. The applications are also mentioned in the vast majority of the general references. The parent compounds or derivatives listed in Tables 1-3 are antitumor agents, (37), (51), (53), and (144); antibacterial and antiparasitic agents, (22), (61), and (148); antiallergy, antiinflammatory, and analgesic agents, (6), (8), (17), (25), (27), (30), (32), and (36); diuretics, (109); antihypertensives, (111) and (116); disinfectants and antiseptics, (117); inhibitors of phosphodiesterase, (30), (34), and (36); a-1-adrenergic and a-2-adrenergic receptor antagonists, (77); folate enzyme inhibitors, (129) and (130); fluorescent labels for DNA, (25) and (101); herbicides, (139); stabilizers for dyes and polymers, (53) and (62); and fireproofing agents for cotton fibers, (193). Compound (155) and its derivatives have been used in the synthesis of natural products which are derivatives of (152) <75CC565,76TL2925).
Copyright © 1996 Elsevier Ltd.
Comprehensive Heterocyclic Chemistry II
SURVEY OF SYSTEMS
1091
8.39.2
THEORETICAL METHODS
1092
8.39.3
EXPERIMENTAL STRUCTURAL METHODS
1092
8.39.3.1 X-ray Diffraction 8.39.3.2 Molecular Spectra 8.39.3.2.1 NMR spectroscopy 8.39.3.2.2 Electronic absorption and fluorescence spectroscopy 8.39.3.2.3 ESR spectroscopy
1092 1092 1092 1093 1093
8.39.4
THERMODYNAMIC ASPECTS
1093
8.39.5
REACTIVITY
1093
8.39.6
SYNTHESIS
1093
8.39.6.1 General Remarks 8.39.6.2 Hetero Analogues of Anthracene (Table 1) 8.39.6.2.1 Formation of the central ring 8.39.6.2.2 Formation of the terminal ring 8.39.6.2.3 Formation of two rings 8.39.6.2.4 Formation of three rings 8.39.6.2.5 Ring transformation 8.39.6.3 Hetero Analogues of Phenanthrene (Table 2) 8.39.6.3.1 Formation of the central ring 8.39.6.3.2 Formation of the terminal ring 8.39.6.3.3 Formation of two rings 8.39.6.3.4 Formation of three rings 8.39.6.3.5 Ring transformation 8.39.6.4 Hetero Analogues of Phenalene (Table 3) 8.39.6.4.1 Formation of one ring 8.39.6.4.2 Formation of two rings 8.39.6.4.3 Formation of three rings 8.39.6.4.4 Ring transformation 8.39.7
8.39.1
1093 1093 1093 1107 1107 1107 1107 1107 1107 1107 1107 1107 1108 1108 1108 1108 1108 1108
APPLICATIONS
1108
SURVEY OF SYSTEMS
This is the first attempt to review all fused heterocyclic systems (6:6:6) containing at least one ring junction heteroatom. There are three classes of these systems, namely heterocyclic analogues of anthracene, phenanthrene, and phenalene, which are surveyed in Tables 1-3 respectively. Please 1091
1092
Three Heterocyclic Rings Fused
(6:6:6)
consult Section 8.38.1 of the preceding chapter regarding the organization of the Tables and additional information concerning the tabulated material. The survey is an integral part of the sections that follow; brevity was necessary in order to review the large number of systems (6:6:6).
8.39.2
THEORETICAL METHODS
INDO/S CI computations have been conducted to predict sites of protonation and explain the absorption and emission spectra of a derivative of (15) <85MI 839-01, 86ZN(A)66l>. Semiempirical MNDO computations predict little charge delocalization in the pyrimidinediium system (38) and a similar dication derived from (39) <86CJC1711>. Htickel-McLachlan calculations have been used to explain the ability of a tetrazine (53) to form charge-transfer complexes and to help interpret PE and ESR spectra <87HCA1661, 94HCA86). The AMI Hamiltonian more accurately predicts a stable conformation of (72) than the MNDO method <89CB1989>. The electronic structure of azaphenalenes (152), (170)-(172), and (181)-(183) has been studied extensively by using HAM/3 semiempirical, STO-3G ab initio and other approximations <69JCS(A)1754, 80JA6068, 84JA2805, 84CCA991, 85JA3884, 86JA17,94JHC929). The HAM/3 computations predict the greatest HOMO and total electron density of (152) at positions 1, 3, 4, 6, 7, and 9 <85JA3884>. Neither the parent systems (40), (70), (73H75) (Table 1), (142), (151) (Table 2), (181), (198) (Table 3) nor their derivatives are known. These systems, however, have generated a considerable theoretical interest and have been examined by theoretical calculations. Numerous predictions have been made for presently unknown compounds. The features of interest are the aromaticity of boron-nitrogen heterocycles (40), (70), (75), (142), (151), (202) <67CJC2059,71CCC1248,84RRC613) and nitrogen heterocycles (164), (167), (173) <93J1C693, 94JHC929) and the potential conductivity or superconductivity of systems (73), (74), (184) (87IC3797,92JPC5184,93JPC4974).
8.39.3 EXPERIMENTAL STRUCTURAL METHODS 8.39.3.1
X-ray Diffraction
The conjugated systems (53) <86HCA1521>, (101) <91MI 839-01 >, (114) <91TL4473>, (171) <84MI 83907>, and (183) <82JA5497> are virtually planar in the solid state. The cation (84) is only approximately planar <71CC426), and a heterocyclic skeleton of the 2,2,3a,5,5,6a,8,8,9a-nonachloro substituted system (198) is not planar at all <72JCS(D)623, 73CJC520>. The molecular structures of noncyclically conjugated derivatives of (31) <90JOC467>, (39) <85JCS(P2)433>, (54) <9UA59io, 92JA6017), (139) (85CC311, 88TL1573), (144) <83JA2350>, and (187) <82TL2891, 83H(20)579, 83H(20)1891> have been solved. X-ray diffraction analysis has also been used to study the conformation of perhydro derivatives of (55) <78JCS(P2)818>, (67) <80JCS(P2)1733>, (69) <85AX(C)122, 87AX(C)170>, (152) <84JOC2217, 92TL1281), (191) <89HCA1125>, (192) <88JOM(34i)i09>, and (199) <84AG30i> in crystal.
8.39.3.2 8.39.3.2.1
Molecular Spectra NMR spectroscopy
The fully conjugated systems (6:6:6) of Table 2 are analogues of biaryls with a two-atom bridge linking positions
Three Heterocyclic Rings Fused (6:6:6) 8.39.3.2.2
1093
Electronic absorption and fluorescence spectroscopy
Detailed spectroscopic and photophysical studies of the following systems or derivatives have been reported: (15) <83JOC2476, 87JCS(F2)1475,90ZN(A)999>, (25) <83CC183, 83JOC2481), (39) <82JPC2049>, (101) <89JCS(P2)1691>, (152) <86JA17>, and (183) <84JPC4324>.
8.39.3.2.3
ESR spectroscopy
Systems (53) <94HCA86>, (62) <91CB2781>, (152) <73JA6702>, and a 6,7-dihydroderivative of (139), diquat, <93JPC7800> are easily oxidized to stable cation radicals. The ESR spectrum of the unstable anion radical resulting from reduction of (152) has been obtained <73JA6702>.
8.39.4
THERMODYNAMIC ASPECTS
The concept of topological resonance energy was introduced to provide a relative measure of aromaticity <77JA1692>. In a newer approach, the absolute hardness, or HOMO-LUMO gap, as the measure of aromaticity is denned to be in the ionization potential of the species minus its electron affinity. The parameters of the absolute hardness and a related relative hardness for (152) are consistent with the high reactivity of this compound <89JA737l).
8.39.5
REACTIVITY
The reactions of heterocyclic compounds composed of fused systems (6:6:6), such as electrophilic and nucleophilic attack at a ring or a substituent and partial reduction, are often highly selective. Unfortunately, there are few unifying features among the reactivities of the three different classes of systems, and a detailed treatment of the reactivity is beyond the scope of this concise chapter. All references to the chemistry of a particular parent compound and derivatives are given in Tables 1-3.
