Comparison of phenanthridine with other aza-aromatic heterocycles

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Iowa State University Capstones, Theses and
Retrospective Theses and Dissertations
Dissertations
1956
Comparison of phenanthridine with other aza-
aromatic heterocycles
John Joseph Eisch
Iowa State College
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Recommended Citation
Eisch, John Joseph, "Comparison of phenanthridine with other aza-aromatic heterocycles " (1956).Retrospective Theses and
Dissertations. 12752.
https://lib.dr.iastate.edu/rtd/12752
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GOMPARISON OF PHEilNTHEIDIME WIfH
OTHER IZ^-lROMAflC HEfEROCXCLlS
John Joseph Eleoh.
A Dissertation Subffiltted to tti«
&rattiat@ Faculty in Partial Fulfillatnt of
The lequlrementB for the Degrs© of
DOGfOR OF PHILOSOPIff
Major Subjeet! Organ!© Chemistry
ApproTed:
Signature was redacted for privacy.
In Charge of Major Work
Signature was redacted for privacy.
lead of Major .D©p&rtkent
Signature was redacted for privacy.
Dean of Graduate College
Iowa, State College
1956
UMI Number: DP12078
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11
TABLE OF CONTENTS
Page
I. iMTHOroCTION 1
II. HISTORICAL—COMPIRISOS OF PHEMASTHRIDIHE WITH
OTHER AZA-AIOMATIG HSTEHOCYGLES ^
A. Introduction ^
B. Aroiiatloltj 6
C. Theoretiosl Vlewi of the ChemlBtry of Aza-
arofflatie Systtme 11
1. Gentral eonsIdtrations 11
2. Bond fixation 12
3. Qu&ntim ffltehanical treatment of az«-
aroa&tlc heterocyclee 15
4-, Transition etrnt® tre&tnent of aromatic
tubetitmtion 25
D. Factors Affecting the Mod® of Attfl,ck on
Aza-aromatic Systems 31
1. Speeiee undergoing attack 31
2. Attacking species 3'
3. ReTersibility 3'
4. Sutoetitutnti 35
5. Catalysts 36
6. Temperature 37
7. Bol^ent 38
E. Ghemioal Propertlte 39
1, Substitution reactions 39
2, Eleetrophilie eubetitution ^1
a. Hitration 4l
b. Halogenstion
c. Siilf©nation 46
d. Mercur&tlon 47
e. Friedel-CraftB alkylation 49
3, Kucleophlllo substitution 49
T1&0S4
111
a. llkflatloti
b, Affilnatlon
e* Hydride loii reduction
d, fiyiroxylatlon
e. Gyanatloii
4. Free radical ewbstltutlon
a. Pfetnylatlon
to. Methylatlon
e. Reduction
,€ Coupling
e. High teaperature reactions
5. Mdltlon reactions
a. Hydrogenetlon
b. Reaction with dlalkyl aeetylene-
dl0arbo:H:ylst©
e. iltrogen coaplexts
l) M-Oxldts
11) Q.mternlzation
ill) Salt foraatlon
6. Ring stability
?•, Coaparlson of characteristic derlvatl-ree
a« iBiln© derlT&tlveB
b, Carboxyllc acid©
0. Dlhydro derivatives
d. Halogen derivatives
e, %droxyl derivative!
