Imidazolium cations, processes for their preparation, and uses therefor

Novel imidazolium compounds of the formula ##STR1## wherein A represents the atomic group necessary to form a heteroaromatic ring, which may be optionally substituted by one or more R substituents selected from the group consisting of aryl, heteroaryl, lower alkyl, hydroxy, halide, or carboxy substitutents; B is an optional substituent which represents the atomic group necessary to form a heteroaromatic ring or a double or triple carbon-nitrogen bond, which may optionally be substituted by one or more R' substituents selected from the group consisting of aryl, heteroaryl, lower alkyl, hydroxy, halide, or carboxy substitutents; C is an optional substituent which represents the atomic group necessary to form an aromatic or heteroaromatic ring, which may optionally be substituted by one or more R"" substituents selected from the group consisting of aryl, heteroaryl, lower alkyl, hydroxy, halide, or carboxy substituents; R" and R'" are each independently a lower alkyl or aryl group, or together with the nitrogen atom to which they are attached, form a heterocyclic ring having from 5 to 7 members, which may optionally contain a sulfur, oxygen, silicon, selenium or an additional nitrogen atom; and X is an anion; are useful in a variety of industrial and medical applications.

BACKGROUND OF THE INVENTION 
This invention relates generally to the preparation of novel imidazolium 
cations, processes for such preparation, and various methods of use for 
the compounds of the invention. 
The Vilsmeier-Haack reaction has been an established method for the 
formylation of aromatic rings. Such formylation however is applicable 
mainly to active substrates, such as amines and phenols, and aromatic 
hydrocarbons which are much more active than benzene such as azulenes and 
ferrocenes. Typically, POCl.sub.3 and dimethylformamide are used as the 
reactants, although other dialkyl amides have been used as well. It is 
also widely used as a method for chlorinating, especially with thionyl 
chloride, under similar reaction conditions. 
OBJECTS OF THE INVENTION 
It is an object of the present invention to provide novel imidazolium 
cations, and salts thereof, which have a variety of utilities. 
It is a further object of the present invention to provide processes for 
the preparation of the aforesaid imidazolium cations and their salts under 
favorable conditions in large quantities. 
A still further object of the present invention is to provide methods for 
using the novel imidazolium cations and their salts produced by the 
processes of the instant invention. These methods include a variety of 
applications, both industrial and medical, which result from the 
properties of the aforesaid imidazolium compounds. 
It is thus a further object of the present invention to provide methods of 
using the compounds of the instant invention as fluorescent dyes for 
textiles, and for the incorporation into polymer matrices so as to enable 
their use in as pigments for waterborne paints, films and articles made of 
polyolefins, e.g. polyethylene or polypropylene. 
It is a further object of the present invention to provide compounds useful 
in the preparation of non-linear optical devices. 
Still further, it is an object of the present invention to utilize the 
compounds of the instant invention for printing fiber materials, for 
example, polyester, cotton or polyester/cotton blend fabrics. 
Another object of the present invention is to utilize the compounds of the 
present invention as fluorescent tags for biomolecules, so as to enable 
the labeling of such molecules and the monitoring of the disposition of 
such molecules by the mammalian body. 
A still further object of the present invention involves the use of the 
compounds of the present invention as components of kits for use in 
assaying biomolecules tagged with the aforesaid compounds. 
Another object of the present invention is to use the process of the 
invention in combinatorial drug invention systems for labeling and for 
therapeutic investigation. The instant invention can be used as a linear 
strategy for combinatorial synthesis. 
SUMMARY OF THE INVENTION 
The present invention relates to novel imidazolium cations and to processes 
for their preparation. More particularly, this invention concerns 
compounds of the formula I 
##STR2## 
wherein A is a heteroaromatic ring, which may be optionally substituted by 
one or more R substituents selected from the group consisting of aryl, 
heteroaryl, lower alkyl, hydroxy, halo, lower alkylamino, amino, nitro, or 
carboxy substituents; 
wherein P or Q are optional substituents, each independently a substituent 
selected from the group consisting of aryl, heteroaryl, lower alkyl, 
hydroxy, halo, lower alkylamino, amino, nitro, or carboxy, or P and Q 
together are a heteroaromatic ring, said P and Q substituents 
independently or together which may optionally be substituted by one or 
more R' substituents selected from the group consisting of aryl, 
heteroaryl, lower alkyl, hydroxy, halo, lower alkylamino, amino, nitro, or 
carboxy substituents; 
C is an optional substituent which is an aromatic or heteroaromatic ring, 
which may optionally be substituted by one or more R"" substituents 
selected from the group consisting of aryl, heteroaryl, lower alkyl, 
hydroxy, halo, lower alkylamino, amino, nitro, or carboxy substituents; R" 
is hydrogen, a lower alkyl or aryl group, or together with R'" and the 
nitrogen atom to which it is attached, form a heterocyclic ring having 
from 5 to 7 members, which may optionally contain a sulfur, oxygen, 
silicon, selenium or an additional nitrogen atom, said ring optionally 
substituted with at least one lower alkyl group; R'" is a lower alkyl or 
aryl group, or together with R" and the nitrogen atom to which it is 
attached, form a heterocyclic ring having from 5 to 7 members, which may 
optionally contain a sulfur, oxygen, silicon, selenium or an additional 
nitrogen atom, said ring optionally substituted with at least one lower 
alkyl group; and X is an anion. 
The process of the instant invention involves the reaction of a compound of 
formula II with an N,N-disubstituted-formamide of formula III in the 
presence of a halogenating agent.

DETAILED DESCRIPTION OF THE INVENTION 
The lower alkyl groups referred to herein preferably contain 1-6 carbon 
atoms and include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the 
corresponding branched-chain isomers thereof. These groups are optionally 
substituted by one or more halo, hydroxy, amino or lower alkylamino 
groups. 
In the instance where R" and R'", together with the nitrogen atom to which 
they are attached, form a heterocyclic ring having from 5 to 7 members, 
which may optionally contain a sulfur, oxygen, silicon, selenium or 
additional nitrogen atom, such heterocyclic rings are typified by 
pyrrolyl, imidazolyl, pyrazolyl, pyrrolidinyl, imidazolidinyl, piperdinyl, 
morpholinyl and piperazinyl groups, which can optionally be substituted by 
lower alkyl groups. Especially preferred for use in the present invention 
are pyrrolodine, morpholino and piperazinyl groups. 
Where the possibility exists for substitution of a phenyl or aryl ring, the 
position of the substituents may be ortho, meta, or para to the point of 
attachment of the phenyl or aryl ring to the nitrogen of the hydrazine 
group. Preferably, the substituents are para or meta to the point of 
attachment, and where more than one is present on the same ring, they are 
preferably in the para and meta positions. 
The halo atoms in the above formula may be fluoro, chloro, bromo or iodo. 
The lower alkoxy groups contain 1-6, and preferably 1-3, carbon atoms and 
are illustrated by methoxy, ethoxy, n-propoxy, isopropoxy and the like. 
The A, C, P and Q atomic groups of the compounds of formula I can be 
selected from a variety of such groups known in the chemical arts. In a 
preferred embodiment of the present invention, the A and the combination 
of the P and Q group are each a pyridyl ring. Other embodiments are those 
wherein the A group is a quinolinyl, piperazinyl, or an anthracenyl group, 
optionally substituted with R, and R' substitutents. 
The compounds of this invention are salts wherein the X- anion is derived 
from an acid, typically one which is biologically and pharmaceutically 
acceptable. The resultant salts can thus be derived from a variety of 
organic and inorganic acids such as sulfuric, phosphoric, hydrochloric, 
hydrobromic, sulfamic, citric, lactic, maleic, succinic, tartaric, 
cinnamic, acetic, benzoic, gluconic, ascorbic, methanesulfonic and related 
acids. 
Of the compounds encompassed by formula I, certain substituents are 
preferred. For instance, the compounds wherein both the A and the 
combination of the P and Q group are a pyridyl ring are preferred, as are 
the compounds wherein the A group is derived from a quinolinyl group and 
the combination of the P and Q group is derived from a pyridyl group. 
These compounds are the result of the reaction of the 
N,N-disubstituted-formamide with the appropriately substituted 
2,2'-bipyridine or 2-(2-pyridyl)-4-carboxyquinoline. Also highly preferred 
due to their utility in biomolecular synthesis and various diagnostic 
applications are the compounds which are the reaction product of an 
N,N-disubstituted-formamide with an amino acid which has been coupled to 
2-(2-pyridyl)-4-carboxyquinoline. 
Representative compounds of the present invention include: 
12-(dimethylamino-5-carboxy)-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchlorate; 
12-(dimethylamino-5-methoxycarbonyl)-pyrido1',2':3,4!imidazo1,5-a!quinoli 
n-11-ium perchlorate; 
12-(dimethylamino-5-methoxycarbonyl)-pyrido1',2':3,4!imidazo1,5-a!quinol 
in-11-ium perchlorate; 
12-(diethylamino-5-carboxy)-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchlorate; 
6-(dimethylamino)-dipyrido1,2-c:2',1'-e!imidazol-5-ium perchlorate; 
6-(dimethylamino)-2,10-bis(carboxy)-dipyrido1,2-c:2',1'-e!imidazol-5-ium 
perchlorate; 
6-(dimethylamino)-2,10-bis(methylcarbonyl)-dipyrido1,2-c:2',1'-e!imidazol- 
5-ium perchlorate; 
6-(dimethylamino)-6-(2-pyridinyl)-pyrrido1',2',:3,4!imidazo 
1,5-a!pyrazin-5-ium perchlorate; 
6-11-bis(dimethylamino)-bis-pyrido1',2':3,4!imidazo1,5-a:5',1'-c!pyrazine 
-5,10-diium diperchlorate; 
12-(dimethylamino)-6-(2-pyridnyl)-pyrido1',2':3,4!imidazo1,5-a!quinoxalin 
-11-ium perchlorate; 
6,13-bis-(dimethylamino)-bispyrido1',2':3,4!imidazo1,5-a:5',1'-c!quinoxal 
ine-5,12-diium diperchlorate; 
12-(dimethylamino)-6-(2-pyridinyl)-pyrido1',2':3,4!imidazo1,5-a!anthacen- 
11-ium perchlorate; and 
6,13-bis(dimethylamino)-bispyrido1',2':3,4!imidazo1,5-a:5',1'-c!anthacen- 
5,10-diium diperchlorate. 
