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Subject Index
A
N-alkyl-meso-tetraphenylporphyrins,
354-357
Acetic acid, solvent for porphyrin retaliation, 405
electronic spectra, 355
nmr spectra, 354
Acetoacetic acid derivatives, nitrosation,
107
preparation, 354
Alkyls
Acetonedicarboxylic esters, nitrosation, 107
Acetoxymethylpyrroles, synthesis, 149
cobalt, 470
iron, 470
Acetoxyporphyrinogens, 277
Allomerization of chlorophylls, 326
Acetyl acetonates, for porphyrin metalla-
Alumina, porphyrin chromatography, 567
tion, 405
,407
N-Acetylcorroles
electronic spectra, 362
Aluminum porphyrins, 429
m-oxo
dimers, 429
Ammonium mucate, pyrrole synthesis, 129
nmr spectra, 361
Amyl nitrite, nitrosating agent, 107
synthesis, 361
p-Anion radicals, phthalocyanins, 377
4-Acetyldeuteroporphyrin diethyl ester,
Antimony porphyrins, 436, 439
synthesis, 259
Antimony octaethylporphyrin, X-ray struc-
3-Acetyl-8-ethyldeuteroporphyrin
ture, 437
dimethyl ester, synthesis, 259
Aplysioviolin, nomenclautre, 20
Acid lability, metalloporphyrins, 418
Apomyoglobin, reconstitution with Yb
Acylation, oxophlorins, 277
N-alkylcorroles, 357-361
mesoporphyrin, 431
Arsenic porphyrins, 436, 439
electronic spectra, 358
N-Arylcorroles, 360
mass spectra, 360
meso-Arylporphyrins
nmr spectra, 357
rearrangements, 358
b-substituted, 89
synthesis, 88
synthesis, 357
Aroyldipyrrylmethanes, 90
X-ray structure, 358
Atropisomers, 89
3-Alkyl-2,4-pentanediones, 104
meso-Alkylporphyrins, synthesis, 90
Azafulvenium ions, in porphyrin synthesis,
93
6-Azaindole, precursor of porphobilinogen,
electrophilic attack, 271
nomenclature, 14
135
oxidation to bilenes-/?, 255
Azaporphyrins, 365-388
5-oxo,255
from biladienes-ac, 249
Azines, pyrrole precursors, 132
Bilatrienes, nomenclature, 14
Bilatrienes-abc from biladienes-abc, 246
Bilenes, nomenclature, 14
B
Bilenes-a, from bilenes b, 244, 253
Bilenes-b
Bacteriochlorin(s), nomenclature, 4, 13
from bilanes, 255
Bacteriochlorophyllgg, nomenclature, 25
copper promoted cyclization, 252
Bacteriopheophorbide a, nomenclature, 13
cyclization to porphyrins, 249-257
Bacteriopheophytina, nomenclature, 13
1,19-dicarboxylate esters,
Barium porphyrins, 426
cyclization with orthoformate, 257
Basicity
cyclization to porphyrins, specific
monazaporphyrins, 367
examples, 260
N-substituted porphyrins, 344, 347
l,19-dimethyl,256
Benzonitrile, solvent for porphyrin metallation, 405,407
Benzoyl chloride, Vilsmeier formylation of
pyrroles, 146
Benzyl 3-(2-methoxycarbonylethyl)-4,5dimethylpyrrole-2-carboxylate,
synthesis, 115, 116
Benzyl 4-(2-methoxycarbonylethyl)-3,5-
from 1,19-dimethylbiladienes-rtc,
258
from dipyrrylmethanes, 249
electronic spectra, 273
l-formyl-19-methyl,256
from 5-formyldipyrrylmethanes,
250
1-methyl, 256
dimethylpyrrole-2-carboxylate,
properties, 249
synthesis, 114
rearrangement to bilenes-a, 249,
Benzyl 3-(2-methoxycarbonylethyl)-4methoxycarbonylmethyl-5-methylpyrrole-2-carboxylate, synthesis, 113
Benzyl pyrrolecarboxylates, hydrogenolysis, 145
253
1-thioformyl, 257
Bilin, nomenclature, 15
Bilirubin, nomenclature, 18
Biliverdins, nomenclature, 17
Beryllium porphyrins, 425
Biological markers, 486
Biladienes, nomenclature, 15
Biosynthesis
Biladienes-ac
to azaporphyrins, 249
heme, 45, 65, 317
chlorophyll, 36
from 5-bromo-5'-bromomethylpyr-
2-2'-Bipyrroles, nomenclature, 3
romethenes, 242
N,N-bisethoxycarbony lmethylporphyrins
conversion to monoazaporphyrins, 366
copper promoted cyclications, 238
nmr spectra, 350
synthesis, 350
cyclization to porphyrins, 238-249
Bismuth porphyrins, 439
to 1-methyltetradehydrocorrins,
Bitumen, porphyrin occurrence, 517
246
from 5-methyl-5-unsubstituted
pyrromethanes, 242
properties, 244
synthesis, 238, 242
Bilanes
from bilenes-b , 255
dehydrogenation to bilenes-/?, 255
electronic spectra, 273
Bohr effect, 47
Books, in porphyrin field, 38, 393
Boron octaethylporphyrin [(B2O(OR)2(OEP)],
X-ray structure, 399
Boron porphyrins, 429
Brominative decarboxylation, pyrrole carboxylic acids, 154
5-Bromo-5'-bromomethylpyrromethene,
conversion to biladienes-ac\ 242
1-Bromo-19-methylbiladienes, cyclization
to porphyrins, specific examples and
experimental details, 261
nomenclature, 7
preparation, 327
Chlorin e6
Bromoporphyrins, hydrogenolysis, 282
t-Butyl hypochlorite
nomenclature, 7
preparation, 326
methylpyrrole chlorination, 148, 150, 159
Chlorinp6, nomenclature, 7
oxidation of bilanes to bilenes-6, 255
Chlorobium chlorophylls
oxidation of methylpyrrylketones, 269
nomenclature, 25
t-Butyl pyrrole carboxylates, removal of
t-butyl group, 153
synthesis of related porphyrins, 257
Chlorocruoroporphyrin, see Spirographis
porphyrin
Chloroethylporphyrins, 281
Chlorohemin, synthesis, 33
C
Chloromethypyrroles, synthesis, 148
5-Chloromethylpyrrylketones, 269
Cadmium porphyrins, 426
Calcium carbonate, chromatographic support for porphyrin chromatography, 556
Chlorophyll(s)
allomerization, 326
biosynthesis, 36
Calcium porphyrins, 426
conversion to porphyrins, 324-329
Capped porphyrins, 455
nomenclature, 24
2-Carbethoxy-4-alkyl-3,5-dimethylpyrroles, 104
structures, 510
Chlorophyllin, 325
N-Carbethoxyglycine esters, pyrrole pre-
Chloroporphyrine4, nomenclature, 7
cursors, 134
Chloroporphyrinp6, nomenclature, 7
meiso-Carbon atom, nomenclature, 3
meso-Chloropyrrylmethene, 220
Carbonyl complexes
Chromatography of porphyrins and metal-
hemes, 457
loporphyrins, 553-580
iron porphyrins, 457
carboxyl containing porphyrins, 560
osmium porphyrins, 463, 466
choice of method, 554
rhodium porphyrins, 471
column, 563
ruthenium porphyrins, 463, 466
high pressure liquid, 492, 558, 574
Carbonyl diimidazole, 332
metalloporphyrins, 419
Catalytic hydrogenation, iodopyrroles, 124
paper, 559, 565
Cellulose, column chromatography of por-
precautions, 557
phyrins, 563
thin layer, 562
tic of porphyrins, 562
Chromium (acac)3, 403
Ceric ammonium nitrate, oxidation of dipyr-
Chromium porphyrins
rylmethanes to pyrrylketones, 220
Cerium porphyrins, 424
Charge transfer bands, metalloporphyrins,
417
Chemical fossils, 486
Chlorin(s)
oxygenation by dioxygen, 440
synthesis, 440
Cis and trans effects, 465
Cobalt N-methyl-ra^so-tetraphenylporphyrin, X-ray structure, 356
Cobalt porphyrins
N,N-dimethyl, 353
dioxygen adducts, 468
nomenclature, 4, 13
ligand exchange, 452, 468
removal from porphyrins, 90
metal alkyls, 470
mpso-tetraphenyl, 89
N-Co methylene bridged, 350
N,Af,AMrimethyl, 353
redox chemistry, 452
Chlorin, 5
nomenclature, 8
Chlorin e4
synthesis, 449, 468
Coboglobin, 456
Colloquia, in porphyrin field, 40
Conferences, in porphyrin field, 40
Coordination-types of metalloporphyrin,
Cytodeuteroporphyrin
preparation, 310
structure determination, 310
396
Copper deuteroporphyrin dimethyl ester,
Vilsmeier formylation, 302
synthesis, 240
Cytoporphyrin, nomenclature, 11
Copperetioporphyrin I, synthesis, 239