8.39.6
SYNTHESIS
8.39.6.1
General Remarks
All synthesis references are printed in boldface in Tables 1-3. The many synthetic methods reported have been classified below into several general approaches according to a one-pot construction of one, two, and three fused rings, and ring transformation of a fused ring system substrate. The references listed in Tables 1-3 are not duplicated here if a particular ring system (6:6:6) has been constructed using one approach only. It should be noted that the particular approach according to this classification may involve different types of chemistry.
8.39.6.2 8.39.6.2.1
Hetero Analogues of Anthracene (Table 1) Formation of the central ring
The most widely used method involves an intermolecular cyclization of two one-ring components substituted with appropriate functional groups. This approach provides an efficient synthetic entry to (1), (6), (7) <78CB2297, 86ZC290, 91LA1215), (8), (9), (11) <86CB1070>, (12), (15) <81TL449, 83JHC575, 83JOC2476), (16) <72CB743, 86ZC290>, (20), (24), (25), (28), (30), (32), (34), (35), (39), (49), (51)-(56), (58), (62), (63), (65)-(68), and (71). An intramolecular cyclization of a substrate composed of two six-membered heterocycles and bridged by a one-atom unit has been applied to the synthesis of derivatives of (5), (15) <75JHC477,85JHC173,94JHC81), (17), (26), (27), (38), (43), (45), (46), and (69).
Table 1 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (2508) for the tricyclic skeleton. (References in bold refer to synthesis.) 10
\ / 7
l O a ^
6
T
10 11 .10a
1
;CTD
) \
-^ 3 4
7
Type i
io
r
11 /~-
5a " - ^ 4 a 5 4
6
4
6
Type ffl
Type II 1
12
6
J3 ' 5~\ / 4
10 ,,
12
1
6
4
7
5
4
Type VI
Type VII
13
6
5
4
Type IX Positions of ring heteroatoms
A One ring junction nitrogen atom A.I Two ring heteroatoms (1) II M.JV6 (2) II OX, N6
(3) A.2 Three ring (4) (5) (6)
III
02, MO
heteroatoms II NX,N3,N6 I NX,N5,NX0 III M , N5, MO
Ring identifier (Chem. Abstr.)
Type VIII
14 '
(8)
III
N2, N5, MO
2508.693
(9) (10)
II I II III I I
JV2, N6, NX 1
2508.674 2508.753 2508.149 2508.715 2508.754 2508.752
SX,N5, 08
6
4
I
Type XI Parent system
li/-Dipyrido[l,2-a:4',3'-rf|pyrimidine
Nl,N6, Ml
(12) (13) (14)
TypeX
2//-Pyrimido[4,5-6]quinolizine 2H-Pyrimido[l,2-g]naphthyridine l//-Dipyrido[l,2-a: 3',2'-rflpyrimidine 2//-Dipyrido[l ,2-a: 2',3'-
II
(H)
4
2//-Pyrido[l ,2-^]-l,6-naphthyridine 2i/,5//-Pyrano[2,3-6]quinolizine l//,3H-Pyrano[4,3-/>]quinolizine
(7)
NX, N5, 0 8 Ol,JV6,jVll O2, NS, MO Ol, W5, O8
7^ ^ 5 6
B
2508.86 2508.99 2508.855
2508.88 2508.759 2508.675 2508.144
5
7
N'
Type
5
Type IV
6
7
TypeV
Tricyclic system
5a
v. 2
9 R
5
N'
2//-Dipyrido[l,2-o: 3,4'-
References
57MI 839-01, 81CJC106 72LA(761)2S, 80M93, 83M48S 94H(38)81
70YZ127 89MIP890S809, 90JHC189 86ZC290 71JHC637, 71JOC2192, 78CB2297, 86ZC290, 91LA1215, 92JHC25 87JCS(P1)9O9, 87JHC1473, 87MI839-01,87MI839-02, 87T1157, 88MI 839-01, 93OMS(28)18 86ZC290 89LA1241 86CB1070, 90ZC98, 93MIP9323398 87JHC1557 89LA1241 89LA1241
A3 Four ring heteroatoms II (15)
N1,N3,N+6,NU
2508.146
Pyrido[l ,2-a]pyrimido[4,5-(flpyrimidin-6-ium
N\,N4,N5,N\0 N\,N5,N\0,Nll N\,04,NS,NIO Nl,N6,01,N\l N1,N5,NIO,SU N\,N6,S9,NU SI, N5, Si, Nil
2508.215 2508.631 2508.814 2508.698 2508.377 2508.145 2508.657
1 #-Pyrido[2,1 -A]pteridine 2//-Pyrido[2,3-t?]pyrimido[l,2-a]pyrimidine lff,77/-Pyrido[l',2': l,2]pyrimido[4,5-A][l,4]oxazine Pyrido[2',3': 4,5]pyrimido[l,2-6][l,2]oxazine 2H,6ff-Pyrido[3,2-e]pyrimido[2,1 -b][l ,3]thiazine Pyrido[2',3':4,5]pyrimido[2,l-c][l,4]thiazine 4',3': 4,5]pyrimido[2,1-6][1,3]thiazine
A.4 Five ring heteroatoms II (23) (24) II (25) II
N\,N2,N5,N6,NU N\,Ni,N5,N6,NU Nl,N3, N6, M, Nli
2508.736 2508.524 2508.406
2//-Pyridazino[3,4-e]pyrido[l ,2-b][ 1,2,4]triazine 2i/-Pyrido[l ,2-A]pyrimido[4,5-e][l ,2,4]triazine 2i/-Dipyrimido[l,6-a:4',5'-rf|pyrimidine
(26) (27) (28) (29) (30) (31)
N\, JV3, N6, N9, Nil N\,N4,N5,N6,N\0 N\,N3,N6,M,OU Nl, N3, N5, N\0, SU Nl, N3, S5, N6, Nil Nl,N3,N6,S9,Nll
2508.860 2508.216 2508.535 2508.625 2508.299 2508.147
2//-Pyrazino[l,2-a]pyrimido[4,5-rf)pyfiniidine 1 //-Pyrimido[2,1 -6]pteridine 2//,7//-Dipyrimido[6,l-A: 5',4'-e][l,3]oxazine 2i/,6W-Pyrido[3',2': 5,6][l,3]thiazino-[3,2-a]-l,3,5-triazine Pyrido[l ,2-i]pyrimido[4,5-e][l ,2,4]thiadiazine Pyrimido[4',5': 4,5]pyrimido[2,l-c][l,4]thiazine
(16) (17) (18) (19) (20) (21) (22)
(32) (33)
III I III II I II I
I III II I II II
11 III
A.5 Six ring hiHeroatoms (34) II (35) II (36) IV (37) IV
Nl,N3, N6, N10, S\\ Nl, N4, JV5, S6, AflO
2508.448 2508.450
2,l-6 : 5',4'-e][l,3]thiazine l//,7tf-[l,3]Triazino[2,3-%teridine
N\,N3,S5,N6,M,N\\ N\,m,S5,N6,N9,NU N\, S3, N5, N6, Ni, Nil P\,O2,N4,N5,N6,N\\
2508.301 2508.300 2508.148 2508.801
Pyridazino[l,6-6]pyrimido[4,5-e][l,2,4]thiadiazine Pyrazino[l,2-6]pyrimido[4,5-e][l,2,4]thiadiazine Pyrimido[4',5': 4,5]pyrimido[l ,2-d\[\ ,3,4]thiadiazine l//,3i/-Pyrido[2',3': 4,5]pyrimido[l ,2-c][l,3,5,2]oxadiazaphosphorine
2508.341
Dipyrido[l,2-c: 2',l'-:/]pyrimidinediium
B Two ring junction heteroatoms B.I Two ring heteroatoms (38) V JV+5, N+l
74USP3836533, 75JHC477, 81TL449, 83JHC575, 83JOC2476, 85JHC173, 85MI 839-01, 86JPC5820, 86ZN(A)661, 87JCS(F2)1475, 88JHC959, 90ZN(A)999, 94JHC81 72CB743, 86ZC290, 92MI839-01 85JHC193, 86MIP8606375, 93CCC1130 91IJC(B)839 87JHC175,91JHC2071 73JIC358 73CPB770 85M1 839-02
