208 Index
Pyridines (continued )
4-fl uoro-, from 4-aminopyridine 43
2-, 3- and 4-Grignard reagents, preparation 38
halo-, relative reactivities 36
hydrochloride 33
2-hydroxy-, tautomerism 41
4-hydroxy-, tautomerism 41
2-lithio-, from pyridine 38
3-lithio-, from 3-bromo- 38
3-lithio-4-t-butoxycarbonylamino-, from
4-t-butoxycarbonylamino- 38
3-lithio-4-chloro-, from 4-chloro- 38
3-lithio-2-pivaloylamino-, from 2-pivaloylamino- 17
4-lithio-3-fl uoro-, from 3-fl uoro- 38
mesomeric structures 5
2-methoxycarbonyl-3-trifl oxy-, in Heck reaction 26
2-methyl-, reaction with phenacyl bromide 147
side-chain acylation 40
deprotonation 40
silylation 40
3-methyl, conversion into 2-cyano-3-methylpyridine 37
4-methyl, condensation at methyl 18
from 4-methylpyrylium 72
nitration 34, 37
nitrogen lone pair 5
nucleophilic substitution, regioselectivity 35
numbering 2
N-oxidation 33
N-oxides 33
3,5-diamino-2,6-dinitro- (DADNPO) 185
2,3-dimethyl-, reaction with Ac 2 O 42
4-methoxy-, N-deoxygenation 42
reaction with Ac 2 O 42
reaction with PCl 3 42
4-nitro-, reaction with methoxide 42
nitration 42
palladation and cross-coupling at C-2 30
reaction with phosphoric trichloride 42
2-(2-oxopropyl)-, reaction with tosyl azide 147
2-phenylation 35
polarization 5
radical substitution 15
reaction with (CF 3 CO) 2 O–HNO 3 then KCN 37
with N 2 O 5 37
reduction 39
-side-chain, oxidation via N-oxide 42
sulfur trioxide complex 33
structure 5
sulfur trioxide complex, in ring synthesis of pyrylium 75
1,2,3,6-tetrahydro-1-Boc-2-methoxycarbonyl-, ring
synthesis by metathesis 157
2-(thien-2-yl)-5-phenyl-, ring synthesis via Diels–Alder
reaction 141
3-(tri-n-butylstannyl)-2-bromo-, preparation 38
2-trifl oxy-, in Sonogashira reaction 27
2-trifl oxy-, in cross-coupling with CO–PhB(OH) 2 27
from 2-pyridone 41
3-trimethylstannyl-, preparation 38
Pyridinium cations
N-amino- 33
1-(t-butydimethylsilyl)-, addition of Grignard 37
1,4-dimethyl-, condensation at side-chain methyl 41
3-hydroxy-, deprotonation then dipolar-cycloadditions 40
mesomeric structures 5, 6
1-methoxycarbonyl, addition of Grignard 36
1-methyl-, iodide 33
1-phenoxycarbonyl-, addition of Grignard 37
polarization 5, 6
nucleophilic addition 36, 37
oxidation to pyridones 40
reduction to piperidines 39
to tetrahydropyridines 40
Pyrido[3,4-b]indole, see -Carboline 87
2-Pyridone 41
chlorination of 1-methyl- 35
3-chloro-5-ethoxycarbonyl-1-methyl-, ring
synthesis 55
conversion into 2-trifl oxypyridine 27
3-cyano-4-ethoxycarbonyl-6-methyl-, ring synthesis 46
N-deprotonation 41
Diels–Alder reaction 40
from 2-pyrone 74
4-methoxy-, from N-oxide 42
reaction with phosphoric trichloride 41
with trifl ic anhydride 41
4-Pyridone 41
from 4-aminopyridine 43
from 4-pyrone 74
1-methyl-3-phenyl, ring synthesis 44
nitration 35
Pyridostigmine (Mestinon) 172
Pyridoxal phosphate 161
Pyridoxine, see Vitamin B 6
Pyrimidines
4-amination (Chichibabin) 14, 50
2-amino-
bromination 50
reaction with iodomethane 57
tautomerism 48
2-amino-4,6-dimethyl-, ring synthesis 59
4-amino-
basicity 57
tautomerism 48
basicity 10, 48
5-boronic acid, from 5-lithio- 53
bromination 49
5-bromo-2-methylthio-, cross-coupling with
hexa-n-butylditin 25
5-bromo-, cross-coupling in Negishi reaction 54
in Suzuki–Miyaura reaction 54
reaction with PhCO radical 52
5-boronic acid-2,4-di-t-butoxy-, in Suzuki–Miyaura
reaction 53
5-carboxaldehyde, preparation 53
2-chloro-, reaction with trimethylamine 51
with tri-n-butylstannyl anion 51
2-chloro-6-methoxy-, reaction with tri-n-butylstannyl
anion 54
4-chloro-6-benzylamino-, reaction with MeNHOMe 51
4,5-dicarboxylic acid dimethyl ester, ring synthesis via
Diels–Alder reaction 141
2,4-dichloro-, nucleophilic substitution 14
electrophilic addition to N 49
2-iodo-4-methoxy-, formation of Grignard 53