Other especially preferred compounds are the derivatized amino acids: 
5-(L-glycyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-i 
um perchlorate; 
5-(L-glycylmethylester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!qu 
inolin-11-ium-perchlorate; 
5-(L-leucinyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11 
-ium-perchlorate; 
5-(L-leucinemethyl 
ester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-ium-pe 
rchlorate; 
5-(L-histidInyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin- 
11-ium-perchlorate. 
(L-histidinylmethyl 
ester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-ium-pe 
rchlorate; 
5-(L-glycylglycyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinoli 
n-11-ium-perchlorate; 
5-(L-glutamyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11 
-ium-perchlorate. 
Many suitable starting materials for the compounds of the instant invention 
are generally known in the art. For instance, Balzani et al., Chemical 
Reviews, 1996, Vol. 96, No. 2, pp. 759-832 and Juris et al., Coordination 
Chem. Reviews, 1988, Vol. 84, pp 85-277, contain details of the 
preparation of numerous compounds which can be utilized as starting 
materials for the processes of the instant invention due to their 
inclusion of the N--C--C--N moiety. Many suitable compounds are also 
commercially available, for instance, from Aldrich Chemical Co. 
Some particularly suitable starting materials for use in the practice of 
the instant invention are the following known compounds: 
2,2'-bipyridine; 
4-chloro-2,2'-bipyridine; 
4-bromo-2,2'-bipyridine; 
4-amino-2,2'-bipyridine; 
4-dimethylamino-2,2'-bipyridine; 
4-methoxy-2,2'-bipyridine; 
4-nitro-2,2'-bipyridine; 
4-benzyl-oxy-2,2'-bipyridine; 
4-(triethylphophonio)-2,2'-bipyridine; 
6-methyl-2,2'-bipyridine; 
6-p-styryl-2,2'-bipyridine; 
6-p-tolyl-2,2'-bipyridine; 
3,3'-dimethyl-2,2'-bipyridine; 
2cyanopyridine; 
3,3-dicarboxyisopropyl-2,2'-bipyridine; 
4,4'-dimethyl-2,2'-bipyridine; 
4,4'-dichloro-2,2'-bipyridine; 
4,4'-dibromo-2,2'-bipyridine; 
4,4'-dinitro-2,2'-bipyridine; 
4,4'-diamino-2,2'-bipyridine; 
4,4'-disulphonate-2,2'-bipyridine; 
4,4'-bis(diethylamino)-2,2'-bipyridine; 
4,4'-diethoxy-2,2'-bipyridine; 
4,4'-diphenoxy-2,2'-bipyridine; 
4,4'-dibenzyloxy-2,2'-bipyridine; 
4,4'-diphenyl-2,2'-bipyridine; 
4,4'-dibezyl-2,2'-bipyridine; 
4,4'-distyryl-2,2'-bipyridine; 
4,4'-dicarboxy-2,2'-bipyridine; 
4,4'-di-tert-butyl-2,2'-bipyridine; 
4,4'-dinonadecyl-2,2'-bipyridine; 
4,4'-distearyl-2,2'-bipyridine; 
4,4'-dicarboxymethyl-2,2'-bipyridine; 
N,N'-di(dodecyl)-2,2'-bipyridine-4,4'-dicarboxyamide; 
N,N'-di(hexadecyl)-2,2'-bipyridine-4,4'-dicarboxyamide; 
4,4'-dicarboxyethyl-2,2'-bipyridine; 
4,4'-dicarboxyisopyl-2,2'-bipyridine; 
4,4'-dicarboxycyclohexyl-2,2'-bipyridine; 
4,4'-dicarboxybenzyl-2,2'-bipyridine; 
4,4'-dicarboxynapth-2-yl-2,2'-bipyridine; 
4,4'-dicarboxynaphthan-1-yl-2,2'-bipyridine; 
4,4'-dicarboxydihydrocholesteryl-2,2'-bipyridine; 
N,N'-di(ethyl)-2,2'-bipyridine-4,4'-dicarboxamide; 
4-carboxy-4'-methyl-2,2'bipyridine; 
4-vinyl-4'-methyl-2,2'-bipyridine; 
5,5'-dimethyl-2,2'-bipyridine; 
5,5'-dicarboxyethyl-2,2'-bipyridine; 
5,5'-bisacetoamido-2,2'-bipyridine; 
5,5'-dicarboxyisopropyl-2,2'-bipyridine; 
6,6'-dimethyl-2,2'-bipyridine; 
4,4',5,5'-tetramethyl-2,2'-bipyridine; 
2,2'-bipyrazine; 
protonated 2,2'-bipyrazine; 
2,2'-bipyrimidine; 
4,4'-dimethyl-2,2'-bipyrimidine; 
6,6'-dimethyl-4,4'-bipyrimidine; 
3,3'-bipyridazine; 
4-methyl-2(2'-pyridyl)-pyrimidine; 
6-methyl-4-(2'-pyridyl)-pyrimidine; 
2-(2-aminoethyl)pyridine; 
o-phenanthroline-5,6-diimine; 
pyridyl-2-imine; 
2-(2-pyridyl)imidazolate anion; 
2-(2-pyridyl)imidazole; 
2,2'-biimidazote dianion; 
2,2'-diimidazote anion; 
2,2'-biimidazole; 
2,2'-dibenzimidazolate dianion; 
2,2'-dibenzimidazolate anion; 
2,2'-dibenzimidazole; 
1-(2-pyridyl)-3,5-dimethyl-pyrazole; 
2-(2'-thiazolyl)-pyridine; 
2-(2'-pyridyl)-4-methyl-thiazole; 
4,4'-bithiazole; 
2,2'-bi-2-thiazoline; 
2-p-tolyl-pryidinecarboxaldimine; 
2,2'-biquinoline; 
4,4'-dimethyl-2,2'-bipyridine; 
2,3-bis(2-pyridyl)-(pyrazine); 
2,3-di-2-pyridylquinoxaaline; 
2,3,7,8-tetra-2-pyridylpyrazino2,3-g!quinoxaline; 
2,2',3,3'-tetra-2-pyridyl-6,6'-biquinoxaline; 
1,2-bis4-(4'-methyl-2,2'-bipyridinyl)!ethane; 
1,5-bis4-(4'-methyl-2,2'-bipyridinyl)!petane; 
1,4-bis4-(.alpha.-ethyl)-4'-methyl-2,2'-bipyridyl!benzene; 
1,12-bis4,(4'-methyl-2,2'-bipyridyl)dodecane; 
2,2',2"-tripyridine; 
4'-phenyl-2,2',2"-tripyridine; 
4,4',4"-triphenyl-2,2',2"-tripyridine; 
2,4,6-tripyridyl-s-triazine; 
4-ethynyl-2,2'-bipyridine; 
1,12-bis(4-methyl-2,2'-bipyrid-4'-yl)-2-11-diazadodecane; 
1,11-bis(4-methyl-2,2'-bipyrid-4'-yl)-6-methyl-2,6,10-triazaundecane 
trans-1,2-bis(4'-methyl-2,2'-bipyrid-4-yl)-ethene; 
1,4-bis(4-methyl-2,2'-bipyridin-4'-yl)buta-1,3-diene; 
1,4-bis(4-methyl-2,2'-bipyridin-4'-yl)buta-1,3-diene; 
1,4-bis2-(2,2'-bipyridin-5-yl)ethenyl!-bicyclo2.2.2!octane; 
1,4-bis(4-methyl-2,2'-bipyridin-4'-yl)-2-cyclohexene-5,6-dicarboxylic acid 
diethyl ester; 
10-bis(2,2'-bipyridinyl-5-yl)carbonyl!-enzylamino!methyl!anthracene; 
1,3,5-tris(2,2'-bipyridyl-5-yl)carbonyl!-benzylamino!methyl!benzene; 
1,3,5-tris5-(ethoxycarbonyl-(2,2'-bipyridyl-5-yl)carbonyl)benzylamino!me 
thyl!phenyl!benzene; 
1,3,5-tris4-(2,2'-bipyridyl-5-ylcarbonyl)benzylamino!methyl!phenyl!benze 
ne; 
2,2':6,2":6",2"-quaterpyridine; 
2,2':4',4":2",2"-quaterpyridine; 
1,2-bis(6'-methyl-2,2'-bipyridin-6-yl)-ethane; 
1,4,7,10,13,16-hexakis(2,2'-bipyridin-6-yl)methyl!-1,4,7,10,13,16-hexaazac 
yclooctodecane; 
2,2':3',2":6",2'"-quaterpyridine; 
2,3-bis(2-pyridyl)pyrazine; 
2,5-bis(2-pyridyl)pyrazine; 
2,3-bis(2'-pyridyl)quinoxaline; 
6,7-dimethyl-2,3-bis(2-pyridyl)quinoxaline; 
6,7-dichloro-2,3-bis(2-pyridyl)quinoxaline; 
2,3-bis(2'-pyridyl)benzog!quinoxaline; 
2,2',3,3'-tetra-2-pyridyl-6,6'-biquinoxaline; 
2-pyridylacetonitrile; 
2,2'-biquinoline; 
2,2'-biquinoline-4,4'-dicarboxylic acid; 
2,2'-biquinoline-4,4'-dicarboxylic acid dipotassium salt trihydrate; 
2,2'-biquinoline-4,4'-dicarboxylic acid disodium salt dihydrate; 
2,4-bis(5,6-diphenyl-1,2,4-triazin-3-yl)pyridine; 
3-(2-pyridyl)-5,6-di(2furyl)-1,2,4-triazine-5',5"-disulfonic acid disodium 
salt; 
3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine; 
3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-4'-4"-disulfonic acid monosodium 
salt; 
2,4,6-tri(2-pyridyl)-s-triazine; 
2,3-diaminopyridine; 
1,2-dicyanobenzene; 
1,2,4,5-tetracyanobenzene; and 
S(-)-1-formyl-2-(methoxymethyl)pyrrolidine 
In certain cases, the preparation of the compounds of the instant invention 
involves the preparation and use of novel starting materials. A general 
scheme for the preparation of several of such starting materials is shown 
below as Scheme I. In this scheme, the preparation of several necessary 
starting materials for the process of the instant invention are the novel 
compounds of formula I wherein A represents the atomic group necessary to 
form a quinoline ring, and B represents the atomic group necessary to form 
a pyridyl ring is shown, using the known starting materials isatin and 
2-acetylpyridine. In step A, isatin and 2-acetylpyridine are reacted in 
the presence of a strong base, such as sodium or potassium hydroxide to 
form the sodium or potassium salt of 2-(2-pyridyl)-4-carboxyquinoline. 