89CB1935, 90CB1415, 91CB1477, 92JAP(K)04015644 79DIS(B)5678 74CPB2086, 83CC183, 83JOC2481, 86JPC5820, 87ZN(A)485, 90ZN(A)999 94JHC81 86MIP8606375, 93CCC1130 80KGS992 85FES65 69GEP(O)1809013 66MI 839-01, 67CPB1178, 67CPB1183, 67JAP05000302, 67JAP42005665, 67JAP42009834, 67JAP42020070, 67JAP42025916, 68CPB1773, 68JAP43005397, 68JAP43010631, 68JAP43019553, 68JAP43019958, 68JAP43019959, 69JAP44030276, 72YZ27, 73CPB770, 74MI 839-01, 75MI839-01, 90JOC467 76IJC(B)759 77ACS(B)167, 78CB971, 93HCA431 69GEP(O)1809013 69GEP(O)1809013 70CPB1201, 70GEP(O)1954275, 72JAP47050120 89MI 839-01
69JC250, 69MI 839-01, 70T3369, 73JOC1098, 74OMR(6)253, 76JCS(P2)418, 86CJC1711, 88SM371
re
3
3
Table 1 (continued) Trkyclic system
Type
(39)
VI
Positions of ring heteroatoms N5,NU
Ring identifier (Chem. Abstr.) 2508.342
(40)
2508.2
B.2 Three ring heteroatoms (41) VII N\,N6tNU
Dipyrido[l,2-a: l',2'-
Borino[l,2-rf]pyrido[l,2-a][l,4]azaborine
2508.87 2508.66 2508.350
Pyridazino[l,2-a]pyrido[2,3-rf|pyridazine Pyridazino[l,2-a]pyrido[3,4-rf]pyridazine 2//-Dipyrido[l,2-o:2',r-rf|[l,3,5] triazin-5-ium
N 5, N 7, Sel2
2508.849 2508.366 2508.474
11#-Pyrido[l',2':3,4]pyrimido[l,6-A][1,2] thiazine 2tf-Dipyrido[2,l-fc: )',2'-e][l,3,5] thiadiazinediium 2ff-Dipyrido[2,l-A: r,2'-e][l,3,5] selenadiazinediium
Nl,N4,N6, Nil Nl,N5,Nl,Nll NI,N6,N7,N12 N2, Nl, N6, Nl 1 N2, N5, NS, Nl 1
2508.205 2508.799 2508.343 2508.67 2508.601
Pyrazino[2,3-rf]pyridazino[l,2-a] pyridazine Pyrazino[l,2-a: 4,5-a']dipyrimidine Pyrazino[l,2-i: 4,5-A']dipyrimidine Dipyridazino[l,2-o:4',5'-
(42)
VII
7V2, JV6, JV11
(43)
V
r5,iV7,iVI2
(44) (45) (46)
IX V V
SI,NIO,N12
B.3 Four ring heteroatoms (47) VII (48) VI (49) VIII (50) VII VI (51)
Parent system
iV+5, AT+7, S I 2 +
+
(52) (53)
VIII VI
N2, N6, M, N12 N5,N6,Nll,Nl2
2508.522 2508.357
Dipyrido[l,2-ft:l',2'-e][l,2,4,5]tetrazine
(54) (55)
VI VIII
02, JV+5, 08, W+i; 05, JV6, O i l , JV12
2508.779 2508.365
Pyrazino[2,l-c:5,4-c']bis[l,4]oxazinediium 1#,7//-Dipyrido[l ,2-b: l',2'-e][l ,4,2,5] dioxadiazine
(56)
VI
52, JV5, S8, Nl I
2508.510
l#,6#-Pyrazino[2,l-c:5,4-c']bis[l,4]thiazine
2508.784
l//,7//-Bisphosphorino[l,2-i:r,2'-e][l,4,2,5]dithiadiphosphorine
References
67EGP55860, 70G421, 70JCS(D)482, 72CCC4060, 72TL1437, 73CCC1940, 73CCC1957, 74CPB157, 78JCR(S)224, 81 MI 83901, 82JPC2049, 84MI 839-01, 85JCS(P2)433, 85JOC2910, 86CJC1711 71CCC1248
70AQ561, 73JCS(P1)26 70AQ561 69MI 839-01, 73JOC1098, 74OMR(6)253, 82SM31, 86H(24)1893, 86JPC5820, 86S402, 86USP4594413, 88ZOB1685, 89ZOR1354 93SL551 67NAT381,68T2697 78ZN(B)118 70AQ561 90JCR(S)304 71JCS(C)526, 71RRC1107, 73MI 839-01 68JCS(C)2857, 75JHC95 84DIS(B)202, 85JMC1228, 89USP4871736, 93MIP9323075 80MI 839-01, 81RRC879, 94JHC1707 67CB2467, 73JOC4259, 75JPR561, 77ZOR948, 86HCA1521, 86HCA1531, 87HCA1661, 88JAP(K)63229455, 90HCA81, 94HCA86 89USP4871736, 91JA5910, 92JA6017 72LA(759)183, 78JCS(P2)818, 82M339, 92OS(70)265 79KGS1211, 87MI839-03
11
(57)
90HAC37
*. • • ^
c^ k^
1
B.4 Five ring heteroatoms IX (58) (59) VIII (60) VIII
N2,N5,m,N+Vj,Nl2 Nl, O4, N5, N+6, Nil Nl,SA,Ni, N+6,Nl2
2508.662 2508.692 2508.626
li/-Dipyrimido[l ,6-a:6', 1 '-d\[ 1,3,5]triazin-10-ium l#,8tf-Pyrido[l',2':l,6][l,2,4]triazino[3,4-6][l,3,4]oxadiazin-6-ium l//,8frPyrido[l',2':l,6][l,2,4]triazino[3,4-6][l,3,4]thiadiazin-6-ium
B.5 Six ring heteroatoms (61) V (62) VI (63) VIII (64) VIII (65) VI
Nl,N3,N5,NT, N9, Nil NI.N5, N6, NT, Nl\, N12 N2,N5,N6,M,Nll,Nl2 N2,O5,N6,M,Oll,Nl2 O2,NS,N6,OS,Nll,Nl2
2508.457 2508.443 2508.442 2508.425 2508.358
2i/,6i/-Pyrimido[l ,6-a:3,4-a']bis[l ,3,5]triazine Dipyrimido[l,2-A:l',2'-e][l,2,4,5]tetrazine Dipyrimido[l ,6-b: l',6'-e][l ,2,4,5]tetrazine l//,7//-Dipyrimido[l,6-6:l',6'-e][l,4,2,5]dioxadiazine l//,6.ff-Bis[l,4]oxazino[4,3-fc4',3'-e][l,2,4,5]tetrazine
2508.364
Bis[l,2,4]triazino[4,3-A:4',3'-e][l,2,4,5]tetrazine
C. Four ring junction heteroatoms C.I Four ring heteroatoms (67) X NS, NT, N12, N14
2508.370
6H, 13//-Dipyridazino[l ,2-a: 1 ',2'-a\l ,2,4,5]tetrazine
C.2 Six ring heteroatoms (68) X (69) X (70) XI
2508.596 2508.612 2508.4
l//,6H,8#,13//-Bis[l,3,4]oxadiazino[3,4-a:3',4'-(/][l,2,4,5]tetrazine 6ff,13//-Dipyridazino[l,2-a:l',2'-rf|[l,2,4,5,3,6]tetrazadiphosphorine 6i7,13/f-Bis[l,2]azaborino[l,2-a:2',l'-rf|[l,3,5]triazatribonne
2508.700
6//,13//-Bis[l,2,4,5]tetrazino[l,2-a:l\2'-d][l,2,4,5]tetrazine
85CI(L)797, 86H(24)1893, 86USP4594413 86JCR(S)460 84S697 77CR(C)25, 80EJM341 76RTC282, 89EGP272303, 91CB2781 76M1241, 90ZC133 75CB3387 65JA393
B.6 Eight ring nitrogen atoms (66)
VI
ATI, JV2, N5, N6, NT, NS, NU.N12
O2, JV5, NT, O9, N12, JV14 NS, P6, NT, ATI 2, P13, Afl4 NS, B6,NT,B12,N13,B14
C.3 Eight ring heteroatoms X N2, m, NS, NT, N9, NIO, (71) N12,N14 • (72) X 02, O3, NS, NT, O9, 010, N12,N14 C.4 Fourteen ring heteroatoms Ol,N2, N3, O4, N5, 06, (73) NT, O$,N9, NIO, Oil, N12, 0 1 3 , JV14 (74) SI, Ar2, AG, S4, NS, S6, NT, S8.A/9, AT10, S l l , AT12, S13, ATI4 ATI, B2, AR, B4, NS, B6, (75) XI
67CB2585, 87S1134
63JOC1144, 72JA3138, 74JA576, 74JCS(P2)948, TO1 76JA5748, 78LA1505, 79CB853, 80JCS(P2)91, ?? 80JCS(P2)1733, 87MI 839-04 g
84ZOR510 85AX(C)122, 87AX(C)170, 89PS(41)235 71CCC1248
60LA(635)73, 79JCS(P2)1133, 89CB1989
2508.371
l//,4//,6//,8H,ll//,13//-[l,2,4,5]Tetrazino[l,2-rf:4,5rf|bis[l,2,4,5]dioxadiazine
2508.820
Bis[l,4,2,3,5,6]dioxatetrazino[2,3-A:2',3'-e][l,4,2,3,5,6]dioxatetrazine
92JPC5184
2508.835
Bis[l,4,2,3,5,6]dithiatetrazino[2,3-ft:[l,4,2,3,5,6]dithiatetrazine
93JPC4974
2508.5
6i/,13//-Bis[l,3,5,2,4,6]triazatriborino[l,2-a:2',l'-rf|[l,3,5,2,4,6]triazatriborine
84RRC613
NT,B8,N9,BlO,Nll, B12,N13,B14 9 10 1 O 9a O 1Oa O H Si Si' S i ' "Si' (76) O 6
,Si, 5 5aa
O O 5
, 4a
2508.372
O 4
H
l,4,5,6,9,10-Hexaoxa-2,3,4a,5a,7,8a,9fl,10a-octasilaanthracene
I
88CB815
63MI 839-01
ON
Table 2 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (2404) for the tricyclic skeleton. (References in bold refer to synthesis.)