Copper porphyrins, 471
D
electronic spectra, 472
redox chemistry, 473
synthesis, 449
Copper uroporphyrin, 33
Coproporphyri n(s)
chromatography, 560
nomenclature, 7
Coproporphyrin I
preparation, 320
synthesis, 211
Coproporphyrin II
Dealkylation, N-Substituted porphyrins, 347
Decarbonylation, formylpyrroles, Wilkinson's catalyst, 163
Decarboxylation
enzymatic, 280, 323
uroporphyrinogen I, 280
Dehalogenation, catalytic hydrogenation of
halopyrroles, 154
Dehydration, hematoporphyrin, 298
from protoporphyrin, 329
Deiodination, iodopyrroles, 124
synthesis, 246
Demetallation of porphyrins, 417
tetramethyl ester synthesis, 248, 258
Coproporphyrin III
preparation, 320
tetramethyl ester synthesis, 226, 228
Coproporphyrin IV
synthesis
tetramethyl ester synthesis, 257, 260, 275
Coproporphyrinogen III, enzymatic decarboxylation, 280
Coproporphyrin IV, enzymatic decarboxylation, 323
Corphin, nomenclature, 21
Corroles
N-acetyl, 361
Deoxophylloerythroetioporphyrin
nomenclature, 12
synthesis, 252, 256, 262
8-Desmethyldeuteroporphyrin, see
Cytodeuteroporphyrin
Deuterated porphyrins, 285, see also Isotopically labelled porphyrins
Deuterohemin
dimethyl ester, Vilsmeier formylation, 302
electronic spectrum, 294
from protohemin, 295
purification, 295, 465
pyridine hemochrome, electronic spec trum, 295
Deuteroporphyrin
N-alkyl, 357-361
chromatography, 296
N-aryl, 360
diacetyl, 226, 294, 300
N,N-dialkyI, 359
dibromo, 294
N-methyl, X-ray structure, 358
diformyl, 302
nomenclature, 19
Countercurrent distribution, porphyrins,
584
dihyroxymethyl, 294
dimethyl, 228, 332
dimethyl ester electronic spectrum, 295
Cruentine, 34
Cryptopyrrole, 104
synthesis, 117
Crystallization of porphyrins, hemes, and
heme proteins, 55, 585
Cyanovinyl, protecting group for formylpyroles, 146
synthesis, 243, 262
dipropionyl, 294
dipropionyl-hemin, 300
electronic spectrum, 294
formyl vinyl, 302
isomer se
Cyanovinylpyrroles, properties, 147
hydroxyethyl v
Cytochrome c, crystallization, 56
nitro, 294
paration, 562
inyl,
292
nomenclature, 11
N,N-Diethylformamide, synthesis and use,
preparation, 295
180
Diacetyldeuterohemin
Diethyl malonate, nitrosation, 107
purification, 301, 564
Diethyl oximinomalonate, 104
pyridine hemochrome, electronic spec-
3,4-Diethylpyrrole, synthesis, 127
trum, 300
Diformyldeuterohemin
synthesis, 300
pyridine hemochrome, electronic spec-
Diacetyldeuterohemin dimethyl ester, 301
trum, 302
demetallation, 301
synthesis, 302
Diacetyldeuteroporphyrin dimethyl ester,
Diformyldeuteroporphyrin dimethyl ester
259, 300
electronic spectrum, 302
synthesis, 226, 250, 259
purification, 303
3,7-Diacetyldeuteroporphyrin III, synthesis,
synthesis, 302
240
Diiminoisoindolene, 382
Diagenetic r eactions of
p orphyrins, 505, 53
N ,N-Dialkylcorroles
mass spectra, 360
nmr spectra, 360
synthesis, 359
/V, N-Dialkylporph yrins
basicity, 347
6
b-Diketones, synthesis, 129
g-Diketones, in pyrrole synthesis, 130
1,19-Dimethylbiladienes-ac
cyclization to porphyrins, 238
synthesis, 238
1,19-Dimethylbilenes-b, copper promoted
cyclization to porphyrins, 256
dealkylation, 347
N,Nr-Dimethylchlorins, 353
electronic spectra, 349
Dimethyldeuteroporphyrin
mass spectra, 349, 355
from deuteroporphyrin, 332
nmr spectra, 348, 354
dimethyl ester synthesis, 228
synthesis, 346, 352, 354
Diatomaceous earth, porphyrin chromatography, 567
Diazabenzoporphyrins, synthesis, 384
Diazaporphyrins
Dimethylformamide, solvent for porphyrin
metallation, 405, 408
Dinitrogen complexes, osmium porphyrins,
465
Dioxygen complexes
electronic spectra, 369
chromium porphyrins, 440, 443
metal complexes, 369
cobalt porphyrins, 468
synthesis, 369
Griffith model, 456
Diazomethane, reaction with protohemin,
213
Diborane
hemes, 455
infrared spectroscopy, 456
iron porphyrins, 455
reduction of acylpyrroles, 127
myoglobin, 457
reduction of formylpyrroles, 271
Pauling model, 456
reduction of pyrrylketones, 271
b-Dicarbonyl containing compounds, nitrosation, 107
Dichloromethyl methyl ether, formylation of
porphyrins, 283
picket fence-X-ray structure, 456
superoxide formulation, 457
2,3-Diphosphoglycerate, 48
Dipropionyldeuterohemin, synthesis, 300
Dipyrroketones, see pyrrylketones
Dichloromethylpyrroles, 151
2,2-Dipyrrolylketones, see pyrrylketones
5-Dichloromethylpyrrylketones, 269
2,2'-Dipyrrolylmethanes, see dipyrryl-
1,19-Dideoxybiladienes-ac, see biladienes-ac
1,19-Dideoxybilatrienes-abc, see bilatrienes-abc
1,19-Dideoxybilenes-b, see bilenes-b
methanes
Dipyrromethanes, see dipyrrylmethanes
Dipyrrylmethanes
meso-aroyl 90
meso-chloro, 220
condensation with 5,5'-diformylpyr-
coprohemin-pyridine hemochrome, 319
rylketones, 223
coproporphyrin I tetramethyl ester, 319
conversion to bilenes-/?, 249
coproporphyrin III tetramethyl ester, 319
conversion to porphyrins, 175
deoxophylloerythroetioporphyrin, 493
conversion to pyrrylmethanes, 206
deuterohemin, 295
conversion to tripyrrenes, 254
deuterohemin-pyridine hemochrome, 295
couplingwith pyrromethenes, 213
deuteroporphyrin, 294
detection on tic plates, 174
deuteroporphyrin dimethyl ester, 295
5,5'-dicarboxylates, decarboxylation,
diacetyldeuterohemin-pyridine hemo-
179,184
chrome, 300
differential protection of rings, 279
5,5'-diformyl, 182, 185, 187
5,5'-diunsubstituted
diacetyldeuteroporphyrin dimethyl
ester, 300
N,N-dialkylporphyrins, 349
conversion to porphyrin, 175
diazaporphyrins, 369
coupling with pyrrylketones, 215
diformyldeuterohemin-pyridine
synthesis, 179
hemochrome, 302
5-formyl, precursors of bilenes-/?, 252
5-formyl-5-unsubstituted, synthesis,
diformyldeuteroporphyrin dimethyl
ester, 302
190
etioporphyrin I, 493
formylation, 180
geoporphyrins, 493
meso-hydroxy, 220
harderoporphyrin trimethyl ester,
nomenclature, 3
323
oxidation to pyrrylketones, 220
properties, 163-175
hematohemin-pyridine hemochrome,
297
rearrangements, 180
hematoporphyrin dimethyl ester, 297
synthesis
heme a-pyridine hemochrome, 309
from acetoxymethylpyrroles, 169
hemec-pyridine hemochrome, 308
from azafulvenium cations, 167
hemin chloride-pyridine hemo-
from bromomethylpyrroles, 169
chrome, 209
from formaldehyde, 166
hyper type, 415
from lithium pyrrole carboxylates, 174
hypo type, 416
unsymmetric, 167
hypso type, 415
Vilsmeier-Haack formylation, 182
iron octaethylporphyrin fluoride, 414
Dipyrrylthioketones, see Pyrrylthioketones
Dry column chromatography of porphyrins,
563
iron octaethylporphyrin M-oxo dimer,
414
iron porphyrins, 466
Dyestuffs, phthalocyanines, 379
iron meso -tetra(p-tolyl)-porphyrin
chloride, 415
isospirographis hemin-pyridine hemochrome, 304
E
isospirographis porphyrin dimethyl
ester, 303
Electronic spectra
mesohemin-pyridine hemochrome, 299
N-acetylcorroles, 361
mesoporphyrin dimethyl ester, 299
N-alkylcorroles, 358
metalloporphyrins, see also specific
alio type, 416
compounds, 412-417
analysis and interpretation, 48