This salt can then be converted to the free acid by treatment with a 
dilute solution of a strong mineral acid, such as hydrochloric or sulfuric 
acid. Treatment of the free acid with the appropriate alkanol and a strong 
acid affords the alkyl ester of the acid. This alkyl ester can then be 
reduced, using, for instance, sodium borohydride or another reducing agent 
to give the corresponding alcohol. Alternatively, the free acid can be 
converted to the corresponding acyl halide by treatment with thionyl 
chloride with or without the presence of a non-polar hydrocarbon solvent. 
As can be expected the acyl halide can serve as a starting material to 
produce additional compounds, such as the ethylene glycol ester, as well 
as the corresponding amide compounds such as by reaction with a diamine. 
These compounds have a reactive termini that can be used to generate 
additional novel compounds for use with the instant invention. 
In a similar fashion, the pyrazine analogs of the compounds in Scheme I can 
be prepared by substituting 2-acetylpyrazine for 2-acetylpyridine. For 
example, 2-(2-pyrazinyl)-4-carboxyquinoline, 
(4)2-(2-pyrazinyl)-4-carboxymethylquinoline, 
(5)2-(2-pyrazinyl)-4-hydroxymethylquinoline, 
(6)2-(2-pyrazinyl)-4-carboxyquinoline acid chloride; 
(7)2-(2-pyrazinyl)-4-carboxyquinoline ethylene glycol ester; and 
2-(2-pyrazinyl)-4-carboxyquinoline, methyl benzyl ester, can be prepared 
by use of the appropriate 2-acetylpyrazine starting material. 
##STR3## 
A particularly useful embodiment of the present invention involves the 
reaction of acyl halide compounds with a natural or synthetic amino acid. 
As shown in Scheme II below, this reaction results in a starting material 
which links the amino acid to the carbonyl moiety. Generally, this 
reaction is conducted in an anhydrous polar solvent, such as anhydrous 
acetonitrile, in the presence of an acid acceptor, such as triethylamine. 
Preferred for use in this reaction are the naturally and non-naturally 
occurring amino acids and their alkyl, especially methyl, or benzyl 
esters. The reaction can also be extended to include peptides of two or 
more amino acids, and the alkyl or benzyl esters of amino acids and can 
thus function as a method of synthetically preparing a "tag" or label of 
such a peptide. Since non-natural amino acids and peptides can be derived 
from .beta.-lactams fluorescent .beta.-lactams, can be generated by the 
instant methodology. Particularly useful are fluorinated amino acids and 
.beta.-lactams. 
______________________________________ 
##STR4## 
##STR5## 
R' R Amino acid used 
______________________________________ 
H H Glycine 
CH.sub.3 
H Glycine, methyl ester 
##STR6## L-Leucine 
CH.sub.3 
##STR7## L-Leucine, methyl ester 
H 
##STR8## L-Histidine 
CH.sub.3 
##STR9## L-Histidine, methyl ester 
H 
##STR10## GlyGly 
H 
##STR11## Aspartic Acid 
H 
##STR12## Glutamic acid 
______________________________________ 
The novel process of the instant invention involves the reaction of a 
starting material of the general formula 
##STR13## 
wherein A, C, P, R, R' and R"" are as hereinbefore defined, with an 
N-substituted or N,N-disubstituted formamide of the formula 
##STR14## 
wherein R" and R'" are as herein before defined, in stoichiometric 
amounts, in the presence of a halogenating agent. 
Suitable halogenating agents are those such as thionyl chloride 
(SOCl.sub.2), thionyl bromide (SOBr.sub.2), phosphorus oxychloride 
(POCl.sub.3), phosphorus tribromide (PBr.sub.3), phosphorus triiodide 
(PI.sub.3), phosgene (COCl.sub.2), phosphorus thiochloride (PSCl.sub.3), 
thiophosgene (CSCl.sub.2), oxalyl chloride (ClCOCOCl), oxalyl bromide 
(BrCOCOBr), phosphorous pentachloride (PCl.sub.5) and phosphorus 
trichloride (PCl.sub.3). Of these, phosphorus oxychloride (POCl.sub.3), 
oxalyl chloride (ClCOCOCl), and thionyl chloride (SOCl.sub.2) are highly 
preferred. 
Depending upon the nature of the reactants, a solvent can be used or the 
reaction can proceed neat. When a solvent is utilized, it is typically a 
nonpolar aprotic solvent, such as benzene, toluene, hexane, etc. but polar 
solvents such as acetonitrile can also be used. 
Reaction conditions for the instant process vary depending upon the nature 
of the starting materials, and the presence or absence of a solvent. 
Typical temperatures range from 0.degree. C. to room temperature. With 
highly reactive starting materials, a somewhat lower temperature may be 
desirable, as well as the use of an inert atmosphere, such as a nitrogen 
or argon atmosphere, to inhibit side reactions. 
Anhydrous conditions will also help to minimize possible side reactions, 
especially where more than one set of reactive nitrogen atoms are 
available. Where the various R, R'" and R"" substitutents would allow side 
reactions, they can be suitably protected, prior to the conduct of the 
reaction, to avoid such reactions. Typical protecting groups useful for 
such procedures are well-known in the art, and can be removed after 
isolation of the imidazolium compound. 
Where the structure of the starting materials contains more than one 
N--C--C--N moiety, it will be appreciated that both reactive sites can be 
the subject of the instant process by use of two equivalents of the 
disubstituted formamide reactant. Numerous "monomer" (containing a single 
imidazolium ring) and "dimer" (containing two imidazolium rings) compounds 
of this type can be produced by the judicious choice of starting 
materials. 
The process of the instant invention provides a convenient and facile 
process for use in combinatorial synthesis, especially as described by 
Armstrong et al., Acc. Chem. Res., 1966, 29. pp. 123-131, Ellman, Acc. 
Chem. Res., 1996, 29 pp. 132-143, and Gordon et al., Acc. Chem. Res., 
1996, 29, pp. 144-154. 
The compounds of the instant invention possess valuable properties which 
make them useful in numerous commercial applications, both industrial, 
medical and therapeutic. 
The compounds of the instant invention possess interesting spectroscopic 
properties, especially fluorescent properties, which enable their use in a 
variety of commercial applications. For instance, the compounds can be 
used as fluorescent dyes in a range of blue, red, green, yellow colors, 
and especially blue and green colors. The color of fluorescence may be 
different from the absorption color. They can be utilized directly for the 
dyeing of textiles, and/or may be incorporated into commercially available 
polymer matrices, in typically, but not limited to, an amount of about 
1-3% by weight, based upon the polymer matrix. Preferred apolar polymer 
matrices are selected from the group consisting of polymethyl 
methacrylate, polystyrene, polybutadiene-modified polystyrene, 
polycarbonate, polyvinyl chloride and polyamide, with polymethyl 
methacrylate and polystyrene matrices being particularly preferred. Other 
polymer matrices which can also be used include polycondensates based upon 
urea and formaldehyde or polyamide. 
The fluorescent pigments are prepared in a conventional manner, such as is 
illustrated in U.S. Pat. No. 5,470,502, whose teachings are herein 
incorporated by reference. Generally, the fluorescent compound of the 
instant invention is incorporated into the polymer matrix by extrusion or 
injection molding. The process of incorporation generally operates at a 
temperature range of about 150.degree. C. to about 250.degree. C., 
depending upon the polymer matrix utilized. When polymethyl methacrylate 
is used, the temperature is generally at a range of about 200.degree. C. 
to about 240.degree. C. 
The novel fluorescent pigments formed by mixing the compounds of the 
present invention with a polymer matrix are highly suitable for pigmenting 
waterborne paints and films and articles made of polyolefins, e.g. 
polyethylene or polypropylene, and for printing fiber materials, for 
example, fabrics in polyester or cotton or polyester/cotton blends. 
Such fluorescent pigments possess high luminenscence and advantageous 
application properties, for example, high lightfastness and a low 
migration tendency. 