o oo
Type XII
Type XIII
Type XIV
8
Type XVIII
Type XVII Tricyclic system
Type
Positions of ring heteroatoms
A One ring junction nitrogen atom A.I Two ring heteroatoms (77) XIII JV1, Nl +
Ring identifier (Chem. Abstr.)
Parent system
2404.656
l//-Pyrido[l,2-A]-l,7-naphthyridine
(78)
XIV
N\,N U
2404.328
Pyrido[l,2-a][l,8]naphthyridin-ll-ium
(79) (80) (81) (82)
XIII XIV XIV XIII
N2,N7 N2, Nl 1 N3, N\ 1 N4,N7
2404.233 2404.692 2404.290 2404.234
1 tf-Pyrido[2,1 -a][2,7]naphthyridine 2//-Pyrido[l ,2-a][l ,7]naphthyridine 2//-Pyrido[l,2-a][l,6]naphthyridine l//-Pyrido[2,l-/][l,6]naphthyridine
(83)
XIII
04, Nl
2404.235
Nl, N2, N*l Nl,N2,Nll Nl, JV3, A'l 1 Nl, N5, A'l 1 Nl, N6, Nl 1
2404.274 2404.687 2404.532 2404.827 2404.330
Pyridazino[3,4-fl]quinolizin-7-ium 2//-Pyridazino[4,3-c]quinoIizine 2//-Pyrimido[5,4-6']quinolizine 2i7-Dipyrido[l ,2-a: 3',2'-e]pyrazine 2i/-Dipyrido[l,2-a: 3',2'-e]pyrimidine
Nl, N7,NU
2404.329
2//-Pyrimido[l ,2-a][l ,8]naphthyridine
2404.849
2i/-Pyrazino[l,2-a][l,8]naphthyridine
A.2 Three ring (84) (85) (86) (87)
heteroaloms XIII XIV XIV XIV XIV
(88) (89) (90)
XIV XIV
NS Nil
I? s
7
l//,6//-Pyrano[3,2-a]quinolizine
References
85EUP154142, 87EUP216247, 87USP4690928, 87USP4710504, 88JMC641 78H(9)1717, B-79MI 839-01, 80CPB220, 80FES1052, 81CPB2526, 84MI 839-02, 89UKZ839, 92S798, 93T2691 67ACSS80 86UKZ506 71USP3SS7100, 86MI 839-01, 86UKZ506 67ACS580, 67NAT381, 68AX(A)252, 70CPB124, 72MI 839-01, 81CJC106, 94T9909 72LA(761)25, 83M349
71CC426, 73AJC389 86MI 839-01 80CL817 91S982, 92JHC529 83M1197, 85EJM61, 86H(24)3075, 86JHC509, 87MIP554364 66G1443, 67G1262, 67G1274, 69G677, 71G129, 71JCS(C)2985, 72G2S3, 77JCS(P1)789, 90JHC881 92S798, 93H(36)1337
(91) (92) (93) (94) (95) (96) (97) (98) (99)
XIV XIV XIV XIV XV XIV XIV XIV XIV
2404.738 2404.844 2404.359 2404.639 2404.482 2404.850 2404.764 2404.832 2404.851
2//-Pyrimido[4,5-c]quinolizine 2//-Dipyrido[l,2-a: 3',4'-ejpyrazine 2//-Pyrimido[l ,2-a][l ,6]naphthyridine 2/f-Dipyrido[l,2-a: 2',3'-e]pyrazine 1 i/-Pyrimido[ 1,2-a][ 1,5]naphthyridine [l,4]Oxazino[4,3-«][l,8]naphthyridine Dipyrido[2,3-6: l',2'-rf)[l,4]oxazine 27/,5i/-Pyrano[3',2': 5,6]pyrido[t,2-
2404.718 2404.714
2//-Pyrido[2', 1': 2,3]pyrimido[4,5-c]pyridazine 2i/-Pyrido[2,1 -%teridine
Nl,S6,NT,Nll
2404.533 2404.275 2404.246 2404.689 2404.690 2404.691 2404.471 2404.564 2404.608 2404.484 2404.678 2404.553 2404.769 2404.717 2404.485 2404.716 2404.486 2404.751 2404.887 2404.546
2//-Pyrido[l,2-a]pyrimido[5,4-c]pyrimidine l//-Pyrido[l,2-a: 3,4-A']dipyrazine Pyrido[3,2-rf]pyrimido[l,2-/>]pyridazin-5-ium 2//-Pyrido[4,3-rf|pyrimido[l,2-/i]pyridazine 2//-Pyrido[3,4-rf|pyrimido[l,2-A]pyridazine 2i/-Pyrido[2,3-rf]pyrimido[1.2-A]pyridazine 2//-Pyrido[3,2-e]pyrimido[l,2-e]pyrimidine 2//-Pyrido[4,3-£]pyrimido[l,2-c]pyrimidine 2//-Pyrido[3',2': 5,6]pyrazino[l,2-a]pyrimidine 2//-Pyrazino[l,2-a]pyrido[3,2-e]pyrazine 2//-Pyrido[3,2-e]pyrimido[l,2-a]pyrimidine 1//-Pyrido[l ,6-b: 3,2-c']dipyridazine l//-Pyrido[l,2-e]pyrimido[5,4-e]pyrimidine 2//-Pyrido[4',3': 5,6]pyrazino[l,2-a]pyrimidine 2//-Pyrazino[l,2-a]pyrido[4,3-e]pyrazine 2//-Pyrido[3',4': 5,6]pyrazino[l,2-a]pyrimidine lff-Pyrazino[l,2-a]pyrido[2,3-e]pyrazine 2//,8//-Pyrazino[2,l-A]pyrido[2,3-rfl[l,3]oxazine Pyridazino[4',5': 5,6]pyrido[2,l-c][l,4]oxazine 2i/,8//-Pyrido[2,3-rf|pyrimido[2,1 -b][ 1,3]thiazine
Nl,N2,NS,N6,N& Nl,N2,NS,N6,Nll Nl,Ni,NS,NT,Nll Nl,N3,N6,NT,Nll Nl,NA,N5,NT,Nll Nl,N5,N6,NS, N10 Nl, N6,NT,NS,Nll N2, NA, NS, NS, Nl I N2, NA, NS, N9, Nl I
2404.247 2404.276 2404.607 2404.753 2404.828 2404.752 2404.679 2404.506 2404.355
2//-Pyrido[2',3', :4,5]pyridazino[6,l-c][l,2,4]triazine 2//-Pyrido[3',2':4,5]pyridazino[6,l-c][l,2,4]triazine 2H-Pyrimido[2,1 -/i]pteridine 1//-Dipyrimido[l,2-/): 4',5'-d]pyridazine 1 //-Pyrimido[ 1,2-c]pteridine 2//-Dipyrimido[l,2-6:5',4'-
Nl,NA,N6,ST,Nll
2404.447 2404.505 2404.393
2/f,8//-[l,3]thiazino[3,2-a]pteridine Pyrido[3',2',: 5,6][l,4]thiazino[3,4-c][l,2,4]triazine 2//,6a//,8//-[l,3]Oxazino[2,3-/;]pyrimido[4,5-rfl[l,3]oxazine
N2, NA, N\ 1 A3, NS, N\ 1 A 3 , NT, A'l 1
NA, NS, Nl 1 NA, NT, N\ 1 AT1.O8, JV11
N4, OS, Nl 1 Ol,N9, Nil Nl,SS,Nll
A.3 Four ring heteroaloms XIV (100) Nl, N2,N6, Nl 1 XIV (101) Nl,Ni,N5,Nll (102) (103) (104) (105) (106) (107) (108) (109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121)
XIV
XIII XII XII XII XII XII XII XIV XIV XIV XV
XIII XIV XIV XIV XV XIV XIV XIV
A.4 Five ring heteroatoms XII (122) XII (123) XIV (124) XIII (125) XIII (126) XII (127) XIV (128) XIV (129) XIV (130) (131) (132) (133)