N-methylporphyrins, 343
bilanes, 273
monoazabenzoporphyrins, 383
bilenes-b, 273
monoazaporphyrins, 368
charge-transfer bands, 417
nickel porphyrins, 472
copper porphyrins, 472
normal type, 415
octaethylporphyrin, 414
diprotonated, 414
osmium porphyrins, 466
Enzymatic decarboxylation
coproporphyrinogen III, 280
coproporphyrinogen IV, 323
oxobilanes, 273
Epoxyporphyrins, 246
oxorhodo type,294
Esterification
pemptoporphyrin dimethyl ester, 321
photoprotoporphyrins (isomers 1 and 2)
dimethyl ester, 304
hematoporphyrin, 298
protohemin, 293
N-ethoxycarbonylmethylporphyrin
phthalocyanins, 376
nmr spectra, 350
y-phyllohemin-pyridine hemochrome,
rearrangements, 351, 356
329
synthesis, 350, 356
g-phylloporphyrin XV, 493
X-ray structure, 346
g-phylloporphyrin XV methyl ester,
3-Ethyl-8-acetyldeuteroporphyrin dimethyl ester, synthesis, 259
329
platinum octaethylporphyrin, 414
Ethyl a-oximinoacetoacetate, 102
platinum ra^Y;-tetra(/?-tolyl)-porphyrin,
Etioporphyrin, nomenclature, 7
Etioporphyrin I, synthesis, 211, 226
415
porphyrin a dimethyl ester, 309
Etioporphyrin II, synthesis, 258
protoporphyrin dimethyl ester, 290
Etioporphyrin III
pyridine hemochromes, see specific compounds
pyrrohemin-pyridine hemochrome, 327
from mesohemin, 300
from mesoporphyrin, 331
Etioporphyrin IV, synthesis, 228, 259
pyrroporphyrin methyl ester, 327
pyrrylketones, 267, 271
rhodohemin XV-pyridine hemochrome,
F
328
rhodoporphyrin XV, 493
rhodoporphyrin XV dimethyl ester, 328
Familial ferrihemoglobinemia, 31
rhodo type, 294
Ferritin, 64
ruthenium porphyrins, 466
Fischer porphyrin synthesis, 209
S-411 porphyrin tetramethyl ester, 322
Formaldehyde, incorporation into porphy-
Spirographis hemin-pyridine hemo-
rins, 249
chrome, 304
Spirographis porphyrin dimethyl
ester, 303
Formylation
copper deuteroporphyrin, 302
deuterohemin, 302
N-substituted porphyrins, 343, 355
dipyrrylmethanes, 180, 182
tetraazaporphyrins, 372
formation of pyrrylketones, 267
m e s o - t e t r a (p-tolyl)-porphyrin, 415
diprotonated, 415
N,N,N-trialkylporphyrins, 349
pyrroles, 146
1 -Formyl- 19-methylbilenes-/?, cyclization
to porphyrins, 256
urohemin-pyridine hemochrome, 316
Formylporphyrins, synthesis, 282
uroporphyrin I octamethyl ester, 316
Formylpyrroles
uroporphyrin III octamethyl ester, 316
acetals as protecting groups, 156
zinc octaethylporphyrin, 414
conversion to pyrromethenes, 199
zinc meso-tetra p-tolyl-porphy rin,
415
Electrophilic substitution
diborane reduction, 271
Girard hydrazones as protecting groups,
156
bilanes, 271
protection, 146
pyrromethenes, 207
synthesis, 146, 151
pyrrylketones. 268
5-unsubstituted, 151
Electrophoresis, porphyrins, 584
5-Formylpyrrylketones, 209
Formylvinyldeuteroporphyrins, 302
occurrence
isomer separation by column chroma-
petroleum and bitumens, 517
tography, 564
sediments, 511
isomer separation by tic, 562
shales, 533
2-Formyl-4-vinyl-deuteroporphyrin, see
Spirographis porphyrin
a-Free
petroporphyrins
distribution, 520
pyrroles
mass spectra, 519
conversion to pyrromethenes, 199, 204
structural characterization
reaction with acetoxymethylpyrroles, 169
number of isomeric porphyrins, 531
reaction with bromomethylpyrroles, 169
number of petroporphyrins, 528
synthesis, 162
oxidation and mass spectra, 525
oxidation to maleimides, 521
properties, 511
G
vanadyl porphyrins, 513, 517
Germanium porphyrins, 436
Gallium porphyrins, v-oxo dimers, 429
Glaucobilin, nomenclature, 18
Gas chromatography of geoporphyrins, 488
Glyoxylic acid, reductive alkylation of pyr-
of porphyrins, 569
roles, 124
Gatterman formylation, 146
Gold porphyrins, 471
Geeldikkop, 32
redox chemistry, 473
Gel filtration of porphyrins, 564
synthesis, 449
Geochemistry of porphyrins, 51
Griffith model of oxygenation, 456
Geological time scale, 549
Geoporphyrins
formation, diagenetic reactions
H
alkylation, 543
Diels-Alder adducts, 544
dimerization, 545
Hafnium porphyrins, 436
formation, Treibs' scheme, 505
Hafnium octaethylporphyrin, X-ray struc-
diagnetic reactions, 505, 536
ture, 436
aromatization, 539
Half-stercobilin, nomenclature, 20
decarboxylation, 540
Halogenated phthalocyanines, 376
demethanation, 542
porphyrins, 89
desterification, 538
Hantzsch, pyrrole synthesis, 129
devinylation, 541
Harderoporphyrin, isolation, 323
etio series formation, 542
Harderoporphyrin dimethyl ester, 281
redox reactions, 538
Harderoporphyrin trimethyl ester, synthesis, 278
fractionation, 488
HCl number, porphyrins, 585
gas chromatography, 488
high pressure liquid chromatography,
492
Hematin, 460
magnetic properties, 461
nomenclature, 25
free base porphyrins, 512, 518
Hematohemin, pyridine hemochrome, elec-
geological time scale, 549
tronic spectrum, 297
identification
Hematoporphyrin
electronic spectra, 493
dehydration, 298
GC/MS,502
dimethyl ether, 297
mass spectroscopy, 498
esterification, 298
via maleimides, 503, 547
iron insertion, 298
isolation, 488
nomenclature, 11
kerogen porphyrins, 534
preparation, 297
nickel porphyrins, 514, 535
to protoporphyrin dimethyl ester, 292
Hematoporphyrin dimethyl ester, electronic
spectrum, 297
Hematoporphyrinuria, 36
Heme, biosynthesis, 45, 65, 317
Hemetf
High pressure liquid chromatography of
porphyrins, 492, 558, 574
Histohematins, 30
History
metalloporphyrins, 393
of porphyrin and derivatives, 29-99
isolation, 310, 313
structure determination, 310
purification, 312
Homeostasis, hemoglobin, 62
Homoazaporphyrins, nomenclature, 21
Homoporphyrins, 351, 356
pyridine hemochrome, electronic spec trum,
309
Hydrides, rhodium porphyrins, 471
Hydrobilins, nomenclature, 16
Heme proteins
Hydrodic acid
crevice conformation, 46
iron content, 55
deiodination of iodopyrroles, 124
H3PO2, reductive alkylation, 124
resistance to denaturation, 58
Hemes
Hydropyrrins, nomenclature, 17
1- Hydroxy-2-desvinyl-2-formylethylidene-
carbonyl complexes, 457
dioxygen complexes, 455
ligation, 454
protoporphyrin, see Photoprotoporphyrin i
somer 2
3-Hydroxy-4-desvinyl-4-formylethylidene-
nitrosyl complexes, 458
protoporphyrin, see Photoprotoporphyrin
nomenclature, 25
isomer 1
redox chemi
stry, 454
Hemichrome salts, 461
infrared spectra, 461
nmr spectra, 461
meso Hydroxdipyrromethanes
220
2- Hydroxymethylpyrrole, porphyrin precursor, 86
Hyperelectronic spectra, 415
Hemin
Hypo electronic spectra, 416
iron removal, 291
Hypophosphorous acid, reductive alkyla-
isolation from blood, 291
tion of pyrroles, 124
nomenclature, 25
to protoporphyrin dimethyl ester, 291
Hemin(s),459
magnetic properties, 460
I
Hemin chloride, pyridine hemochrome,
electronic spectrum, 290
Hemochromatosis, 31
Imidines, intermediates in phthalocyanine
synthesis, 380
Hemochromogens, 55
Indium porphyrins, 429
Hemoglobin
Infrared spectra
crystallization, 55
characteristic vibrations of metal-axial
homeostasis, 62
Iigand chromophores, 422