The possession of fluorescent properties further enables the use of the 
compounds of the instant invention in a variety of medical, pharmaceutical 
and diagnostic applications. Fluorescent clonal markers can be utilized to 
elucidate various biological mechanisms, in both animal and plants such as 
the embryogenesis of an organism, drug binding sites, and drug disposition 
in the body. 
For instance, by attaching a fluorescent compound of the instant invention 
to a biomolecule such as the end of one arm of a probe sequence of nucleic 
acids, and a non-fluorescent quench moiety to the end of the other arm of 
a probe sequence of nucleic acid, the synthesis of specific nucleic acids 
can be monitored. Similarly, when such fluorescent compounds are used in 
nucleic acid amplification assays, gene detection is homogeneous and 
sensitive. Still further, nucleic acid probes containing the fluorescent 
compounds of the instant invention can be introduced into living cells, 
thus enabling the origin, movement, and fate of specific mRNAs to be 
traced. Such methods of attaching fluorescent compounds to such probes 
have been described in the art, for example in Tyagi et al., Nature 
Biotechnology, 14, pp. 303-308, and T. Stein Chem. Eng. News, Jul. 18, 
1994, pp. 34-44. By utilizing the various compounds of the instant 
invention which emit light of a different wavelength, detection of many 
different targets in the same solution can be identified. For example, a 
two-dimensional array of immobilized molecular beacons derived from the 
compounds of the instant invention can be used in a single assay to carry 
out an extensive survey of an amplified genomic region. Fluorescence is 
especially useful to probe proteins, and DNA. 
In similar fashion, the compounds of the instant invention can be utilized 
as fluorescent tags for any variety of biomolecules to enable the tracking 
and the disposition of such molecules. Especially important biomolecules 
which can be tagged by the instant compounds include amino acids, 
peptides, proteins, .beta.-lactams, oligonucleotides, RNA, DNA, and 
lipids. The compounds of the instant invention can thus be included in 
kits to utilize as labeling agents for such biomolecules in various 
diagnostic and research applications. Methods for utilizing such 
fluorescent tags for biomolecules are described in, for instance, Rich et 
al., J. Am. Chem. Soc., (1995), 117, 733-739, Bakthavalam et al., J. Med. 
Chem., (1991), 34, 3235-3241, Kraus et al., Chem. Rev., (1996), 96, 
523-527, and Wilchek et al., Analytical Biochemistry, (1988), 171, 1-32, 
whose teachings are herein incorporated by reference, especially those 
pertinent to the development of biotin related-systems. 
A further alternative to labeling already formed biomolecules involves the 
ab initio synthesis of biomolecules using amino acids which have been 
reacted in accordance with the process of the instant invention to contain 
the fluorescent tag within their structure. Typically, a solution of the 
amino acid, ester thereof or a .beta.-lactam in an anhydrous polar 
solvent, such as acetonitrile, is reacted with a compound of the instant 
invention which contains an acyl halide functional group, such as, for 
instance, the acyl chloride of 2-(2-pyridyl)-4-carboxyquinoline, in the 
presence of an acid acceptor such as triethylamine. This reaction is 
typically conducted at temperatures of about 0.degree. to about 20.degree. 
C. Typical reaction times range from about 1 to 10 hours depending upon 
the exact nature of the reactants. Using this method, one can prepare 
fluorescent amino acids, both natural and synthetic, which can then be 
utilized directly in the synthesis of biomolecules to provide fluorescent 
versions thereof. .beta.-lactams so modified can be used to generate 
non-naturally occuring amino acids incorporating flourescent 
characteristics. 
Further, the compounds of the instant invention can be used as fluorescent 
sensors for transition metals due to the advantages of using a fluorescent 
tag which can be detected at a very low concentration level. Such usage is 
described, for instance, by Fabbrizzi et al., Chem. Euro. J., (1996), 2, 
pp. 75 et seq., whose teachings are herein incorporated by reference. 
Another utility wherein the instant compounds can be used is in the 
preparation of non-linear optical polymers. By dissolving a compound of 
formula I in a polymer, subjecting the polymer to a large electric field 
at or above its glass transition temperature, and cooling the polymer, 
there is obtained a material with second-order optical non-linearity as 
described by Marder et al., Science, (1994) 263, pp 1706-1715. 
The compounds of the instant invention can also be utilized to label 
various therapeutic agents to enable their disposition in the body. As 
such, therapy with such labeled therapeutic agents can be closely 
monitored with respect to target organs and tissues. This is particularly 
useful in the treatment of various cancers, especially those of a solid 
tumor type, where localization of the chemo-therapeutic agent is extremely 
important, and dosage, due to the possibility of side-effects, must be 
closely monitored. Similarly, the use of such labeled antibiotics can 
assist in efficacy determinations of penicillins and antibiotics. 
The compounds of the invention additionally exhibit antifungal and 
antimicrobial activity against Candida albicans, as well as antiviral 
activity (HSV). By virtue of such properties, they can be formulated into 
pharmaceutical compositions, and used to treat infestations and infections 
caused by these invasive organisms. 
The invention will be further illustrated by the following Examples, which 
are to be considered illustrative of the invention, and not limited to the 
precise embodiments shown. 
PREATION OF STARTING MATERIALS 
EXAMPLE A 
Preparation of Sodium 2-(2-pyridinyl)-4-carboxyquinoline carboxylate 3 
Isatin 1 (8.0 g), and acetylpyridine (6.0 g) 2 are thoroughly mixed in a 
250 mL beaker. To this is added, while stirring with a glass stirring rod, 
30 g of 33% NaOH, which has been previously cooled to 5.degree. C. 
Stirring is continued until the contents harden (at this point the 
temperature is approximately 60.degree. C.). Water (30 mL) is then added, 
resulting is a fine purple/red slurry (has a metallic sheen). Cooling to 
50.degree. C., followed by filtration gives the crude product (3) as a 
red/purple solid. The solid is washed with ethanol and then acetone, and 
allowed to dry (10-15 g). Repeated crystallizations from a minimum amount 
of hot water (decolorizing-carbon which is used to remove the colored 
impurities) gives 10 g of 2 as a white solid. 
.sup.13 C (100 MHz, D.sub.2 O): .delta. 116.326(C--H), 123.11 (C--H), 
123.987 (C) 125.210 (C--H), 126.110 (C--H), 128.287 (C--H), 128.546 
(C--H), 131.115 (C--H), 138.727(C--H), 147.633 (C), 148.171 (C), 149.312 
(C--H), 155.072 (C), 156.160 (C), 175.457 (C.dbd.O) 
EXAMPLE B 
Preparation of 2-(2-pyridinyl)-4-quinoline carboxylic acid 4 (trivial name: 
2-(2-pyridyl)-cinchoninic acid) 
##STR15## 
The free acid is prepared by neutralizing an aqueous solution of the sodium 
2-(2-pyridyl)-4-carboxyquinoline carboxylate 3 with 10% HCl. The acid is 
somewhat soluble in acidic solution, and care should be taken not to 
overacidify; a pH of 7 is optimum. The solid is filtered, washed with 40 
mL of acetone and allowed to air dry. 
EXAMPLE C 
Preparation of 4-carboxymethyl-2-(2-pyridyl)-quinoline 5 
##STR16## 
Dry methanol (250 mL) is placed into a 500 mL round bottom flask and cooled 
to 0.degree.-5.degree. C. in an ice bath. To the stirring methanol is 
added 10 g of 2-(2-pyrininyl)-4-quinoline carboxylic acid 4, and 20 mL of 
H.sub.2 SO.sub.4 (98%). The mixture is then refluxed for 18 hours. The 
resulting solution is poured over 500 mL of ice water. The solid is 
filtered (crude 5) and the filtrate is extracted with chloroform 
(3.times.200 mL). The extracts are combined, dried over anhydrous sodium 
sulfate, and the solvent removed under reduced pressure. The solids are 
combined, and recrystallized from hot toluene (activated carbon), yielding 
8.0 g of the title compound 5 as a fluffy white solid. .sup.1 H NMR 
(CDCl.sub.3, 300 MHz): .delta. 3.22 (s, 3H), 7.32 (dd, J=7.7, 4.5 Hz, 1H), 
7.60 (ddd, J=7.70, 7.70, 1.3 Hz, 1H), 7.72 (ddd, J=8.3, 7.7, 1.3 Hz, 1H), 
7.80 (ddd, J=7.7, 7.7, 1.0, 1H), 8.18 (d, J=8.3 Hz, 1H), 8.60 (d, J=7.8 
Hz, 1H), 8.78 (d, J=7.8 Hz, 1H), 9.04(s, 1H). .sup.13 C NMR (CDCl.sub.3, 
300 MHz) .delta. 52.55 (CH), 120.25 (CH), 121.60 (CH), 124.29 (CH), 125.01 
(C), 125.49 (CH), 128.23 (CH), 129.71 (CH), 130.31 (CH), 135.42 (C), 
136.93 (CH), 148.73 (C), 149.10 (CH), 155.32 (C), 155.46 (C), 166.67 (C). 
EXAMPLE D 
Preparation of 4-hydroxymethyl-(2,2-pyridinyl)-quinoline 6 
##STR17## 
Dry methanol (250 mL) is placed into a 500 mL round bottom flask. To the 
stirring methanol is added 2.5 g of 
4-carboxymethyl-2-(2-pyridyl)-quinoline 5, and 7.0 g of sodium 
borohydride. The solution is then refluxed for 5 hours. After cooling to 
room temperature, the reaction mixture is poured into a saturated solution 
of ammonium sulfate (500 mL), and extracted with chloroform (3.times.200 
mL). The extracts are combined and dried over anhydrous sodium sulfate. 