XIV XV XIV
Nl,N3,N6,NU Nl, NA, NT, NIQ Nl, N+S, Nb, NS Nl, NS, N6, N9 Nl, N5, N6, N10 Nl,N5, N6, Nil Nl, N5, NT, NS N\, NS, NT, N9 Nl,NS,NT,Nll Nl,NS,NS,Nll Nl,N6,NT,Nll Nl,NT,NS,Nll N2, NA, NS, NT N2, NS, NT, Nl 1 JV2, NS, NS, Nl 1 A3, NS, NT, Nil A3, N6, NT, Wl 1
Nl,O6,m,NU N2, A3, O8, A'l 1
A 3 , JV4, S6, NT, Nl 1
A'l, A3, O6,OT,NU
88MI 839-02 92JHC529 74JHC151 85IJC(B)182, 89MI 839-02, 94FES259 78PJC1395 92S798 90JAP(K)02096580 92T349 92S798
88CB2049 87T3955, 89JCS(P2)1691, 89MIP148975, 90CJC2164, 91JA1756, 91 MI 839-01, 91MI 839-02, 92MI839-02 80CL817, 85JHC173, 87KGS677 64MI 839-01 71JOC2457, 85MI839-03 85MI 839-03 85MI 839-03 85M1839-03 78JHC877 82EUP46446 83IJC(B)1233, 88EUP257508 79USP4138564 86JHC509, 87MIP554363 81JA7011 90MI839-01, 91TL4473, 93JOC6976 88EUP257508 79USP4138564 88EUP257508, 93BRP2257360, 93MI 839-01 79USP4138564 89MI 839-03 94H(37)171 81JHC495
70M303 70M303 83IJC(B)1233 89T4485 91CCC2288 89T4485 86JHC509, 90AF1349 82JMC161 74GEP(O)2330984,75B3338,81JMC1086,83B1005, 84MI 839-03, 87B522 77ACS(B)167 79URP638068, 93KGS559 75USP3860596
I I
Table 2 (continued) Tricydic system
Type
Positions of ring heteroatoms
Ring identifier (Chem. Abstr.)
Parent system
o o References
A.5 Six ring heteroatoms (134) XIII M,iV3, JV5, JV6, iV7, M l
2404.622
(135) (136)
2404.673 2404.504
li/-Dipyrimido[l,2-c: 4',5'-e][l,2,3]triazine 2i/-Pyrimido[2',l',: 2,3]pyrimido[5,4-rf][l,2,3]triazine Pyrimido[5',4': 5,6][l,4]thiazino[3,4-c][l,2,4]triazine
84JCS(P1)1475 86JCS(P1)711 93KGS559
2404.674
2//-Pyrimido[4,5-e][l ,2,4]triazino[4,3-c][l ,2,3]triazine
86JCS(P1)711
2404.864
2//-Pyridazino[3,4-
93MI839-02
2404.285
Dipyrido[l,2-a: 2', 1 '-c]pyrazinediium
XIV XIV
N2,N3,N4,N6,N7,NU N2,N4,S5,N7,NS,NU
A.6 Seven ring heteroatoms XII N\,N2,N5,N6,N7,N9, (137) Ml (138) XIV Nl,N2,N5,N6,N7,NlO, Ml B Two ring junction atoms B.I Two ring heteroatoms XVI N+5,N+% (139)
General chemistry: 67AJC1213, 68AJC2951, 68JCS(C)926, 68T4411, 68T5433, 68TL2599, 69CCC2037, 69E1247, 69JA3822,69JCS(C)610, 69T4781, 70JCS(D)494, 71JHC29, 72AX(B)1244, 72AX(B)3065, 72JCS(P1)138, 72JHC1165, 72JMR(8)207, 73JCS(P2)80, 74CPB157, 74JHC303, 76JA1711, 76ZN(B)115, 77AJC657, 77JCS(P2)445, 78JCS(F1)665, 78JPC1181, 82AJC1341, 82JCS(P1)125, 83JA2350, 84ANC1030, 84H(22)803, 84LA1731, 85BBA(810)385, 85JOC2910, 86CJC1711, 86CL2139, 86JC265, 86TAL745, 87CJC2425, 87JA2876, 87JOC521, 87MI 839-05, 88CL373, 88JA8232, 88JOC4745, 88TL1569, 89AG462, 89CB1023, 89GEP(O)3717071, 89JA5782, 90CL493, 90MI 839-02, 90URP1594175, 91BCJ1821, 91CPB956, 91EUP431547, 91JOC4678, 91MI 839-03, 91MI 839-04, 91SM1819, 92MI 839-03,92TL1771,93JC271,93JPC7800,94CC51,94JC217, 94MI 839-01 Applications: 67AJC1195, 67NAT381, 68NAT1067, 69NAT464, 70MI 839-01, 71MI 839-01, 72CI(L)195, 72MI 839-02, 72MI 83903, 73JA3411, 73LA324, 75GEP(O)2500409, 75MI 839-02, 75MI 839-03, 76JCS(F1)2416, 77CJC2601, 77MI 839-01, 78IC1827, 78JA579O, 78JPC2662, 79JCS(F1)1912, 79JEC283, 79M1 839-02, B-79MI 839-03, 80CPL(74)314, 80JMOC539, 80JPC2762, 80MI 839-02, 80MI 839-03, B80MI 839-04, 81JA4727, 81JA7270, 81JMOC261, 81JOC1255, 82IJ117, 82IJ147, 82JA2683, 82JA3618, 82JA7519, 82JEC211, 82MI 839-01, 82MI 839-02, 83CC1140,83IC1672,83JA5617,83JCS(F1)1135,83MI83901, 83NJC15, 84ANC866, 84JCS(F 1)2255, 84JCS(F 1)2693, 84JPC2009, 84JPC5845, 84MI 839-04, 84TL2867,
I? s ft
3
I (ft
O\
85AG584, 85CC311, 85CC314, 85IC451, 85ICA129, 85IC3399, 85JA2632, 85JA4647, 85JCS(P2)607, 85JMOC119, 85MI 839-04, 85MI 839-05, 85TL1681, 85TL1685, 86BCJ1709, 86JA3380, 87AG939, 87BCJ3663, 87CC1054, 87CC1058, 87CC1061, 87CC1066, 87GEP(O)3616923, 87ICA135, 87JAP(K)62062881, 87JAP(K)62201803, 87MI 839-06, 87MI 839-07, 87MI 839-08, 87TL6267, 88CC52, 88ICA55, 88JA6586, 88JA6673, 88MI 839-03, 88NKK569, 88PAC467, 88TL1573, 89B6057, 89CC1874, 89H(28)359, 89JA1128,89JPC294,89JPC7130,89MI839-04,89MI839-05,90B6102, 90BCJ2710, 90MI 839-03, 90MI 839-04, 91CE9, 91CE603, 91JCS(D)1691, 91JPC1348, 91JPC3780, 91JPC10694, 91MI 839-05, 91MI 839-06, 92JA1881, 92JA3784, 92JA9504, 93BCJ1764, 93CC522, 93JPC6492, 94ANC1817, 94BCJ847, 94HCA351, 94JC688, 94JCS(P1)995,94JCS(Pl)1009,94JPC3865,94MI839-02,94MI 839-03, 94MI 839-04, 94MI 839-05
N5,N+l2
2404.331 2404.333
2//-Dipyrido[l ,2-a: 1 ',2'-c]pyrimidin-5-ium Dipyrido[l ,2-b: 2', 1 '-y]pyridazinediium
(142)
2404.2
Borinof 1,2-6]pyrido[2,1-f\[ 1,2] azaborine
B.2 Four ring heteroatoms (143) XVI NI,N5,NZ,N12
2404.545
Pyrazinofl ,2-a: 4,3-a']dipyrimidine
(144)
XVI
N2, N5,NS, N\ 1
2404.548
Dipyrazino[ 1,2-a:2', 1 '-cjpyrazine