iron content, determination, 52
T and R states, 69
hemichrome salts, 401
iron porphyrins, 450
Hemoglobinometry, 52
carbonyl complexes, 457, 466
Hemoglobinopathies, 31
metalloporphyrins, 422
Hemopexin, 60
molybdenum porphyrins, 445
Hemoproteinurias, 61
pyrrylketones, 267
Hemopyrroles, synthesis, 117, 119, 127
rhenium porphyrins, 445
Heptacarboxylic acid porphyrins, Type III,
tungsten porphyrins, 445
synthesis, 280
Inositol hexaphosphate, 48
Hexacarboxylic acid porphyrins, Type III,
synthesis, 2
Hexapyrrenes, 251
80
Iodination, of pyrroles, 162
Iodinative decarboxylation, pyrrole carboxylic acids, 124
Iodopyrroles
Isopemptoporphyrin dimethyl ester, synthe-
deiodination, 163
sis, 244, 257, 275, 281
synthesis, 162
Isoporphyrin, nomenclature, 9
Ionic radius
Isopurpurin 5, nomenclature, 8
effect on oxidation states of metallopor-
Isorhodinporphyring5, nomenclature, 7
phyrins, 411
Isospirographis hemin, electronic spectrum,
of metal, effect on porphyrin metallation,
411
304
Isospirographis porphyrin
Iridium porphyrins, synthesis, 449
electronic spectrum, 303
Iron
from photoprotoporphyrin, 305
sorption, 64
in heme and heme proteins, 55
insertion into hematoporphyrin, 298
migration in body, 63
pyridine hemochrome, electronic spectrum, 304
Isotopically labelled porphyrins, 244, 248,
284,285
removal from hemin, 291
raeso-tetraphenylporphyrin-M-oxo dimer
X-ray structure, 400
transfer into cells, 64
K
Iron octaethylporphyrin fluoride, electronic
spectrum, 414
Iron octaethylporphyrin /u-oxo dimer,
electronic spectrum, 414
Iron porphyrins, see also Hemes, Hemochromes, Hemins, Hematins, Hemichrome salts and specific compounds
carbonyl complexes, 457
infrared spectra, 457, 466
cis and trans effects, 465
Kerogen porphyrins, geochemical, 534
Keto esters, nitrosation, 107
Kinetics of porphyrin metallation, 409
Knorr synthesis of pyrroles, 102-128
execution, 107
Johnson variation, 104
Kleinspehn variation, 104
Knorr's pyrrole, 104
dioxygen complexes, 455
electronic spectra, 466
infrared spectra, 450
ligand exchange, 448
L
magnetic properties, 450
metal alkyls, 470
nitrido complexes, 462
nitrosyl complexes, 458
nomenclature, 25
Lanthanide porphyrins, 428, 432
Lead porphyrins, 436
Lead tetraacetate
oxidation of dipyrrylmethanes to pyrryl-
picket fence porphyrins, 455
redox chemistry, 448, 462
synthesis, 448
ketones, 220
oxidation of methylpyrroles, 149
Ligands
Iron protoporphyrin chloride, X-ray struc-
cobalt porphyrins, 452, 468
ture, 396
exchange, metalloporphyrins during
Iron meso tetra-p-tolyporphyrin chlo ride,electronic spectrum, 415
Isocoproporphyrin tetramethyl ester, synthesis, 278,280
Isoharderoporphyrin dimethyl ester, synthesis, 281
Isoharderoporphyrin trimethyl ester, syn-
chromatography, 420
hemes, 454
identification, metalloporphyrins, 421
iron porphyrins, 448
nickel porphyrins, 472
osmium porphyrins, 452
rhodium porphyrins, 452
thesis, 278
Lithium nitrite, nitrosating agent, 107
Isolation of natural porphyrins, 289
Lithium porphyrins, 424
M
pyridine hemochrome, electronic spec trum,299
MacDonald porphyrin synthesis, 177
Mesoporphyrin
Magnesium, insertion into porphyrins, 427
conversion to etioporphyrin III, 331
Magnesium alkoxides, magnesium insertion,
conversion to 1,3,5,8-tetramethyl-
409
Magnesiumchlorinp6, preparation, 325
2,4-dimethyl-6,7-dipropylporphyrin,
333
Magnesium 3,5-di-/-butyl-4-hydroxy-
nomenclature, 7
toluene, magnesium insertion, 427
Mesoporphyrin dimethyl ester
Magnesium octaethylporphyrin, photo-
electronic spectrum, 299
oxidation, 417
synthesis, 242, 257, 260, 261, 269, 274,
Magnesium porphyrins, 425
role in photosynthetic pigments, 427
synthesis, 427
Magnetic properties
hematins, 461
275, 277, 299
Mesoporphyrin II dimethyl ester, synthesis,
226
Mesoporphyrin III dimethyl ester, synthesis, 240
hemins, 460
Mesoporphyrin XI, synthesis, 275, 278
iron porphyrins, 450
Mesoporphyrin XI dimethyl ester, synthe-
Maleimides
from azaporphyrins, 342
from geoporphyrins, 503, 547
from petroporphyrins, 528
Manganese porphyrins
manganoglobin, 443
fi-oxo dimer, 444
reaction with dioxygen, 443
kk
role,, in photosynthesis, 443
synthesis, 442
sis, 257
Mesoporphyrin XIII dimethyl ester, synthesis, 228
Mesotetraphenylporphyrin see also Metaloporphyrins
chromatography, 571
synthesis, 89
Metal alkoxides, for porphyrin metallation,
49
Metal alkyl
cobalt porphyrins, 470
Manganoglobin, 443
iron porphyrins, 470
Mannich bases, pyrrolic, porphyrin precur sors , 87
for porphyrin metallations, 408
Mass spectra
N-alkylcorroles, 360
N,N-dialkylcorroles, 360
N,N-dialkylporphyrins, 349, 355
geoporphyrins, 498
metalloporphyrins, 422
Metal carbonates, see Porphyrin chromatography, 567
Metal carbonyls, for porphyrin metallation,
409
Metallation of porphyrins, 390, see also
Metalloporphyrins
petroporphyrins, 519
MetalIo /V-substituted porphyrins, 342
phthalocyanines, 378
Metallodiazaporphyrins, 369
N,N,N-trialkylporphyrins, 348, 354
Metallophthalocyanines, 377
Meconium, isolation of porphyrins, 322
Mercury porphyrins, 426
synthesis, 427
Mesobilirhodins, nomenclature, 20
heats of sublimation, 587
synthesis, 374, 377
Metalloporphyrins, 389-483, see also specific
compounds and Porphyrin, metallo
Mesobilirubin, nomenclature, 18
acid lability, 418
Mesobilirubinogen, nomenclature, 18
alkali metals, 424
Mesobiliverdin, nomenclature, 18
alkaline earth metals, 425
Mesohemin
alio complexes, 416
conversion to etioporphyrin III, 300
axial ligand identification, 421
preparation, 299
charge transfer bands, 417
purification, 564
chromatography, 419, 553-580
choice of method, 554
metal carbonyls, 408, 409
column, 564
metal complexes, 405
high pressure liquid, 558, 574
phenol as solvent, 408, 409
Iigand exchange, 420
pyridine as solvent, 405, 407
paper, 561, 565
tetramethylureaas solvent, 408
precautions, 557
zinc complexes, 425
thin layer, 563
Metallotetraazaporphyrins, 371
classification, 395
Metallotriazabenzoporphyrins, 386
coordination types, 396
b-Methoxypyrroles, 134
demetallation by acids, 417
1-Methyl-19-alkyltetradehydrocorrins
electronic spectra, 412-417, see also
conversion to meso-alkylporphyrins,
Electronic spec tra, and sp ecific
compounds
esters, paper chromatography, 565
thin layer chromatography, 567
hyper, 415
hypo,415
normal, 415
group(s)
la, 424
IIa and lib, 425
IIIaand IIIb, 428
IVa, IVb, Va, and Vb, 432
247
synthesis, 247
1- Methyl-19-bromobiladienes-flc
cyclization to por
phyrins, 242
synthesis, 242
Methyl 4-(2-methoxycarbonylethyl)-3methoxycarbonylmethyl-5-methylpyrrole-2-carboxylate, synthesis, 111
2- Methyl-3-oxobutyraldehyde, 105
5-Methyl-5'-unsubstituted pyrromethenes,
conversion to biladienes-^c, 242
l-Methylbiladienes-ac, cyclization to por phyrins,-
Via and Via, 440
specific examples and experi-
VIIIa and lb, 447-474
mental details, 258
heats of sublimation, 587
I-Methylbilenes-/?