Solvents are then removed under reduced pressure using a rotary 
evaporator. The resulting oil is allowed to solidify, and recrystallized 
from hot toluene (activated carbon) to yield 1.5 g of the title compound 
as a colorless solid. 
.sup.1 H NMR (CDCl.sub.3, 300 MHz): .delta. 5.15 (s, 2H, CH.sub.2), 7.55 
(m, 1H, CH), 7.60 (dd, J=8.2, 8.2 Hz, 1H), 7.80 (dd, J=8.2, 8.2 Hz, 1H), 
8.00 (dd, J=8.0, 8.0 Hz), 8.10 (d, J=8.2 Hz, 1H), 8.15 (d, J=8.15 Hz, 1H), 
8.62 (d, J=7.0 Hz, 1H), 8.72 (s, 1H), 8.76 (dd, J=6.3, 1 Hz). .sup.13 C 
NMR (CDCl.sub.3, 75 MHz): .delta. 60.40 (CH2), 115.62 (CH), 121.71 (CH), 
123.85 (CH), 125.12 (CH), 125.93 (C), 127.33 (CH), 130.04 (CH), 130.10 
(CH), 137.95 (CH), 147.18 (C), 149.56 (CH), 149.67 (C), 155.35 (C), 155.47 
(C). 
EXAMPLE E 
Preparation of 2-(2-pyridinyl)-4-carboxyquinoline acyl chloride 7 
Thionyl chloride (20 ml) and benzene (30 mL) are added to a 100 mL round 
bottomed flask containing 2.0 g of 2-(2-pyridyl)-4-carboxyquinoline 4. The 
mixture is then heated at reflux for 90 minutes. The yellow/green solution 
is allowed to cool, and traces of the unreacted acid (4) are removed by 
filtration. Solvents are removed under reduced pressure giving 2.1 g of 
the title crude acid chloride. This is further dried under vacuum 
(.about.0.01 torr) for 1 hour. Fresh preparations of this compound can be 
used in subsequent reactions. 
EXAMPLE F 
Preparation of 2-(2-pyridinyl)-4-carboxyquinoline ethylene glycol ester 8. 
##STR18## 
Ethylene glycol (50 mL) is added to a 100 mL round bottomed flask fitted 
with a magnetic stirring bar. With efficient stirring, the acid chloride 7 
(prepared as detailed in Example E) is added to the ethylene glycol in 
small portions. The solution is allowed to stir for an additional 30 
minutes. The solution is then poured into 300 mL of cold water, resulting 
in the immediate precipitation of a white solid. The mixture is made basic 
by the addition of solid sodium bicarbonate (foaming|), and filtered. The 
solid is allowed to dry, giving 3.6 g of the crude title product. 
Crystallization from ethanol gives 2.1 g of the title product, as a white 
solid. 
.sup.1 H NMR (CDCl.sub.3, 300 MHz): .delta. 3.60 (t, J=7.5 Hz, CH.sub.2, 
2H), 3.65 (Broad, 1H, OH), 4.50 (t, J=7.5 Hz, 2H, CH.sub.2), 7.50 (dd, 
J=7.5, 4.8 Hz, 1H), 7.70 (dd, J=7.7, 7.5 Hz, 1H), 7.84 (dd, J=7.7, 7.5 Hz, 
1H), 7.98 (dd, J=8.0, 7.5 Hz, 1H), 8.15 (d, J=8.4 Hz, 1H), 8.55 (d, J=8.0 
Hz, 1H), 8.65 (d, J=8.4 Hz, 1H), 8.75 (d, J=4.8 Hz, 1H), 8.95 (s 1H). 
.sup.13 C NMR (CDCl.sub.3, 75 MHz): .delta. 58.77 (CH.sub.2), 67.35 
(CH.sub.2), 119.12 (CH), 120.90 (CH), 124.00 (C), 124.59 (CH), 124.88 
(CH), 125.17 (CH), 128.41 (CH), 129.78 (CH), 130.19 (CH), 135.85 (C), 
137.37 (CH), 147.87 (C), 149.22 (CH), 154.04 (C), 154.85 (C), 165.67 
(C.dbd.O), 206.31 (C). 
EXAMPLE G 
Preparation of (S) or (R)-2-(2-pyridinyl)-4-carboxyquinoline, 
methylbenzylamide 9 
##STR19## 
Freshly prepared acyl chloride 7 (prepared as described in Example E) (2.0 
g, 7.5 mmole) is added to a solution containing triethylamine (2.0 g, 20 
mmol) in 50 ml of dry chloroform. (S)- or (R)-methylbenzyl amine (0.9 g, 
7.4 mmole) is then added in a single portion, with stirring. The solution 
is stirred for an additional 30 minutes at room temperature. The solvent 
is then removed under reduced pressure, and crystallization from hot 
benzene (carbon) yields the title product as a fluffy white solid (2.5 g). 
.sup.1 H NMR (DMSO, 300 MHz): .delta. 1.5 (vbs, 3H), 3.3 (vbs, 1H), 5.7 
(vbs, 1H), 7.1-7.6 (vbm, 3H), 7.75 (vbs, 1H), 8.0 (vbs, 2H), 8.5 (vbs, 
2H), 8.8 (vbs, 1H). .sup.13 C NMR (DMSO, 75 MHz): .delta. 22.69, 49.10, 
116.44, 121.58, 124.77, 125.37, 125.71, 126.51, 127.29, 128.13, 128.83, 
130.10, 130.68, 137.95, 143.80, 144.77, 148.01, 149.80, 155.07, 155.45, 
166.37. 
EXAMPLE H 
General Procedure for the Preparation of 
N-(2-(2-pyridinyl)-4-quinolinyl!carbonyl amino acids 10-18 
SEE SCHEME II FOR FORMULA 
A solution is prepared containing 10 mmole of the amino acid or amino acid 
ester (for instance, 1.31 g leucine 1.45 g leucine methyl ester, 0.75 g 
glycine, 1.28 g of glycylglycine, 1.55 g histidine, 1.69 g histidine 
methyl ester, 1.32 g aspartic acid or 1.46 g glutamic acid), 50 mL of cold 
(5.degree. C.) dry acetonitrile and 2.0 g of dry triethylamine. To this 
solution, with efficient stirring and while in an ice bath, is added 10 
mmol (2.5 g) of freshly prepared acid chloride 7. Stirring is continued at 
5.degree. C. for 30 minutes, then the ice bath is removed and the solution 
stirred for an additional 8 hours. The desired amino acid coupled to the 
acyl group of the cinchonic acid acyl chloride product is collected by 
filtration, washed with acetonitrile (20 mL) and used in subsequent 
preparations without further purification. Yields are: (3.0 g Leucine, 3.2 
g Leucine methyl ester, 2.0 g glycine, 2.5 g of glycyl glycine, 3.2 g 
Histidine, 3.4 g Histidine methyl ester, 3.6 g aspartic acid and 3.0 g 
glutamic acid derivatives). 
EXAMPLE I 
Preparation of 2,2'-bipyridine-4,4'-dicarboxylic acid, N,N-diethyl amide 38 
______________________________________ 
##STR20## 
##STR21## 
______________________________________ 
35 R = H (Aldrich) 41 R = H 
36 R = CO.sub.2 H (Aldrich) 
42 R = CO.sub.2 H 
37 R = CO.sub.2 CH.sub.3 (Aldrich) 
43 R = CO.sub.2 CH.sub.3 
38 R = CON(C.sub.2 H.sub.5).sub.2 
44 R = CON(C.sub.2 H.sub.5).sub.2 
(Possibly new Prepared from 31) 
##STR22## 
##STR23## 
##STR24## 
##STR25## 
______________________________________ 
X = ClO.sub.4, Cl, or PF.sub.6 
2,2'-Bipyridine, 4,4'-dicarboxylic acid (1.0 g, 4.1 mol) is refluxed in 10 
mL of thionyl chloride for 5 hours. The thionyl chloride is removed under 
reduced pressure, and added to 100 mL of toluene. The mixture is brought 
to a boil and filtered (gravity) into a cold stirring solution containing 
diethylamine (600 mg, 8.2 mmol), triethylamine (836 mg, 8.3 mmol) and 50 
mL of toluene. The resulting solution is allowed to stir at room 
temperature for 30 minutes. The solution is poured into 100 mL of 
saturated sodium carbonate solution, and the layers are separated. The 
aqueous phase is extracted twice with 50 mL portions of chloroform. The 
extracts are combined with the toluene, and the volume reduced to about 10 
mL by distillation. Heptane (50 ml) is added to the residue, and the 
resulting solid is filtered giving 2,2'-bipyridine-4,4'-dicarboxylic acid, 
N,N diethyl amide, as a low melting solid (500 mg). 
EXAMPLE J 
Preparation of 5,6-dipyridinyl 2,3-pyrazinedicarbonitrile 49 (Trival name: 
2,3-dicyano-5,6-dipyridylpyrazine) 
Into a 250 mL round bottomed flask are placed, 2,2'-pyridil (8.48 g, 40 
mmol), diaminomaleonitrile (4.32 g, 40 mmol) and 125 mL of ethanol. The 
flask is fitted with a magnetic stirrer and a condenser, and refluxed for 
30 minutes. The mixture is allowed to cool, and 10 mL of water is added. 
Filtration yielded 8.9 g of crude product as a beige solid. The solid is 
boiled in benzene (400 mL) and filtered hot. The red filtrate is discarded 
giving 5.2 g of the title compound as a pale beige solid. 