(145) (146)
XVI XVII
N5,N6,JV7, S\,N5,SS,N12
2404.334 2404.488
Dipyrido[l ,2-d: T, 1 '-J\[\ ,2,3,4]tetrazine 2//,6//,9//,12a//-Pyrimido[2,l-6:4,3-//]bis[l,3]thiazine
B.3 Six ring nitrogen atoms (147) XVII N\,N3,N5,N8,NIO,N12 (148) XVI N2, N4, N5, NS, N9, N\ 1 (149) XVI 7V2,JV5, N6,Nl, NS, N\ 1
2404.453 2404.803 2404.469
2//,6//-Pyrimido[l ,2-a: 3,4-#']bis[l ,3,5]triazine Pyrazino[2,1 -/: 3,4-/]bis[l ,2,4]triazine Dipyrazino[l,2-d: 2 ,1'-_/] 1,2,3,4]tetrazine
B.4 Seven ring nitrogen atoms (150) XVII M , N2,N5, N6, NS,N9, N12
2404.813
(140) (141)
XVII XVIII
70LA(737)l, 71IJQ221, 76S201, 93BCJ1222 71GEP(O)2017343
i? 71CCC1248
81TL1711,84EUP113582,88MI839-04, 89MI839-05,90JCR(S)304, 92JCS(P1)561, 93JOC5753 81JMC1329, 83JA2350, 83MI 839-02, 85JMC1111, 92USP5130426, 93MIP9323075 73AG50, 74GEP(O)2327545, 78HCA1622, 94CB2073 79LA334 ON
,6//-Bis[l ,2,4]triazino[4,3-6:4',3'-d][l ,2,4]triazine
77CR(C)25, 80EJM341, 82MI 839-03 90TL7665, 92ZOR589 78HCA1622 91FES379
C Four ringjunction atoms C.I Six ring heteroatoms
(151)
2404.3
Bis[l,2]azaborino[l,2-a: r ^ ' -
71CCC1248
Table 3 Fused heterocyclic systems (6:6:6) with Chemical Abstracts ring identifier (1784) for the tricyclic skeleton. (References in bold refer to synthesis.)
8
8
8
Type XX
Type XIX
9a
N
Type XXI
3a
9b
9a
X
8
Type XXII Tricyclic system
Type
Positions of ring heteroatoms
A One ringjunction heteroatom A.I One ring heteroatom (152) XX N9b
(153) (154) (155)
XXI XXI XXI
S+9b P9b B9b
N
1784.152 1784.151 1784.1
8
X
6a
6a
Type XXIII
Type XXIV
Ring identifier (Chem. Abstr.)
1784.137
3a
N i
I 8
X
Parent system
Pyrido[2,1,6-de]quinolizine
96-Thioniaphenalene 96-Phosphaphenalene 9^-Boraphenalene
•3 References
General chemistry: 68YZ900, 69CC24, 69JCS(A)1754, 72BSB649, 72CC626, 72T3613, 72T3635, 72T3657, 72TL1767, 73JA6702, 73MI 839-02, 74AJC2025, 74TL409, 75CC565, 75T1541, 76CJC473, 76CJC1494, 76CJC1807, 76CPB2270, 76JCS(P1)341, 76TL2925, 77IJC(A)238, 77JA1692, 77JOC3210, 77JST(42)85, 77YGK739, 78AHC(22)321, 78JST(49)415, 79JA7032, 79TL1991, 80JA6068, 80TL1027, 80TL1093, 80TL1097, 81DIS(B)4524, 82H( 18)37, 84CCA991, 84JOC2217, 84JPC1376, 85JA3884, 85JOC4028, 86DIS(B)1919, 86JA17, 86MI 839-06, 87ZC28, 88DIS(B)1662, 89CPB1226, 89JA7371, 89PAC2117, 91CC1261, 92HAC19, 92SC3115, 92TL1281, 93EJM869, 94JHC929, 94T3139 Applications: 71C307, 71 El380, 72C74, 73MI 839-03, 74MI 839-02, 75E145, 78MI 839-01, 81KPS764, 86EUP172427, 91EUP451055, 91 MI 839-07, 92MI 839-04, 92MI 839-05, 93MI 839-03 72IZV2817, 73ZOR636, 74MI839-03 69USP3435076
Co Hi
ON
General chemistry: 67JA5478, 68LA(717)21, 69JA1226, 71JA7319, 73TL141, 74JOC861, 74LA54, 75CC565, 75DIS(B)1232, 76GEP(O)2608584, 76TL2925, 78CC805, 78JA3343, 78JOM(156)111, 78USP4082810, 79JMC401, 79JOC5604, 80JOM(188)1, 81T2359, 83OS(61)103, 84JOC2217, 85JOC520, 88ZOR742, 89CC1639, 93T8311 Applications: 81USP4251422 A.2 Two ring heteroatoms (156) XX
N\,N9b
1784.160
Pyrimido[2,1,6-de]quinolizine
(157) (158) (159)
XIX XIX XX
N2, Nba Ol,N6a 01, N9b
1784.113 1784.333 1784.138
1H,4#-Pyrido[3,2,1 -ij ][ 1,6]naphthyridine 4//-Pyrano[2,3,4-//]quinolizine 2H-[ 1,3]Oxazino[2,3,4-de]quinolizine
(160)
XIX
02, N6a
1784.114
l//,3//,4//-Pyrano[3,4,5-//]quinolizine
74CPB1424, 74CPB1939, 74YZ50, 75CPB2759, 75YZ1431, 76CPB2270, 78JST(49)415, 85JOC4028, 87H(26)2757, 88CPB4307, 89CPB1188, 89CPB1226, 92JAP(K)04338762 68KPS371, 73JA8427, 86CPB2018 91MIP9116894 72TL1767, 73MI 839-04, 74AJC2025, 76CJC473, 76CJC1494, 80M783, 88TL2229,93JA8851 58CPB222, 59CPB241
OS
A.3 Three ring heteroatoms
(161) (162)
XX XX
Nl,N3,N9b Nl,N4,N9b
1784.345 1784.167
[1,3,5]Triazino[2,1,6- dejquinolizine 1,4,96-Triazaphenalene
(163) (164) (165)
XX XX XX
Nl, N6, N9b Nl, m, N9b Nl, N9, N9b
1784.168 1784.365 1784.166
1,6,96-Triazaphenalene 1,8,96-Triazaphenalene 1,9,96-Triazaphenalene
1784.224
1//,5//-Pyrimido[5,6,1 -ij][l ,6]naphthyridine
1784.363
2,5,96-Triazaphenalene
(168)
1784.230
l/f,4//,7//-8-Oxa-2,3a-diazaphenalene
A.4 Four ring heteroatoms («9) XIX Nl, N2, N+6a, N9 (179) XX Nl,N3,N4,N9b
1784.280 1784.178
1H-1,2,9-Triaza-6a-azoniaphenatene 1,3,4,96-Tetraazaphenalene
(166)
(167)
XX
N2, N5, N9b 2
92DIS(B)6403 75YZ13, 77ACS(B)235, 78CPB680, 84CS170, 85CPB3034, 87H(26)2757, 87YZ344, 89CPB1188 75CPB1629, 85JOC4028, 87(26)H2757 93JIC693 74CPB2765, 75YZ13, 76ACS(B)466, 77JHC671, 78YZ623, 87H(26)2757, 89CPB1188
81CPB1193, 82KGS518, 83MI 839-03
93JIC693, 94JHC929
82KGS518
85MI839-03 77ACS(B)235, 85JA3884,92HAC19
>3
Table 3 (continued) Positions of ring heteroatoms
Ring identifier (Chem. Abstr.)