historical aspects, 393
copper promoted cyclization to porphy-
infrared spectroscopy, 422
rins, 256
lanthanides, 428
cyclization to porphyrins, specific exam-
Ligand exchange during chromatography,
420
mass spectroscopy, 422
Mossbauer spectroscopy, 423
ples and experimental details, 259
N-Methylchlorins
nmr spectra, 353
synthesis. 352
naturally occurring, 393
/V-MethylcoiTole, X-ray structure, 358
oxidation states, 412
Methylene bridged porphyrins (N-Co), 350
periodic table of, 394
purification, 419
Raman spectroscopy, 423
N-Methyletioporphyrins, 381
N-Methylporphyrins, electronic spectra,
343
stability, 417
meso-Methylporphyrins, synthesis, 242
stability index, 418
Methylpyrroles
stability TPPvsOEP, 419
acetoxylation, 149
stable oxidation states, 411
conversion to aldehydes, 150
synthesis
conversion tocarboxylic acid, 156, 159
acetic acid as solvent, 405
conversion to pyrromethenes, 204
benzonitrile as solvent, 405, 407
conversion to trichloromethylpyrrole, 160
DMFas solvent, 405, 408
halogenation, 148, 150, 156
effect of ionic radius, 411
1-Methyltetradehydrocorrins, from
effect of oxidation state of metal, 410
biladienes ac, 246
kinetics, 409
Miranda family, 33
metal acac, 405, 407
Modification of natural porphyrins, 289
metal alkoxides, 405, 408
Molybdenum porphyrins
infrared spectra, 445
Niobium meso-tetraphenylporphyrin
synthesis, 441
(Nb2O3 TPP), X-ray structure, 400
X-ray structures, 444
Niobium meso-tetraphenylporphyrin oxo
Molybdenum meso-tetraphenyIporphyrin
dioxo complex, X-ray structure, 398
Monoazabenzoporphyrins
complex, X-ray structure, 398
M-Nitrido iron porphyrins, 462
Nitrosation, /3-dicarbonyl containing com-
electronic spectra, 386
pounds, 107
synthesis, 383
Nitrosyl complexes
Monoazaporphyrins, 365-368
basicity, 367
hemes, 458
iron porphyrins, 458
from biladienes-tfc, 366
Nmr spectra
electronic spectra, 368
N-acetylcorroles, 361
reduction, 367
N-alkylcorroles, 357
synthesis, 365
N,N-dialkylcorroles, 359
from verdohemins, 366
N,N-dialkylporphyrins, 348, 354
Monobenztetraazaporphyrins, 380
N-ethoxycarbonylmethylporphyrin, 350
Monographs, in porphyrin field, 38
N,N-bis ethoxycarbonylmethylporphyrin,
Monohydroxyethyldeuterohemin resorcinyl
ether, 296
350
hemichrome salts, 461
Monohydroxyethyl monovinyldeuteroporphyrin, 292
N-methylchlorins, 353
N-methylporphyrins, 344
Mbssbauer spectroscopy, metalloporphyrins, 423
Nomenclature, 1-27
annelated systems with fused rings, 10
Myoglobin
lineartri- and tetrapyrroles, 14-19
crystallization, 56
metal complexes, 21-25
oxygenation, 457
IUPAC rules, 23
Myohematins, 30
trivial names, 24
porphyrins, 4-14
parent systems, 4, 9
trivial nomenclature, 6, 10
N
type nomenclature, 5, 10
pyrroles, 2
Naturally occurring metalloporphyrins,
393
Naturally occurring porphyrins, isolation
and modification, 289
Neoporphyrin, 4
ring contracted and ring expanded systems, 19
semisystematic nomenclature, 11
systems with two pyrrole rings, 3
b-Norbiladienes-ac, 241
nomenclature, 10
Neopurpurins, nomenclature, 8
Nickel octaethylporphyrin. X-ray struc-
O
ture, 396
Nickel porphyrins
Octaalkylporphyrins, chromatography
crystalline, naturally occurring, 535
column, 570
electronic spectra, 472
paper, 570
geochemical, 514, 535
ligand exchange, 472
redox chemistry, 473
synthesis, 449
tic, 570
Octaethylporphyrin
diprotonated electronic spectrum, 414
electronic spectrum, 414
Niobium octaethylporphyrin, X-ray struc-
HI3 adduct, X-ray structure, 401
ture, 436
metal complexes compared to me so-tetm-
Niobium porphyrins, 435
phenylporphyrin, 395
P
synthesis, 88
Octamethylporphyrin, synthesis, 87
Ooporphyrin, 33
Paal-Knorr, pyrrole synthesis, 129
Oorhodein, 33
Palladium octaethylchlorin, 407
Orientation reversal sequence, synthesis of
Pauling model of oxygenation, 456
formylpyrroles, 156
Osmium porphyrins
carbonyl complexes, 463, 466
Pemptoporphyrin
isolation, 321
nomenclature, 11
cis and trans effects, 465
synthesis, 244, 252
dinitrogen complexes, 465
Pemptoporphyrin dimethyl ester, synthesis,
dioxocomplexes, 464
278,281
electronic spectra, 466
Pentacarboxylic acid porphyrins Type III,
ligand exchange, 452
redox chemistry, 452, 464
synthesis, 449
synthesis, 280
2,4-Pentanedione, Michael addition to acryIate, 126
Oxidation, see also Redox
Periodic table of metalloporphyrins, 394
metalloporphyrins, 412
Peroxytitanium octaethylporphyrin, 435
of metals, effect on porphyrin metallation,
Petroleum, porphyrin occurrence, 517
410
porphyrinogens, 94
stable, metalloporphyrins, 411
Petroporphyrins, see Geoporphyrins
Phenol, solvent for porphyrin metallation,
405, 407
using eerie ammonium nitrate, 220
Pheophorbides, nomenclature, 8, 13
lead tetraacetate, 149, 220
Pheophorbide a, 326
sulfuryl chloride, 148, 150, 159, 220
Pheophytin(s), nomenclature, 13, 14
t-butyl hypochlorite, 148, 150, 159, 255,
Pheophytina, 326
269
Pheoporphyrins, nomenclature, 8
2,3-Oxidoporphyrins, 247
Oximes, reduction, 108
Pheoporphyrin a5, from Rhodoporphyrin,
332
Oxobilanes
Phlorin, nomenclature, 13
a-oxobilanes, 255
Phorbin, nomenclature, 4
cyclization to porphyrins, 269
Phosphorus porphyrins, 436
reduction, 271
Photooxidation
synthesis, 270
b-oxobilanes
conversion to oxophlorins, 276
cyclization to porphyrins, 274
synthesis, 274
electronic spectra, 273
Oxo complexes, osmium porphyrins, 464
m-Oxo dimers
aluminum, 429
gallium, 429
magnesium octaethylporphyrin, 417
Photoprotoporphyrins
conversion to isospirographis porphyrin,
305
conversion to Spirographis porphyrin,
305
electronic spectra, 304
from protoporphyrin, 293
separation by chromatography, 305
synthesis, 306
manganese, 444
Photosynthesis, magnesium, role, 427, 443
scandium, 431
Phthalocyanines, 374-380
Oxophlorins
acetylation, 277
analogs, 380-383
p-anion radicals, 377
from &-oxobilanes, 276
dyestuffs, 379
reduction, 277
electronic spectra, 376
Oxorhodo-type electronic spectra, 294
halogenation, 376
a-Oxymesoporphyrin, 284
heats of sublimation, 587
b-Oxymesoporphyrin, 284
imidines, intermediates in synthesis, 380
Oxyporphyrins, see Oxophlorins
mass spectra, 378
mechanism of formation, 375
Porphomethene
metal complexes, 374, 377
intermediates in porphyrin synthesis, 98
metal derivatives, 377
nomenclature, 13
oxidation, 376
Porphyrazines, see Tetraazaporphyrins
sulfonated, 376
Porphyria, 31
synthesis, 374
drug induced,36
uranium, X-ray structure, 399
Porphyrin(s), see also geo-, metallo-
X-ray structure, 376
and specific compounds
Phycobiliverdin, nomenclature, 19
meso-alkyl, 242, 247
Phycobiliviolin, nomenclature, 19
aza,365,388
Phycocyanin, nomenclature, 19
bearing labile groups, synthesis, 280
Phycocyanobilin, nomenclature, 19
biological markers, 486