EXAMPLE K 
Preparation 2,3-dipyridyl-1,4,6-triazanaphthalene 
Into a 50 mL round bottomed flask are placed, 0.515 g (4.0 mmol) of 
3,4-diaminopyridine, 0.848 g (4.0 mmol) of 2,2-pyridil and 25 mL of 
ethanol (95%). With stirring, the mixture is refluxed for 30 minutes. The 
mixture is cooled, and treated with activated carbon, brought to a boil 
and filtered hot. Evaporation of the ethanol leaves a pale yellow oil, 
which slowly crystallized to give the title compound (500 mg) as a light 
yellow solid. 
EXAMPLE L 
Preparation of 2,3-dipyridyl-1,4,8-triazanaphthalene 62 
##STR26## 
The preparation of 62 is identical to that of 61 substituting 
2,3-diaminopyridine for 3,4-diamino pyridine (Example K), giving 900 mg of 
the title compound as a white solid. 
PREATION OF COMPOUNDS OF THE INVENTION 
EXAMPLE 1 
Preparation of 
5-carboxy-12-dimethylamino-pyrido1',2':3,4!imidazo1,5a!quinolin-11-ium 
acyl chloride perchlorate 19 
##STR27## 
Thionyl chloride (40 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 20 mmol (5.0 g) of 
2-(2-pyridyl)-4-carboxyquinoline 4 (prepared as described in Example B) is 
added. The orange solution was allowed to stir in the ice bath for 15 
minutes. The solution is then refluxed for 1 hour. The thionyl chloride is 
removed under reduced pressure. The deep orange red residue is then used 
in subsequent preparations without further purification. 
EXAMPLE 2 
General Procedure for the Preparation of Fluorescent Cinchonic Acid 
Derivatives 
Thionyl chloride (40 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 20 mmol of the cinchonic acid derivative 
(5.0 g 4, 5.4 g of 5, 4.72 g of 6, 5.88 of 8, 7.0 g of 9 (R) or (S)) is 
added. In a single portion, 40 mmol (2.92 g) of dimethylformamide (DMF) is 
added, producing an immediate color change (in the preparation of 23 the 
solution is refluxed for 15 minutes). The orange solution is then allowed 
to stir in the ice bath for an additional 15 minutes. The ice bath is 
removed and the solution is stirred for a further 30 minutes. The thionyl 
chloride is removed under reduced pressure, and the solid is dissolved in 
100 mL of water. The solution is filtered, and 4 g of solid sodium 
perchlorate is added, producing a bright yellow precipitate. The mixture 
is cooled to 5.degree. C., and the solid filtered. The solid can be 
recrystallized from methanol giving the perchlorate salts 20-25 as a 
yellow solids. 
A. Preparation of 
5-carboxy-12-dimethylamino-pyrido1',2':3,4,!imidazo1,5-a!quinolin-11-ium 
perchlorate 20 
##STR28## 
yield: 8.1 g, .sup.13 C NMR: (DMSO-d.sub.6) .delta. 39.46, 114.56, 117.59, 
118.09, 119.25, 120.32, 120.87, 121.90, 122.73, 122.96, 126.44, 127.26, 
128.80, 130.26, 131.37, 166.63. MS m/z (positive in FAB) 306.1240, 
M.sup.+ ! Calcd. for (C.sub.18 H.sub.16 N.sub.3 O.sub.2 PF.sub.6) 
306.124251. Anal. Calcd. for C.sub.18 H.sub.16 B.sub.3 O.sub.2 PF.sub.6 C, 
47.9; H, 3.6; N, 9.3. Found: C, 48.17; H, 226; N, 93. 
B. Preparation of 
5-methoxycarbonyl-12-dimethylamino-pyrido1',2':3,4!imidazo1,5-a!quinolin 
-11-ium perchlorate 21 
##STR29## 
yield: 8.2 g, NMR: .sup.1 H(300 MHz, DMSO-d.sub.6): .delta. 3.25 (s, 6H), 
4.0 (s, 3H), 7.65 (dd, J=6.9, 6.8 Hz, 1H), 7.68 (dd, J=6.9, 6.8 Hz, 1H), 
7.85 (dd, J=7.6, 7.3 Hz, 1H), 7.95 (dd, J=7.9, 7.6 Hz, 1H), 8.80 (d, J=9.7 
Hz, 1H), 8.85 (dd, J=9.7, 7.9, 1H), 8.95 (d, J=8.6 Hz, 1H), 9.05 (s, 1H). 
.sup.13 C (DMSO-d.sub.6): .delta. 39.5, 54.0, 116.1, 119.06, 119.09, 
120.46, 121.07, 121.24, 122.84, 123.60, 124.01, 126.54, 127.45, 129.32, 
130.22, 130.45, 132.70, 166. MS m/z (positive ion FAB) 320.21, M.sup.+ !, 
Calcd. for (C.sub.19 H.sub.18 N.sub.3 O.sub.2) 320.1399. 
C. Preparation of 5-methoxy-12-dimethylamino-pyrido1',2':3,4!imidazo 
1,5-a!quinolin-11-ium perchlorate 22 
yield: 6.4 g, 
##STR30## 
D. Preparation of 
5-chlorethoxycarbonyl-12-dimethylamino-pyrido1',2':3,4!imidazo1,5-a!quin 
olin-11-ium perchlorate 23: 
yield 8.4 g, 
##STR31## 
E. Preparation of 
5-carboxy-12-dimethylamino-pyrido1',2':3,4!imadizo1,5-a!quinolin-11-ium 
5(R)-methylbenzylamide perchlorate 24: 
yield 9.4 g, 
##STR32## 
F. Preparation of 
12-diemethylamino-5-carboxy-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
5(S)-methylbenzylamide perchlorate. 25 
yield 9.3 g. 
##STR33## 
G. Using N,N-diethylformamide in place of the N,N-dimethylformide, and 
repetition of the above procedure, there is produced 
5-carboxy-12-diethylamino-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchlorate, NMR: .sup.1 H (300 MHz, DMSO-d.sub.6): .delta. 1.14 (t, J=7.1 
Hz, 6H), 3.6 (m, 4H), 7.6 (dd, J=6.8, 6.8 Hz, 1H), 7.65 (dd, J=6.8, 6.8 
Hz, 1H), 7.85 (dd, J=7.6, 7.6 Hz, 1H), 7.95 (dd, J=7.6, 7.6 Hz, 1H), 8.8 
(d, J=6.8 Hz, 1H), 8.88 (d, J=8.6 Hz, 1H), 9.1 (s, 1H), 9.15 (d, J=8.6 Hz, 
1H). .sup.13 C (DMSO-d.sub.6) .delta. 13.91, 45.89, 117.05, 118.63, 
119.32, 120.94, 122.43, 122.66, 123.57, 124.50, 126.29, 127.98, 129.33, 
130.08, 130.36, 130.78, 166.91. 
H. Using an equivalent amount of N,N-dibutylformamide in place of the 
N,N-dimethylformamide, there is produced 
5-carboxy-12-dibutylamino-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchlorate NMR: .sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 0.78 (t, J=7.3 
Hz, 6H), 1.15 (q, J=7.3, 4H), 1.55 (m, 4H), 3.75 (m, 4H), 7.55 (dd, J=6.8, 
6.8 Hz, 1H), 7.60 (dd, J=6.8, 6.8 Hz, 1H), 7.85 (dd, J=8.0, 7.3 Hz, 1H), 
7.95 (dd, J=7.3, 7.3 Hz, 1H), 8.70 (d, J=6.8 Hz, 1H), 8.78 (d, J=8.6 Hz, 
1H), 8.95 (d, J=8.0 Hz, 1H), 9.02 (s, 1H), 9.05 (d, J=8.6 Hz, 1H). .sup.13 
C (DMSO-d.sub.6) d 14.00, 20.03, 30.50, 51.68, 116.93, 118.78, 119.21, 
120.86, 122.34, 122.52, 123.46, 124.49, 126.19, 127.87, 129.27, 130.01, 
130.33, 131.13, 166.93. 
EXAMPLE 3 
General Procedure for the Preparation of Fluorescent 5-(Amino 
acid)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-ium 
Derivatives 26-34 
Thionyl chloride (5 mL) is placed in a 25 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1 mmol the cinchoninic acid derivative (307 
mg of 10, 321 mg of 11, 363 mg of 12, 370 mg of 13, 388 mg of 14, 401 mg 
of 15, 364 mg of 16, 365 mg of 17, 379 mg of 18) is added. In a single 
portion, 4 mmol (292 mg) of dimethyl formamide is added, producing an 
immediate color change. The orange solution is allowed to stir in the ice 
bath for 15 minutes. The ice bath is then removed and the solution is 
stirred for an additional 30 minutes. The thionyl chloride is removed 
under reduced pressure, and the solid is dissolved in 25 mL of water. The 
solution is filtered, and 2 g of solid sodium perchlorate is added, 
producing a bright yellow precipitate. The mixture is cooled to 5.degree. 
C., and the solid filtered. The solid can be recrystallized from methanol 
giving the perchlorate salts 26-34 as yellow solids. 
______________________________________ 
##STR34## 
##STR35## 
# R' R Amino acid used 
______________________________________ 
26 H H Glycine 
27 CH.sub.3 
H Glycine, methyl ester 
28 H 
##STR36## L-Leucine 
29 CH.sub.3 
##STR37## L-Leucine, methyl ester 
30 H 
##STR38## L-Histidine 
31 CH.sub.3 
##STR39## L-Histidine, methyl ester 
32 H 
##STR40## GlyGly 
33 H 
##STR41## Aspartic Acid 
34 H 
##STR42## Glutamic acid 
______________________________________ 
X = ClO.sub.4, PF.sub.6 or Cl 
Yields: 
5-(L-glycyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11- 
ium perchlorate 26: 550 mg, NMR: .sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 
3.5 (s,6H), 4.5 (d, J=7.7 Hz, 1H), 4.55 (d, J=7.7 Hz, 1H), 7.25 (m, 1H), 
7.30 (m, 1H), 7.85 (m, 1H), 7.95 (m, 1H), 8.22 (d=j 7.0 Hz, 1H), 8.35 (m, 
J=7.0 Hz, 1H), 8.85 (m, 3H). .sup.13 C NMR (75 MHz, DMSO-d.sub.6), DEPT 
(90) Correlations) .delta. 39.33 (CH.sub.3), 61.93 (CH.sub.2), 118.07 
(CH), 118.28 (CH), 119.97 (CH), 120.04 (CH), 1211.59 (CH), 127.62 (CH), 
128.82 (CH), 128.85 (CH), 129.81 (CH), 129.90 (CH). 