Parent system
Tricyclic system
Type
(171)
XX
N\,N3,N6,N9b
1784.139
1,3,6,96-Tetraazaphenalene
(172)
XX
Nl,N4,N7,N9b
1784.141
1,4,7,96-Tetraazaphenalene
(173) (174) (175) (176)
XX XX XX XX
N2, N5, m, N9b 01, N4, Nl, N9b si, N4, N9, N9b 01, 04, 01, N9b
1784.364 1784.142 1784.346 1784.144
2,5,8,96-Tetraazaphenalene 2H-1 -Oxa-4,7,96-triazaphenalene 2H-1 -Thia-4,9,96-triazaphenalene 2H,5H,SH-1,4,7-Trioxa-96-azaphenalene
Nl, N3, N4, N6, N9b,
1784.143
1,3,4,6,96-Pentaazaphenalene
Nl, N3, N4, Nl, N9b, Nl, N3, N5, Nl, N9b, Nl, N3, N6, Nl, N9b
1784.157 1784.181 1784.140
1,3,4,7,96-Pentaazaphenalene 1,3,5,7,96-Pentaazaphenalene 1,3,6,7,96-Pentaazaphenalene
A.5 Five ring heteroatoms (177) XX
(178) (179) (180)
XX XX XX
A.6 Six ring heteroatoms (181) XX (182)
XX
Nl,N3,N4,N6,Nl,N9b
1784.163
1,3,4,6,7,96-Hexaazaphenalene
Nl, N3, N4, N6,NS, N9b
1784.182
1,3,4,6,8,96-Hexaazaphenalene
1784.145
1,3,4,6,7,9,96-Heptaazaphenalene
A.7 Seven ring heteroatoms (183) XX Nl,N3, N4, N6,Nl, N9, N9b
References 72ACS596, 72ACS611, 72ACS624, 73ACS2095, 73ACS3259, 73ACS3264, 74CPB1424, 75CPB1629, 75ACS(B)867, 76JHC1029, 77ACS(B)239, 81 MI 839-02, 82JHC357, 84MI 83902, 85JCS(P2)153, 85JA3884, 85JOC4028, 86JHC381, 87CL675, 87JHC321, 88CPB4307, 88JHC1837, 90JHC1591, 91JHC987, 92HAC19, 93JIC693, 94JHC929 General chemistry: 68JCS(B)760, 69USP3444166, 70M1037, 79JCS(P2)143, 81CAR(89)237, 84CS170, 86JA17, 94JHC929 Applications: 68USP3397167, 69GEP(O)1914955, 74P2519, 74KPS752, 74USP3794609, 84EUP113582 93JIC693, 94JHC929 70M1037, 74P2519 92PS(72)145 76CB650, 77JEC193, 77MI 839-02, 89EGP265428, 91JOC452 72CC1070, 74JHC627, 76JHC127, 77JHC341, 78AX(B)1667, 81JHC75, 82JHC357, 83JHC1095, 84AX(C)2108, 84JA4374, 84JHC429, 85JA3884, 85JCS(P2)153, 85JHC255, 87CL675, 88JHC1837, 89MI 839-06, 92HAC19, 93JIC693, 94JHC929 73ACS2421, 93JIC693, 94JHC929 77JHC679, 93JIC693, 94JHC929 72ACS635, 73ACS359, 93JIC693, 94JHC929 74JHC627, 75MI 839-04, 81JOC1457, 85JA3884, 92HAC19, 93JIC693, 94JHC929 77JHC679, 92HAC19
General chemistry: 71ZOR972, 72ZOB419, 76JC63, 76ZOB1423, 76ZOB1653, 77CR(C)913, 77ZOB1763, 79ZAK385, 80MI 839-04, 80MI 83905, 80URP707917, 80USP4205167, 81MI 839-03, 81MI 839-04, 81MI 839-05, 81ZOB2377, 82JA5497, 82NKK662, 83MI 839-04, 83MI 839-05, 84DIS(B)197, 84JA2805, 84JAP(K)59031861, 84JAP(K)59033353, 84JPC4324, 84MI 83905, 84PJC3, 84PJC13, 85EUP137652, 85JA3884, 86MI 839-02, 86MI839-03, 86MI 839-04, 86MI839-05, 86URP1237668, 87URP1294806,
Si's OS
••
ON
(184)
XXI
(185)
XXI
Sbl, Sb3, Sb4, Sb6, Sbl, Sb9, Sb9b Sil, SB, Si4,5/6, Sil, Si9, SBb
1784.283
1,3,4,6,7,9,96-Heptastilbaphenalene
1784.154
1,3,4,6,7,9,96-Heptasilaphenalene
88USP4775696, 88EUP286478, 89JAP(K)01018907, 89MI 839-07, 89MI839-08, 89URP1490122, 90GEP(O)3908815, 90IZV113, 90JAP(K)02274761, 90URP1539654, 91MI 839-08, 91URP1685939, 92HAC19, 92M1839-06, 92URP1747448, 92URP1775402, 92USP5120821, 93JIC693, 93MI 839-04, 94JHC929 Applications: 79URP697603, 80URP712097, 80URP773139, 81URP817043, 81URP833576, 81URP887612, 84GEP(O)3231540, 84JAP(K)59041360, 84JAP(K)59045352, 85MI 839-06, 86URP902450, 86USP4619735, 89URP770027, 89USP4822825, 89USP4824869, 90MIP1038845, 91EGP296967, 91JAP(K)03202458, 92JAP(K)04239558, 92MI 839-07, 92MI 839-08, 92URP1775428, 93JAP(K)05339417, 94MI 839-06 87IC3797 58AG701, 59ZAAC(299)232, 59ZAAC(299)316, 59ZAAC(302)60
B Two ring junction atoms B.I Two ring heteroatoms
So
(186)
1784.2
3a-Azonia-9A-boraphenalene
B.2 Three ring heteroatoms (187) XXII N2, N+3a, N6a
1784.233
1
(188)
1784.366
4//,9i/-l-Oxa-6a,9a-diazaphenalene
B.3 Four ring heteroatoms (189) XXII N\,N3a,N6a,N9
1784.133
1 H,AHJH-\ ,3a,6a,9-Tetraazaphenalene
81TL1711, 81TL2217, 91T1013
(190)
1784.222
1tf,5/f-Pyrimido[ 1,2,3-(flpteridin-4-ium
81H(15)437
tf,4//-2,6a-Diaza-3a-azoniaphenalene
68TL2707, 71CCC1248
82BEP892120, 82TL2891, 83H(20)579, 83H(20)1891, 85H(23)1093, 85H(23)1167, 85H(23)2549, 88MI839-05
94JAP(K)06148845
I
i
Table 3 (continued) Tricyctic system
Positions of ring heteroaloms
Type
Ring identifier (Chem. Ahstr.)
Parent system
o References
C Three ring junction atoms C.I Three ring nitrogen atoms
(191)
1784.193
l//,4//,7//-6a,9a-Diaza-3fl-azoniaphenalene
1784.134
l//-2,3-a,5,6a,8,9a-Hexasilaphenalene
1784.175 1784.210
1 //,4//,7//-3a,6«,9«-Triaza-9/j-phosphaphenalene m,4W,7//-3a,6a,9a-Triaza-9A-boraphenalene
1784.165 1784.5
1 H,4H,TH-2,3a,6a,9a-Tetraaza-1,3-diphospha-9/>-boraphenalene 1 //,4//,7//-2,3a.6a,9a-Tetraaza-1,3-disila-9i-boraphenalene
1784.4
l//,4//,7//-2,3a,6a,9«-Tetraaza-l,3,9/>-triboraphenalene
1784.149
3a//,6a//,9a//-l,3,4,6,7,9,9A-Heptaaza-2,3a,5,6a,8,9ahexaphosphaphenalene
1784.136
1 H,4H,TH-1,3,4,6,7,9,96-Heptaaza-2,3«,5,6a,8,9flhexaboraphenalene
1784.153
l//,4//,7//-2,3«,5,6a,8,9a-Hexaaza-9A-stiba-l,3,4,6,7,9hexasilaphenalene
1784.155
Tricyclo[7.3.1.05ll]heptasilazane
1784.3
l//,4//,7i/-2,3a,5,6a,8,9a-Hexaaza-l,3,4,6,7,9,9Aheptaboraphenalene
78USP4085106, 80JA6363, 80JA6364, 80JA6365, 80TL3635, 81TL4365, 87AG1216, 87CC886, 87MI 839-09, 87T1903, 88MI 839-06, 89HCA1125, 89POL2333, 90DIS(B)1260, 91TL7755, 92CC507. 93AG640
C.2 Six ring silicon atoms
(192)
H
72ZAAC(390)157, 88JOM(341)109
.5
Si.