f» Methyl derivatives
g. l-Oxldes
P. Phyelcal Properties
1. Molecul&r diffleneloM
2. Molar refraction.
3. Dlpol® »omente
Infrared epectra
5. Ultraviolet spectra
6. fh.©rnioch«ailcal data
CI, PhyBlological Properties
Iv
Page
III. IXPSRIMEMTAL 95
A. Preparation of Biphenyl Intermediates 95
1. 2-lc®t&rol!iio'blplaenyl 95
2. 2-AcetaninO'-5-'bro»ot>lphen|'l 96
3. 2-Ac®tamiiio*.^'-cli,loroblpfeenyl 97
k, 2-AHilno-2'-nltrot!lpfa#n.yl 98
5. 2-Ac@taiilii©--2'-!iitro'biphenyl 99
6. 2-lcetamino-3-iiltroblplien|'l 99
7. 2-BiityraiilnoMph.eEyl 100
8. 2-Valeramln©Mph©nyl 101
9. S»i•-Dl(£-ER€ yi) oxalaMlde 102
B« Phenanthrldlne Derl?atlTes by Cycllzatlon IO3
1. 6-||-Propylphsnsiitlarltiiie 103
2. 6-|i-Butylpiien«nthrldla@ 104
3. 2-BroiBo-6-o@tliylpiienantferl<ilne 105
k, 6-Ketl^l-^-niltropfa.enanthrldlne 105
5. 6-Metjhyl-lO-iiitropiienanthriaine 106
6. 6,6'-Diplienaatlari<ayl (attsapted) 106
a# Phoipfaome oxychlorlde and nitrobenzene 106
b. Polypbosphorlc acid I07
C. Chemletry of tiie Pfaenatittirldine System 107
1, Allylfttlon and arylation I07
a. 6-n~ButylpJEienantta*idine 107
, b* g-^-Propylpiienanthrldlae 109
c. e-^-folyl-Sfe-dihydrophenanthridlne 110
d. Defeydrogiinatlon of 6-o-tolyl-5»6~
dlhydrophenanthrldlni" 111
e. 6-Bsnzyl-5»6-<iibydropiienanthridin© 112
f. 6-BenEoylplierianthridlne 113
g. Bls-6-plienylphenantiarldlne 113
2. Broffllnation 11^
a, M-Broaoeuocinloilde method 11^
b. Phenanthrldine hydrobroialde per bromide
metbod 116
o, Bronlne-glaclal aeetlc acid aethod 117
T
Page
d, Broalne-carbon tetraehlorlde method
(attettpt®d) 118
e, OxlAatlon of the wnkriown
browophenanthridlne 118
f, 2-CfanoplieiianthrldlHe 119
3. Gyanatlon 120
a, Phenanthridine methlodldt 120
to. 6- Cyano-5*-o®thyl- 5 # 6-aihydrophen-
antbrldiiit 121
e. 6-C|-aftopli@n&»thrldlne nethiodidt 121
4. Prled©1-Grafts reaction (attempttd) 122
5. Hydroxylation 122
6. 2-Mltroph@nianthpldln® 123
7. Oxidation 125
a. Oxidation ©f phenanthridlne (attempted) 125
Oxidation of 6-ja-batylpherianthrldlne 125
G. Oxidation of &-n-propyiphenanthrldine 12?
d, ^-Nitrophenanthrldone 128
e, 10-Sltroplie:ii&athrldoB« 128
f, 2-BroBopheRaiithrldon® 129
8. Sulf©nation 130
a. Trial 1 I30
to. Trial 2 132
D. Chemietry of Phenanthrldone 132
1. Acetylatlon Cattenpted) 132
2. Broolnation 133
3. Ohlorlnatlon 13^
k, lodinatlon • 136
5. Mercwratlon (attempted) 137
6. lltratlon 137
7. Sulf©nation 139
8. Heaotion with ||-toutyllltfe.iuii l4l
9. Reaction with phoephortas pentaohlorlde 1^2
E, Chemistry of Phenanthrldone Derivative® 1^3
1. 2-Ac@t&ainophena.nthridone 1^3
2, Broffllnatlon of 2-a.cetafflinophenanthridone 143
Tl
Page
i iitrntlon ©f 2*aceta©lnoplieiianthridone
2-Glilo3ro- 5--ffl®tlijlplienaiitiirl<ione 1^5
5. 5-Mei;%l-2-alt3?oph®nantiirldone
6. 2-Bi*oao~#-.Bltrop,isitn&ntferid6ii© 1^7
7. 2-CihloTO-^-niti'ophenaathriaone 1^8
8. lltratlen of Z-iodophenanthrldon® 1^9
9. Reaetlon ef a-feroiaophenanthriaoae with
jft-.butylllthl«a 1^9
F. Reaetlon of Allylmagnesiuii Bromide with the
AzometblEe Linkage 1,51
1, General prooedwre for the intera-ctlon of
nitrogen heterooyolee with allylaagneslwffl
broffilde 151
&. 4-Allylpyrldln« 153
to* 6-lllfl-5»6-dihytr©phenaiithrMine 15^
00 -.lliyltoensylanlllne 156
d. 9»Allyl»9»10-dihydro&eridine 156
•©* 2,3-l3iallyl-l,2,3,^-tetra.hyaroquinoxallne 157
f, cL -Mlylfeenthydrylaalllnt 15©
2. Strwctiaral proofs of tb® products 159
a» 2-Allylpyrld.in@ 159
1) Meth©5 1 159
11)-lethod 2 160
b* HyflrogenatioR of 4-allylpyrldlne 161
c. 'Mehrottate oxidation of 6-allyl-5»6-
dlhydreptosnanthridine 162
d* Bichromate oxidation of 9-allyl-9»10-
dl%!lr©acrldiiit 162
t* Heaetlon of jj-pi'ppyllithiuffl with
benzophenone" anil C n-propyl)
benzhydrylanllin©) 163
f. Reduction of the hydrolyzed allyl
Q-rignarfl adduct of benzophenone anil
CeonTersion of oc-ftllylbenzhydryl-
anlline to oc. -Cn-propyl) benshydryl-
anlllne 16^
g. Butyrophenone 16^