5-(L-glycylmethylester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!qu 
inolin-11-ium-perchlorate 27: 540 mg, 
5-(L-leucinyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11 
-ium-perchlorate 28: 600 mg, 
5-(L-leucinemethyl 
ester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-ium-pe 
rchlorate 29: 470 mg, 
5-(L-histidinyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin- 
11-ium-perchlorate 30 550 mg, NMR:.sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 
3.3 (s, 6H), 3.75 (m, 2H), 4.00 (s, 3H), 5.10 (m, 1H), 7.55 (m, 2H), 7.80 
(m, 1H), 7.95 (m, 2H), 8.12 (s, 2H), 8.15 (s, 2H), 8.40 (s, 1H), 8.55 (m, 
1H)m 8.90 (m, 1H). .sup.13 C NMR (75 MHz, DMSO-d.sub.6,DEPT (90) 
correlations) .delta. 25.87, 39.01, 51.65, 52.42, 115.07, 117.49, 118.13, 
118.35, 119.83, 121.27, 121.99, 123.59, 124.92, 126.98, 128.73, 129.23, 
129.79, 130.17, 133.81, 164,23, 166.51, 170.38. 
(L-histidinylmethyl 
ester)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11-ium-pe 
rchlorate 31: 666 mg, 
5-(L-glycylglycyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinoli 
n-11-ium-perchlorate 32: 550 mg, 
5-(L-glutamyl)-12-dimethylamino-pyridyl1',2':3,4!imidazo1,5-a!quinolin-11 
-ium-perchlorate 34: 610 mg. 
EXAMPLE 4 
Preparation of Fluorescent Bipyridine Derivatives 41-46 
A. 6-(dimethylamino)-dipyrido1,2-c:2',1'-e!imidazol-5-ium perchlorate 41 
______________________________________ 
##STR43## 
##STR44## 
______________________________________ 
35 R = H (Aldrich) 41 R = H 
36 R = CO.sub.2 H (Aldrich) 
42 R = CO.sub.2 H 
37 R = CO.sub.2 CH.sub.3 (Aldrich) 
43 R = CO.sub.2 CH.sub.3 
38 R = CON(C.sub.2 H.sub.5).sub.2 
44 R = CON(C.sub.2 H.sub.5).sub.2 
(Possibly new Prepared from 31) 
##STR45## 
##STR46## 
##STR47## 
##STR48## 
______________________________________ 
X = ClO.sub.4, Cl, or PF.sub.6 
A solution of 2,2'-bipyridine 35 (1.0 g, 6.4 mmol) in 25 mL of benzene is 
cooled to 0.degree. C. in an ice bath. To a solution containing 800 mg 
(6.78 mmol) of thionyl chloride in 5 mL of benzene is added 495 mg of DMF 
(4.95 mmol) in a single portion. Both solutions are stirred for 5 minutes. 
The mixture of DMF/thionyl chloride is added to the 2,2' bipyridine 
solution with stirring in a single portion. The addition produces a yellow 
solution containing an oily brown residue. The reaction is stirred for an 
additional 15 minutes at 0.degree. C., and then the ice bath is removed, 
and stirring is continued for an additional 30 minutes. As the DMF is 
consumed, the oily brown residue gradually solidifies. The solid is 
filtered, and allowed to dry. The precipitate is dissolved in water, and 
filtered. The addition of 5 g of solid sodium perchlorate produces the 
immediate formation of a bright yellow precipitate (1.7 g). The 
precipitate is dried, and chromatographed on alumina (neutral, Brockman 
Activity I) elution with acetonitrile. The salt elutes as a broad yellow 
band, recrystallization from ethanol (sparingly soluble and acetonitrile 
(soluble), yields 1.5 g (75%) of 1 as a yellow crystalline solid. NMR: 
.sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 3.14 (s, 6H), 7.49 (m, 4H), 8.61 
(d, J=8.89 Hz, 2H), 8.67 (d, J=7.17 Hz, 2H). .sup.13 C (75 MHz, 
DMSO-d.sub.6) .delta. 40.00, 119.32, 119.34, 120.45, 121.30, 122.33, 
127.15. IR (KBr) cm.sup.-1 1658, 1616, 1646, 1561, 1543, 1429. MS m/z 
(positive ion FAB) 212.0 M!.sup.+, Calcd. for (C.sub.13 H.sub.14 N.sub.3) 
212.1. Anal. Calcd for C.sub.13 H.sub.14 N.sub.3 O.sub.4 Cl: C, 50.1; H, 
4.5; N 13.5. Found: C, 49.89; H, 4.21; N, 13.66. 
B. 
6-(dimethylamino)-2-10-bis(carboxy)-dipyrido1,2-c:2',1'-e!imidazol-5-ium 
perchlorate 42 
Thionyl chloride (5 mL) is added to a 25 mL round bottom flask containing a 
stirring bar. The flask is cooled to 0.degree.-5.degree. C. in an ice 
bath, and 550 mg (2.3 mmol) of 36 is added. The mixture is again brought 
to 5.degree. C. To the stirring solution, 150 mg (2.1 mmol) is added in a 
single portion. The ice bath is removed, and the solution is stirred for 1 
hour. The orange solution is cooled to room temperature, and the excess 
thionyl chloride removed under reduced pressure (.about.0.1 torr). The 
residue is dissolved in 125 mL of water, brought to a boil, and filtered 
while hot. The addition of 1 g of sodium perchlorate resulted in the 
immediate precipitation of title compound 42 as a yellow salt. The mixture 
is cooled to 5.degree. C. and filtered. Recrystallization from methanol 
yielded 400 mg (41%) of the title compound as orange crystals. NMR: .sup.1 
H (300 MHz, DMSO-d.sub.6) .delta. 3.20 (s, 6H), 7.84 (dd, J=7.37, 0.86 Hz, 
2H), 8.76 (d, J=7.37 Hz, 2H), 9.52 (bs, 2H). .sup.13 C (300 MHz, 
DMSO-d.sub.6) .delta. 118.52, 120.80, 121.72, 122.38, 124.87, 130.02, 
165.20. IR (KBr) cm.sup.-1 1721(C.dbd.O) 1626, 1563, 1452, 1428, 1327, 
1276, 1258. MS m/z (positive ion FAB) 300.1, M!.sup.+, Calcd. for 
(C.sub.15 H.sub.14 N.sub.3 O.sub.4) 300.1. Anal. Calcd. for C.sub.15 
H.sub.14 N.sub.3 O.sub.8 Cl: H.sub.2 OC, 43.1; H, 3.9; N, 10.1. Found: C, 
43.12; H, 3.79; N, 9.99. 
C. 
6-(dimethylamino)-2,10-bis(methoxycarbonyl)-Dipyrido1,2-c:2',1'-e!imidazo 
l-5-ium perchlorate 43 
Thionyl chloride (5 mL) is added to a 25 mL round bottom flask containing a 
stirring bar. The flask is cooled to 0.degree.-5.degree. C. in an ice 
bath, and 410 mg (1.5 mmol) of 5,5'-dimethylamino carbonyl-2,2'-bipyridine 
37 is added. To the stirring solution, 150 mg of DMF (2.1 mmol) is added 
in a single portion. The ice bath is removed; the solution is stirred for 
30 minutes, and finally brought to a boil. The orange solution is cooled 
to room temperature, and the excess thionyl chloride removed under reduced 
pressure (.about.0.1 torr). The residue is dissolved in 75 mL of water, 
and any solids removed by filtration. The addition of 3 g of sodium 
perchlorate resulted in the immediate precipitation of 43 as yellow salt. 
Recrystallization from methanol yielded 500 mg (78%) of the title compound 
as orange crystals. NMR: .sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 3.21 (s, 
6H), 4.00 (s, 6H), 7.87 (bd, J=7.31 Hz, 2H), 8.80 (d, J=7.38 Hz, 2H), 9.65 
(bs, 2H). .sup.13 C (75 MHz, DMSO-d.sub.6) .delta. 39.51, 52.94, 118.08, 
120.87, 122.01, 122.59, 123.66, 130.46, 164.14. IR (KBr) cm-1 1719, 1622, 
1561, 1438, 1327, 1254, 1093. IR (KBr) cm-1 1719, 1622, 1561, 1438, 1327, 
1254, 1093. MS m/z (positive ion FAB) 328.1, M!+, Calcd. for (C.sub.17 
H.sub.18 N.sub.3 O.sub.4) 328.1. Anal. Calcd. for C.sub.17 H.sub.18 
N.sub.3 O.sub.8 Cl C, 47.7; H, 4.2; N, 9.8. Found C, 47.68; H, 4.21; N, 
9.82. 
D. 
6-(dimethylamino)-2,10-bis(diethylaminocarbonyl)-dipyrido1,2-c:2',1'-e!im 
idazol-5-ium hexafluorphosphate 44 
Thionyl chloride (10 mL) is placed in a 25 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 354 mg (1 mmol) of 38 (prepared as 
described in Example I) is added. In a single portion, 4 mmol (292 mg) of 
DMF is then added, producing an immediate color change. The orange 
solution is allowed to stir in the ice bath for 15 minutes. The ice bath 
is then removed and the solution is stirred for an additional 30 minutes. 