• Si 6a
H
D Four ring junction atoms DA Four ring heteroatoms (193) XXIII N3a, N6a, N9a, P9b (194) XXIII Nia, N6a, N9a, B9b D.2 Seven ring heteroatoms (195) XXIII P\,N2,Pi,Nia,Nba,N9a,B9b (196) XXIII Si\,N2, SB, N3a, N6a, N9a, Bf)b (197) XXIII B\,N2,B3,N3a,Nba,N9a, B9b D.3 Thirteen ring heteroatoms XXIV (198) N\,P2, N3, P3a, NA, Pi, N6, P6a, NT, Pi, N9, P9a, N9b XXIV (199) N\,B2,N3,B3a,N4,B5, N6, B6a, NT, B8, N9, B9a, N9b XXIII (200) Sil,N2,SB,Nia,Si4,N5, Si6, Nba, SiT, NS, Si9, N9a, Sb9b XXIII (201) Sil, N2, SB, Nia, S/4, A"5, Si6, Nba, SiT, N$, Si9, N9a, S»b (202) XXIII B\,N2,Bl,N3a,B4, N5, B6, Nba, BT, N8, B9, N9a, B9b
76USP3996276, 77USP4038312, 78TL4331, 81JA2054 80JA5790, 81JCS(D)511, 81JA6133, 89JCS(P1)2O79, 91IC4524
t
74CB3806 70CB2234, 75CB3109
a.
65IC886
O\
71JCS(D)357, 72JCS(D)623, 73CJC520 67CJC2059, 84AG301 72MI 839-04 71 MI 839-02, 79JAP(K)54093100, 84MI 839-06 67CJC2059
Three Heterocyclic Rings Fused (6:6:6) 8.39.6.2.2
1107
Formation of the terminal ring
This approach involves the construction of a third ring on a suitably substituted fused bicyclic substrate: (2)-(4), (7) <71JOC2192, 92JHC25), (11) <90ZC98>, (16) <92MI 839-01), (18), (22), (23) (89CB1935,90CB1415), (29), (33) <78CB97i>, (37), (41), (42), (47), (50), (59), (60), and (61).
8.39.6.2.3
Formation of two rings
Intramolecular and intermolecular tandem cyclizations of a suitably substituted six-membered heterocycle, which result in a simultaneous formation of two rings fused to the substrate ring, have been reported for (5) <89MlP8905809>, (10), (13), (14), (19), (21), (31) <73CPB770>, (33) <93HCA43i>, (44), and (51) <85JMC1228>.
8.39.6.2.4
Formation of three rings
Derivatives of systems (64), (72), and (76) have been synthesized by one-pot cyclization of acyclic substrates.
8.39.6.2.5
Ring transformation
The synthesis of derivatives of (23) <90CBl4l5>, (36), (48), and (57) involves a one-step ring transformation of a heterocyclic substrate.
8.39.6.3 8.39.6.3.1
Hetero Analogues of Phenanthrene (Table 2) Formation of the central ring
The vast majority of systems in this class has been constructed by cyclization of an unfused heterobiaryl or a substrate composed of two six-membered heterocycles and linked by a two-atom bridge: (78)-(82), (84)-(87), (90M92), (97), (102), (108), (109), (111), (112), (116), (118), (120), (126), (128), (140), (141), and (143). An intermolecular condensation of two appropriately functionalized six-membered heterocyclic substrates provides a facile synthetic entry to (88) <83M1197,86H(24)3075>, (100), (101) <92MI 839-02), (110), (114) (91TL4473, 93JOC6976), (115), (117), (121), (124), (139) <85JOC29io>, (145), (146), (148), and (149).
8.39.6.3.2
Formation of the terminal ring
The cyclization of a substituted fused bicyclic substrate has been used in the preparation of derivatives of (77), (83), (88) <86JHC509>, (93M95), (104)~(107), (114) <90Mi 839-oi>, (122), (123), (125), (127), (129)-(131), (134), (135), (137), and (138).
8.39.6.3.3
Formation of two rings
This approach involves mainly cyclization of substituents at a six-membered heterocycle which becomes the central ring in the product. Derivatives of the following systems have been prepared: (89), (96), (99), (119), (132), (133), (136), (144), (147), and (150).
8.39.6.3.4
Formation of three rings
One-pot cyclization of acyclic substrates provides a facile synthetic entry to substituted derivatives of(103)and(113).
1108
Three Heterocyclic Rings Fused
8.39.6.3.5
(6:6:6)
Ring transformation
Substituted derivatives of (98) and (101) <87T3955, 9UA1756, 91MI 839-02> have been obtained by ring transformations of heterocyclic substrates.
8.39.6.4
Hetero Analogues of Phenalene (Table 3)
8.39.6.4.1
Formation of one ring
Intramolecular cyclizations of ^en-substituted fused bicyclic substrates (6:6) and intermolecular cyclizations that involve the peri positions of unsubstituted systems (6:6) have been applied to the synthesis of the following parent compounds or derivatives: (152) <69CC24,91CC1261), (156)-(158), (160)-(162), (165) <74CPB2765>, (166), (168), (170), (183) <82JA5497, 84JA2805), (186), (187), (190), (191) <92CC507>, and (195)-(197).
8.39.6.4.2
Formation of two rings
A double cyclization of a substituted six-membered heterocyclic substrate provides a synthetic entry to derivatives of (152) <94T3139>, (153), (159), (165) <76ACS(B)466,77JHC67l>, (169), (171), (175), (177)-(182), and (192).
8.39.6.4.3
Formation of three rings
One-pot cyclization of acyclic substrates provides a facile synthetic entry to derivatives of (152) <75CC565,92SC3115), (172), (174), (176), (183) <86Mi 839-05>, (185), (189), and (198)-(201).
8.39.6.4.4
Ring transformation
The synthesis of derivatives of parent compounds (152) <80TLi093> and (163) involves a one-step ring transformation of a heterocyclic substrate. Derivatives of (153)-(155), (191) (80JA6365,80TL3635, 81TL4365), (193), and (194) have been obtained by reactions of macrocyclic compounds.
8.39.7
APPLICATIONS
Diverse applications have been found and many potential uses have been suggested for the parent compounds or derivatives of the three classes of fused heterocyclic systems (6:6:6). A detailed list of reports that deal with these topics can be found in Tables 1-3. When a particular system contains many references the publications describing mostly applications or potential applications are collected separately from the general chemistry references. The applications are also mentioned in the vast majority of the general references. The parent compounds or derivatives listed in Tables 1-3 are antitumor agents, (37), (51), (53), and (144); antibacterial and antiparasitic agents, (22), (61), and (148); antiallergy, antiinflammatory, and analgesic agents, (6), (8), (17), (25), (27), (30), (32), and (36); diuretics, (109); antihypertensives, (111) and (116); disinfectants and antiseptics, (117); inhibitors of phosphodiesterase, (30), (34), and (36); a-1-adrenergic and a-2-adrenergic receptor antagonists, (77); folate enzyme inhibitors, (129) and (130); fluorescent labels for DNA, (25) and (101); herbicides, (139); stabilizers for dyes and polymers, (53) and (62); and fireproofing agents for cotton fibers, (193). Compound (155) and its derivatives have been used in the synthesis of natural products which are derivatives of (152) <75CC565,76TL2925).
Copyright © 1996 Elsevier Ltd.
Comprehensive Heterocyclic Chemistry II