Phycoerythrobilin, nomenclature, 19
bromo, hydrogenolysis, 282
Phyllochlorin, preparation, 327
capped,455
Phylloerythrin
chromatography, 553-580
nomenclature, 11
countercurrent distribution, 584
preparation, 327
crystallization, 585
Phylloporphyrin
nomenclature, 11
electrophoresis, 584
epoxy,246
preparation, 327
esters, chromatography, 565
g-Phylloporphyrin, nomenclature, 7
esterification, 576
g-Phylloporphyrin IV methyl ester, synthe-
vV-ethoxycarbonyl, 350
sis, 261
X-ray structure, 345
g-Phylloporphyrin XV, preparation, 329
a and b faces, nomenclature, 22
g-Phylloporphyrin XV methyl ester, synthe-
Fischer synthesis, 209
sis, 239, 242,261
b-formylation, 282
Phytoporphyrin, nomenclature, 11
from azafulvenium ions, 93
Picket fence porphyrins, 455
from biladienes-flc, 248, 258, 261
Piloty-Robinson, pyrrole synthesis, 132
from bilenes-6, 249, 259, 260
Platinum octaethylporphyrin, electronic
from chlorophylls, 324-329
spectrum, 414
Platinum meso-tetra(p-toly l)porphyrin,
electronic spectrum, 415
Platinum porphyrins, 471
redox chemistry, 472
synthesis, 449
from 5,5'-diformylpyrrylketones and
dipyrrylmethanes, 221
from 1,19-dimethylbilenes-b and copper,
256
from dipyrrylmethanes, 175, 209
from l-formyl-19-methylbilenes-6, 256
Polyamide column chromatography of
from Mannich bases, 87
metalloporphyrins, 564
from meconium, 322
tic of metalloporphyrins, 563
from 1-methylbilenes-b and copper, 256
Polymers, silicon phthalocyanines, 402
from monopyrroles, 85-100
Polypyrromethenes, intermediates in por-
from a-oxobilanes, 269, 275
phyrin synthesis, 95
from b-oxobilanes, 274, 278
Porphin
from porphodimethenes, 98
nomenclature, 4
synthesis, 85
from porphomethenes, 98
from porphyrinogens, 91
Porphinato, nomenclature, 23
from pyrroles, 85-100
Porphobilinogen
from pyrromethenes, 211
from 6-azaindoles, 135
lactam, synthesis, 135
Porphodimethene(s)
and copper, 239
gas chromatography, 569
gel filtration, 564
intermediates in porphyrin synthesis, 98
geochemistry, 51, 485-551
nomenclature, 13
halogenated, 89
HCl-number, 585
conversion to coporporphyrin III, 329
heats of sublimination, 587
isotopically labelled, 244, 248
isotopically labeled, 244, 248, 284
nomenclature, 7
MacDonald synthesis, 177
oxidation to diformyldeuteroporphyrin,
metabolism, regulation, 37
metal insertion, see metalloporphyrins
meso-methyl, 242
302
reduction, 299
Protoporphyrin dimethyl ester
purification, 581-589
chromatography, 292
purity, criteria, 582
electronic spectrum, 290
meso-pyrryl, 240
formation of photoprotoporphyrin, 293
regulation of metabolism, 37
from hematoporphyrin, 292
related to Chlorobium chlorophylls, 257
from hemin, 291
S-411,278
light sensitivity, 293
sublimination, 586
N-substituted, see N-substituted porphy rins
and specific compounds
2+2 synthesis, 224-230
synthesis, see Synthesis and specific
reduction, 299
synthesis, 244, 248, 257, 278
Protoporphyrin I dimethyl ester, synthesis,
278,281
Protoporphyrin IX, see Protoporphyrin
compounds
Protoporphyrin di-tert-butyl ester, 306
mechanistic considerations, 90
Pterobilin, nomenclature, 20
substituent effects, 96
Purification
meso-tetramethyl, 90
hemins, 564
meso-tetraphenyl, 89
metalloporphyrins, 419
vinyl containing, synthesis, 244, 281
porphyrins, 581-589
water soluble, 573
Porphyrins, purification, 312
Purpurin 5, nomenclature, 7
Purpurin 7
Porphyrins dimethyl ester, electronic spec-
nomenclature, 7
trum, 309
preparation, 327
Porphyrinc
Purpurin 9, 7
preparation, 309
Pyridine, solvent for porphyrin metallation,
pyridine hemochrome, electronic spectrum, 308
Porphyrinc tetramethyl ester, electronic
spectrum, 308
Porphyrin S-411, isolation, 322
Porphyrinogens
meso-acetoxy, 277
intermediates in porphyrin synthesis, 91
405
Pyrrocolls, 161
Pyrroketones, see Pyrrylketones
2-(2H-pyrrol-2-ylidenemethyl)-pyrrole,
see Pyrromethenes
Pyrroleacetic acids, from reductive alkylation
of pyrroles, 124
Pyrrole(s)
nomenclature, 4, 13
a-acetoxymethyl, 149
oxidation, 94
from ammonium mucate, 129
N,N,N,N-tetramethyl, 349
azafulvenium ions, 93
Potassium porphyrins, 424
from azines, 132
Protohemin
t-butyl ester
conversion to deuterohemin, 295
cleavage, 124
esterification, 293
containing, 117
purification, 564
from N-carbethoxyglycine esters, 134
reaction with diazomethane, 213
carboxylates, 124
reduction, 299
decarboxylation, 143
Protopheophytins, nomenclature, 13
a-carboxylates, 154, 156, 159
Protoporphyrin
a-chloromethyl, 148
chromatography, 293
crypto, 104, 117
cyanovinyl, 147
Pyrroporphyrin methy l ester , sy nthesis, 24 2
dehalogenation, 124, 154
Pyrroporphyrin XV methyl ester
a-dichloromethyl, 151
preparation, 327
3,4-diethyl, synthesis, 127
synthesis, 262
from g-diketones, 130
Pyrrylcarbinyl cations, see Azaful-
esters, hydrolysis, 143, 153
venium ions
transbenzylation, 125
Pyrrylketones
formyl, acetals, 156
5,5'-bisacetoxymethyl, 216
hydrazones, 156
5,5'-bischloromethyl, 216
to pyrromethenes, 199
5-chloromethyl, 269
synthesis, 146, 151
cleavage by bromine, 217
a-free, synthesis, 162
coupling with dipyrrylmethanes, 215
to dipyrrylmethanes, 169
diborane reduction, 271
to pyrromethenes, 199, 204
5-dichloromethyl, 269
hemo-synthesis, 117, 119, 127
a-hydroxymethyl, 86
5,5'-diformyl, 216, 221
condensation with dipyrrylmethanes,
iodo,162
223
Knorr's, 104
5,5'-dimethyl, oxidation to diformyl, 221
b-methoxy, 134
from dipyrrylmethanes, 220
a-methyl, 148
to p
electronic spectra, 267, 271
yrromethenes, 2
reductive al
04
kylation, 124
electrophilic substitution, 268
5-formyl, 269
saponification, 143
ir spectra, 267
synthesis from acyclic precursors, 101
5-methyl, oxidation with/-butylhypo-
fromp-toluene sulfonyl glycine esters, 134
chlorite, 269
a-trichloromethyl, 160
nomenclature, 3
b-vinyl-containing; precursor synthesis,
properties, 267
121
Pyrrole carboxylic acids, decarboxylation, 124, 144
Pyrroloindolizenes, from 3-acetyldipyrrylmethanes, 251
meso-Pyrrolylporphyrins, 252
reduction to dipyrrylmethanes, 220, 268
synthesis, 217, 220, 266
thio, 218
unsymmetric, 218
meso-Pyrrylporphyrins, synthesis, 240
Pyrrylthioketones, 218
Pyrromethanes, see Dipyrrylmethanes
Pyrromethenes
R
bromination, 207
meso-chloro, 220
cis- and rra/w-isomers, 95
copper catalyzed dimerization
Raman spectroscopy, metalloporphyrins,
423
Rearrangements
coupling with dipyrrylmethanes, 213
7V-alkylcorroles, 358
5,5'-dibromo-porphyrin synthesis, 211
dipyrrylmethanes, 180
5,5'-dimethyl-porphyrin synthesis, 211
A-ethoxycarbonylmethylporphyrin, 351,
from dipyrrylmethanes, 206
electrophilic attack, 207
from a-free pyrroles, 199, 204
a-methyl, oxidation, 206
356
Reconstitution, apo myoglobin-Ytterbium
mesoporphyrin, 431
Redox chemistry, see also oxidation and re-
nomenclature, 3
duction
perbromides, 205
cobalt porphyrins, 452
properties, 198
copper porphyrins, 473
synthesis, 198-207
gold porphyrins, 473
Pyrroporphyrin, nomenclature, 6, 7, 11
hemes, 454
iron porphyrins, 448, 462
nickel porphyrins, 473
osmium porphyrins, 452, 464
platinum porphyrins, 472
rhodium porphyrins, 452, 471
ruthenium porphyrins, 448, 464
Rhodoporphyrin IV diethyl ester, synthesis
261
Rhodoporphyrin V diethyl ester, synthesis,
261
Rhodoporphyrin XII diethyl ester, synthesis, 261
silver porphyrins, 473
Rhodoporphyrin XV, preparation, 328
zinc porphyrins, 427
Rhodoporphyrin XV diethyl ester, synthe sis,
Reduction, see also Redox chemistry
bromoporphyrins, 282
catalytic, iodopyrroles, 124
235, 242, 261
Rhodoporphyrin XV dimethyl ester, synthesis,
278
diborane, 127
Rhodo type electronic spectra, 294
monazaporphyrins, 367
Rothemund porphyrin synthesis, 86, 88
oximes, 108
mechanism, 90
a-oxobilanes, 271
Rubidium porphyrins, 424
oxophlorins, 277
Ruthenium porphyrins
protohemin, 299
carbonyl complexes, 463, 466
protoporphyrin, 299
cis and trans effects, 465
pyrrylketones, 267
electronic spectra, 466
to dipyrrylmethanes, 220
tetraazaporphyrins, 372
redox chemistry, 448, 464
synthesis, 448
xanthoporphyrinogens, 277
Reductive alkylation, pyrroles, 124
Regulation of porphyrin metabolism, 37
S
Reviews, in porphyrin field, 38
Rhenium porphyrins
infrared spectra, 445
synthesis, 442, 446
X-ray structure, 447
bis-(Rhenium tricarbonyl)meso-tetraphenylporphyrin, X-ray structure, 399
Rhodin g3, nomenclature, 7
Rhodin g5
nomenclature, 7
Rhodin g7, nomenclature, 7
preparation, 326
S-411 porphyrin trimethyl ester, synthesis,
278
Sapphyrin, nomenclature, 21
Scandium porphyrins, 431
m-oxo dimers, 431
Sediments, porphyrin occurrence, 511
Sephadex (LH-20) porphyrin chromatography, 568
Shales, porphyrin occurrence, 533
Sideropenia, 31
Rhodinporphyrin g5, nomenclature, 7
Silica-gel tic of porphyrins, 562
bis-(Rhodium dicarbonyl)octaethylpor-
Silicates, porphyrin chromatography, 567
phyrin, X-ray structure, 399
Rhodium N-methyloctaethylporphyrin, 346
Rhodium porphyrins
carbonyl complexes, 471
hydrides, 471
ligand exchange, 452
Silicon phthalocyanine, polymers, 402
Silicon porphyrins, 436
silylated,503
Silver porphyrins
redox chemistry, 473
synthesis, 453
metal alkyls, 470
Sodium porphyrins, 424
redox chemistry, 452, 471
Soret region, 48, 414
synthesis, 448, 470
Spirographis hemin
Rhodochlorin, preparation, 327
Rhodoporphyrin
conversion to pheoporphyrin g5, 332
nomenclature, 6, 7
Rhodoporphyrin I diethyl ester, synthesis,
261
crystallization, 55
electronic spectrum, 304
Spirographis porphyrin
isolation, 304
nomenclature, 12
from photoprotoporphyrin, 305
pyridine hemochrome, electronic spectrum, 304
separation from isospirographis porphyrin, 305
synthesis, 244, 305
Spirographis porphyrin dimethyl ester
bilenes-b, 249, 255
bismuth porphyrins, 439
boron porphyrins, 429
cadmium porphyrins, 426
calcium porphyrins, 426
chlorohemin, 33
electronic spectrum, 303
chromium porphyrins, 440
synthesis, 281
cobalt porphyrins, 449, 468
Stability, metalloporphyrins, 419
copper etioporphyrin I, 239
Stability index, metalloporphyrins, 418
copper etioporphyrin II, 240
Stercobilin, nomenclature, 18
copper porphyrins, 449
Stercobilinogens, nomenclature, 20
coproporphyrin 1,211
Strontium porphyrins, 426
coproporphyrin II, 240
Sublimination
coproporphyrin II tetramethyl ester, 226,
heats of, 587
258
porphyrins, 586
coproporphyrin III, 228
b-Substituted porphyrins, from monopyr-
coproporphyrin III tetramethyl ester, 248,
roles, 87
N-Substituted porphyrins, 341-357
basicity, 344
257, 260, 274, 275,277
coproporphyrin IV tetramethyl ester, 257,
250, 275
demethylation, 343
cytodeuteroporphyrin, 240, 310
electronic spectra, 343, 355
deoxyphylloerythroetioporphyrin, 252,
metal complexes, 342
256, 262
nmr spectra, 344, 354
deuteroporphyrin dimethyl ester, 243, 262
synthesis, 347, 351, 354
diacetyldeuteroporphyrin, 240, 201
X-ray structure, 363
diacetyldeuteroporphyrin dimethyl
Sulfolane, for porphyrin metallation, 408
Sulfuryl chloride
conversion of dipyrrylmethanes to
pyrrylketones, 207
methylpyrrole chlorinations, 148, 150, 159
oxidation of dipyrrylmethanes to
pyrrylketones, 220
Symposia
in porphyrin field, 40
Synthesis
N-acetylcorroles, 361
4-acetyldeuteroporphyrin diethyl
ester, 259
3-acetyl-8-ethyldeuteroporphyrin
dimethyl ester, 259
alkali metal porphyrins, 424
alkaline earth porphyrins, 425
N-alkylcorroles, 357
aluminum porphyrins, 429
antimony porphyrins, 436, 439
arsenic porphyrins, 436, 439
azaporphyrins, 365-384
barium porphyrins, 426
beryllium porphyrins, 425
biladienes-ac, 238, 242, 248
bilatrienes-abc, 246
ester, 226, 250, 259
N,N-dialkylcorroles, 359
N,N-dialkylporphyrins, 346, 352, 354
diazabenzoporphyrins, 383
diazaporphyrins, 369
3,4-diethylpyrrole, 127
diformyldeuteroporphyrin, 302
5,5'-diformylpyrrylketones, 221
b-diketones, 129
1,19-dimethylbiladienes-flc, 238
dimethyldeuteroporphyrin dimethyl
ester, 228
dipropionyldeuterohemin, 300
dipyrrylmethanes, 166
N-ethoxycarbonylmethylporphyrin, 350,
356
N,N-bis-ethoxycarbonylmethylporphyrin,
350
3-ethyl-8-acetyldeuteroporphyrin
dimethyl ester, 259
etioporphyrin I, 211, 226
etioporphyrin II, 258
etioporphyrin III, 300
etioporphyrin IV, 228, 259
formylporphyrins, 282
germanium porphyrins, 436
gold porphyrins, 449
phosphorus porphyrins, 436
hafnium porphyrins, 436
photoprotoporphyrins, 306
harderoporphyrin dimethyl ester, 281
phthalocyanines, 374
harderoporphyrin trimethyl ester, 278
g-phylloporphyrin IV methyl ester, 261
hematoporphyrin, 297
g-phylloporphyrin XV methyl ester, 239,
hemopyrroles, 127
hexacarboxylic acid porphyrins, type III,
280
242, 261
platinum porphyrins, 471
porphyrin c, 309
indium porphyrins, 429
potassium porphyrins, 424
iodopyrroles, 162
protoporphyrin dimethyl ester, 244, 248,
iridium porphyrins, 449, 470
257,278,291
iron porphyrins, 448
protoporphyrin 1 dimethyl ester, 278, 281
isocoproporphyrin tetramethyl ester,
pyrrole(s), 101-128
278,280
pyrromethenes, 198-207
isoharderoporphyrin trimethyl ester, 278,
pyrroporphyrin XV methyl ester, 242, 262
281
isopemptoporphyrin dimethyl ester, 244,
257,275,281
pyrrylketones, 216, 266
meso-pyrrylporphyrins, 240
rhenium porphyrins, 442, 446
isospirographis porphyrin, 305
rhodium porphyrins, 448, 470
lanthanide porphyrins, 428, 432
rhodoporphyrin I diethyl ester, 261
lead porphyrins, 436
rhodoporphyrin IV diethyl ester, 261
lithium porphyrins, 424
rhodoporphyrin V diethyl ester, 261
magnesium porphyrins, 427
rhodoporphyrin XII diethyl ester, 261
manganese porphyrins, 442
rhodoporphyrin XV diethyl ester, 235,
mercury porphyrins, 427
242,261
mesohemin, 299
rhodoporphyrin XV dimethyl ester, 278
mesoporphyrin dimethyl ester, 226, 242,
rubidium porphyrin, 424
257, 260, 261, 269, 274, 275, 277, 299
ruthenium porphyrins, 448
mesoporphyrin III dimethyl ester, 240
S-411 porphyrin, 278
mesoporphyrin XI, 275, 278
scandium porphyrins, 431
mesoporphyrin XI dimethyl ester, 257
silicon porphyrins, 436
mesoporphyrin XIII dimethyl ester, 228
silver porphyrins, 453
metallophthalocyanines, 374, 377
sodium porphyrins, 424
1 -methyl- 19-alkyltetradehydrocorrins,
Spirographis porphyrin, 244, 304
247
1-methyl-19-bromobiladienes-ac, 242
Spirographs porphyrin dimethyl ester,
281
N-methylchlorins, 352
strontium porphyrins, 426
meso-methylporphyiins, 242
N-substituted porphyrins, 347, 351, 354
1-methyltetradehydrocorrins, 246
tantalum porphyrins, 436
molybdenum porphyrin, 441
technetium porphyrins, 442, 446
monazaporphyrins, 365
tetraazaporphyrins, 370, 373
nickel porphyrins, 449
rapso-tetraphenylporphyrins, 89
niobium porphyrins, 436
thallium porphyrins, 429
octaethylporphyrin, 88
thorium porphyrins, 436
octamethylporphyrin, 87
tin porphyrins, 436, 439
osmium porphyrins, 449
titanium porphyrins, 435
a-oxobilanes, 270
N,N,N-triaikyIporphyrins, 347, 354
b-oxobilanes, 274
triazabenzoporphyrins, 384
pemptoporphyrin, 244, 252
tungsten porphyrins, 441
pemptoporphyrin dimethyl ester, 278, 281
vanadium porphyrins, 435
pentacarboxylic acid porphyrins, 280
vinylporphyrins, 244, 281
yttrium porphyrins, 431, 437
Tin octaethylporphyrin, X-ray struc-
zinc porphyrins, 427
ture, 437
zirconium porphyrins, 436
Tin porphyrins, 436, 439
Tin meso tetraphenylporphyrin dichloide,
X-ray structure, 397
T
Titanium octaethylporphyrin, peroxy complex, 435
Talc, metalloporphyrin chromatography,
569
Titanium porphyrins, 435
Titanium meso tetraphenylporphyrin oxo
Tantalum porphyrins, 436
complex, X-ray structure, 397
Technitium porphyrins
p-Toluenesulfonyl glycine esters, pyrrole
synthesis, 442, 446
precursors, 134
X-ray structures, 447
Transbenzylation, of pyrrole carboxylate es ters,
meso-Tetraarylporphyrins
125
unsymmetrically substituted, 89
Trans effect, 465
synthesis, 89
Transferrin, 64
Tetraazabenzoporphyrins, see Phthalocyanines
N N ,N-Trialkylporphyrins
electronic spectra, 349
Tetraazaporphyrins, 370-373
mass spectra, 349, 355
electronic spectra, 372
nmr spectra, 348, 354
metal complexes, 371
synthesis, 347, 354
reduction, 372
3,4,5-Trialkylpyrroles, 143
synthesis, 370, 373
Triazabenzoporphyrins
Tetrabenzoporphyrins, nomenclature,
1 0
l,3,5,8-Tetramethyl-2,4-diethyl-6,7dipropylporphyrin,
metal complexes, 386
synthesis, 384
from
Tribenztetraazaporphyrins, 380
mesoporphyrin,
333
Trichloromethylpyrroles
hydrolysis, 161
synthesis, 160
w^so-Tetramethylporphyrin, 90
N,N,N,N-Tetramethylporphyrinogens, 349
N,N,N-Trimethylchlorins, 353
Tetramethylurea, for porphyrin metalla-
Trimethyloxonium tetrafluoroborate,
tions, 408
porphyrin esterification, 576
meso-Tetra(pentahalophenyl)porphyrins,
Tris(triphenylphosphine)chlororhodium,
decarbonylation of formylpyrroles,
89
meso-Tetraphenylchlorin, 8
9
meso -Tetraphenylporphyrin
1
63
Tripyrrenes, from dipyrrylmethanes, 254
synthesis, 89
Tripyrrins, nomenclature, 17
X-ray structure, 399
Tungsten porphyrins
2HC1 X-ray structure, 401
meso -Tetra(p-tolyl)-porphyrin
diprotonated electronic spectrum, 415
infrared spectra, 445
synthesis, 441
Turacin, 318
electronic spectrum, 415
meso -Tetrasubstituted porphyrins,
chromatography
column, 572
U
tlc, 571
Thallium(III) nitrate, introduction of acetate
into pyrrole, 127
Thallium porphyrins, 429
1-Thioformylbilenes-/?, 257
Thorium porphyrins, 436
a-Unsubstituted biladienes-ac
cyclization to porphyrins, 248
synthesis, 248
5-Unsubstituted-2-formy !pyrroles,
synthesis, 151
Uranium bis phthalocyanine, X-ray struc-
X
ture, 399
Urobilin, nomenclature, 18
Xanththoporphyrinogen, reduction, 277
Urobilinogen, nomenclature, 18
X-ray structures
Urohemin, pyridine hemochrome, elec-
N-alkylcorroles, 358
tronic spectrum, 316
antimony octaethylporphyrin, 437
Uroporphyrin
boron octaethylporphyrin
chromatography, 560
[(B2O(OR)2(OEP)], 399
nomenclature, 5, 7
cobalt TV-methyl meso-tetraphenyl-
''separation" by paper chromatography,
565
porphyrin, 356
N-ethoxycarbonylmethylporphyrin, 346
Uroporphyrin I, preparation, 318
hafnium octaethylporphyrin, 436
Uroporphyrin I octamethyl ester, electronic
iron protoporphyrin chloride, 396
spectrum, 316
iron meso-tetraphenylporphyrin-m-oxo
Uroporphyrin III, isolation, 318
Uroporphyrin III octamethyl ester, electronic spectrum, 316
dimer, 400
N-methylcorrole, 358
molybdenum porphyrins, 444
Uroporphyrinogen I, decarboxylation, 280
molybdenum-meso-tetraphenylporphyrin
dioxo complex, 398
V
nickel octaethylporphyrin, 396
niobium octaethylporphyrin, 436
niobium meso -tetraphenylporphyrin
Vanadyl deoxophylloerythroetioporphyrin
in petroleum and shale, 486
(Nb2O3TPPMOO
niobium meso-tetraphenylporphyrin-oxo
X-ray structure, 487
complex, 398
Vanadyl porphyrins, 435
octaethylporphyrin-HI3, 401
geochemical, 513, 517
oxygenated picket fence, 456
Verdohemins, conversion to monazaporphyrins, 366
phthalocyanines, 376
rhenium porphyrins, 447
Vibrational spectroscopy, see Infrared spec-
bis(rhenium-tricarbonyl)m£S6>-tetra-
troscopy
phenylporphyrin, 399
Vilsmeier-Haack
bis(rhodium dicarbonyl)octaethylpor-
copper deuteroporphyrins, 302
deuterohemin, 302
phyrin, 399
rhodium N-methyloctaethylporphyrin,
formylation of dipyrrylmethanes, 180, 182
346
formylation of pyrroles, 146
N-substituted porphyrins, 363
pyrrylketone formation, 267
technetium porphyrins, 447
Vinyl porphyrins
meso -tetraphenylporphyrin 2HC1,
synthesis, 244, 281
401
from acetyl, 281
meso -tetraphenylporphyrin-free base,
from aminoethyl, 281
399
from hydroxyethyl, 281
tin octaethylporphyrin, 437
Vinyl pyrroles, 121
tin meso -tetraphenylporphyrin, 437
Violins, nomenclature, 19
tin meso -tetraphenylporphyrin dichloride, 397
titanium- meso -tetraphenylporphyrin oxo
W
Water soluble porphyrins, chromatography
column, 573
tlc, 573
complex, 397
uranium phthalocyanines, 399
vanadyl deoxophylloerythroetioporphyrin, 487
zirconium octaethylporphyrin, 436
zirconium octaethylporphyrin diacetate,
Y
synthesis, 427
Zinc meso –tetra (p-tolyl)-porphyrin,
electronic spectrum, 415
Ytterbium porphyrins, 431
reconstitution with apomyoglobin, 431
Zirconium (acac)4, 404
Zirconium octaethylporphyrin, X-ray
Yttrium porphyrins, 431, 432
Z
Zinc octaethylporphyrin, electronic
spectrum, 414
Zinc porphyrins, 425
ring oxidations, 427
398
structure, 436
Zirconium octaethylporphyrin diacetate,
X-ray structure, 398
Zirconium porphyrins, 436