The thionyl chloride is removed under reduced pressure, and the solid is 
dissolved in 50 mL of water. The solution is filtered, and 2 g of solid 
ammnonium hexafluorophosphate is added, producing a bright orange 
precipitate. The mixture is cooled to 5.degree. C. and the solid filtered. 
The solid can be recrystallized from methanol giving the 
hexafluorophosphate salt 44 as an orange solid (420 mg). 
E. 
6-(dimethylamino)-2,10-bis(2'-pyridyl)-dipyrido1,2-c:2',1'-e!imidazol-5-i 
um hexafluorphosphate 45 
Thionyl chloride (10 mL) is placed in a 25 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 310 mg (1 mmol) of the quaterpridine 39 is 
added. In a single portion, 4 mmol (292 mg) of DMF is added, producing an 
immediate color change. The orange solution is allowed to stir in the ice 
bath for 15 minutes. The ice bath is then removed and the solution is 
stirred for an additional 30 minutes. The thionyl chloride is removed 
under reduced pressure, and the solid is dissolved in 50 mL of water. The 
solution is filtered, and 2 g of solid ammonium hexafluorophosphate is 
added, producing a bright yellow/orange precipitate. The mixture is cooled 
to 5.degree. C., and the solid filtered. The solid is then chromatographed 
on alumina (acetonitrile eluent) giving the title compound (350 mg) as an 
orange/yellow solid. 
F. Preparation of Fluorescent Quaterpyridinium Adduct 46 
Thionyl chloride (10 mL) is placed in a 25 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1 mmol of 40 (as its bis PF.sub.6.sup.- 
salt, 630 mg) is added. In a single portion, 4 mmol (292 mg) of DMF is 
added, producing an immediate color change. The purple/red solution is 
allowed to stir in the ice bath for 15 minutes. The ice bath is then 
removed and the solution is stirred for an additional 30 minutes. The 
thionyl chloride is removed under reduced pressure, and the solid is 
dissolved in 50 mL of water. The solution is filtered, and 2 g of solid 
ammonium hexafluorophosphate is added, producing a deep purple 
precipitate. The mixture is cooled to 5.degree. C., and the solid 
filtered. The solid can be recrystallized from methanol giving the 
hexafluorphosphate salt 46 as a deep purple solid (750 mg). 
EXAMPLE 5 
A. Preparation of 
6-(dimethylamino)-1-(2-pyridinyl)-pyrido1',2':3,4!imidazo1,5-a!pyrazin-5 
-ium perchlorate 52 
(monomeric dpp) 
##STR49## 
A 25 mL round bottomed flask containing 10 mL of thionyl chloride is cooled 
to 5.degree. C. in an ice bath. To the flask is added 
2,3-bis-(2-dipyridyl)pyrazine 50 (468 mg, 2.0 mmole), and the mixture 
stirred for 5 minutes. DMF (146 mg, 2.0 mmole) is added dropwise over a 
period of 20 minutes, and the orange solution stirred for an additional 30 
minutes. The thionyl chloride is removed under reduced pressure 
(.about.0.1 torr, 25.degree. C.). The resulting red solid is dissolved in 
150 mL of water, and precipitated by the addition of 2 g of ammonium 
hexafluorophosphate. The resulting yellow solid is filtered and dried. 
Column chromatography (Alumina neutral, acetonitrile) can be used to 
remove traces of the dimer (54). The deep yellow band is collected and 
recrystallized from methanol (sparingly soluble) and acetonitrile 
(soluble). The procedure gives 52 as a yellow solid (300 mg): NMR: .sup.1 
H (300 MHz, DMSO-d.sub.6) .delta. 3.45 (s, 6H), 7.68 (m, 2H), 7.80 (m, 
1H), 7.95 (m, 3H), 8.20 (m, 3H), 8.85 (m, 1H), 8.88 (d, J=2.1 Hz, 1H), 
8.98 (m, 1H). .sup.13 C (75 MHz, DMSO-d.sub.6) .delta. 39.64, 116.28, 
118.88, 119.15, 120.38, 120.86, 122.26, 122.62, 123.29, 124.39, 126.16, 
127.76, 129.15, 130.22, 132.41, 166.83. E.A. 
B. Preparation of 
6,11-di(dimethylamino)-bispyrido1',2':3,4!imidazo1,5-a:5',1'-c!pyrazine- 
5,10-diium diperchlorate 53 (monomeric dimethyl dpp) 
A 25 mL round bottomed flask containing 10 mL of thionyl chloride is cooled 
to 5.degree. C. in an ice bath. To the flask is added 51 (524 mg, 2.0 
mmole), and the mixture stirred for 5 minutes. DMF (146 mg, 2.0 mmole) is 
added in a single portion, and the orange solution stirred for an 
additional 30 minutes. The thionyl chloride is removed under reduced 
pressure (.about.0.1 torr, 25.degree. C.). The resulting red solid is 
dissolved in 150 mL of water, and precipitated by the addition of 2 g of 
ammonium hexafluorophosphate. The resulting yellow solid is filtered and 
dried. Column chromatography (alumina neutral, acetonitrile) can be used 
to remove traces of the dimer (55). The deep yellow band is collected and 
recrystallized from methanol (sparingly soluble) and acetonitrile 
(soluble). The procedure gives 53 as a yellow-orange solid (350 mg). NMR: 
.sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 3.55 (s, 6H), 7.40 (dd, J=7.3, 
7.3 Hz, 2H), 7.52 (dd, J=9.0, 7.3 Hz, 2H), 8.38 (s, 2H), 8.50 (d, j=9.0, 
2H), 8.60 (d, J=7.3 Hz, 2H). .sup.13 C (75 MHz, DMSO-d.sub.6) .delta. 
40.81 (CH.sub.3), 106.653 (C), 114.252 (CH), 118.727 (CH), 119.144 (CH), 
120.347(C), 123.599 (CH), 126.421 (CH), 134.338 (C). 
EXAMPLE 6 
A. Preparation of dimeric dpp 54 
##STR50## 
A 25 mL round bottomed flask containing 10 mL of thionyl chloride is cooled 
to 5.degree. C. in an ice bath. To the flask is added 
2,3-bis-(2-dipyridyl)pyrazine 50 (468 mg, 2.0 mmole), and the mixture 
stirred for 5 minutes. N,N-dimethyl formamide (DMF) (584 mg, 8.0 mmole) is 
added in a single portion, and the orange solution stirred for an 
additional 30 minutes. The thionyl chloride is removed under reduced 
pressure (.about.0.1 torr, 25.degree. C.). The resulting red solid is 
dissolved in 150 mL of water, and precipitated by the addition of 2 g of 
ammonium hexafluorophosphate. The resulting yellow solid is filtered and 
dried. Recrystallization from methanol (sparingly soluble) and 
acetonitrile (soluble). The procedure gives 54 as a yellow solid (700 mg). 
B. Preparation of Dimeric dimethyl dpp 55 
A 25 mL round bottomed flask containing 10 mL of thionyl chloride is cooled 
to 5.degree. C. in an ice bath. To the flask is added 51 (524 mg, 2.0 
mmole), and the mixture stirred for 5 minutes. N,N-dimethyl formamide 
(DMF) (584 mg, 8.0 mmole) is added in a single portion, and the orange 
solution stirred for an additional 30 minutes. The thionyl chloride is 
removed under reduced pressure (.about.0.1 torr, 25.degree. C.). The 
resulting red solid is dissolved in 150 mL of water, and precipitated by 
the addition of 2 g of ammonium hexafluorophosphate. Recrystallization 
from methanol (sparingly soluble) and acetonitrile (soluble). The 
procedure gives 55 as a yellow-orange solid (680 mg). 
C. Preparation of dimeric dicyano dpp 56 
A 25 mL round bottomed flask containing 10 mL of thionyl chloride is cooled 
to 5.degree. C. in an ice bath. To the flask is added 
5,6-dipyridinyl-2,3-pyrzainedicarbonitrile 49 (572 mg, 2.0 mmole, prepared 
as described in Example J), and the mixture stirred for 5 minutes. 
N,N-dimethyl formamide (DMF) (584 mg, 8.0 mmole) is added in a single 
portion, and the orange solution stirred for an additional 30 minutes. The 
thionyl chloride is removed under reduced pressure (.about.0.1 torr, 
25.degree. C.). The resulting red solid is dissolved in 150 mL of water, 
and precipitated by the addition of 2 g of ammonium hexafluorophosphate. 
Recrystallization from methanol (sparingly soluble) and acetonitrile 
(soluble). The procedure gives 56 as a yellow-orange solid (650 mg). 
EXAMPLE 7 
Preparation of 
12-(dimethylamino)-6-(2-pyridinyl)-pyrido1'2':3,4!imidazo1,5-a!quinoxali 
n-11-ium perchlorate 63 (quin momer) 
##STR51## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 500 mg (1.76 mmole) of 
2,3-dipyridylquinoxaline 60, and the mixture stirred for 5 minutes. 
Dimethyl formamide (129 mg, 1.76 mmole) is added to the flask a single 
portion, and the orange solution stirred for 30 minutes. The thionyl 
chloride is removed under reduced pressure (.about.0.1 torr, 25.degree. 
C.). The resulting red solid is dissolved in 150 mL of water, and 
precipitated by the addition of 3 g of ammonium hexafluorophosphate. 
Column chromatography (Alumina neutral, acetonitrile) can be used to 
remove traces of the dimer (64). The resulting yellow/orange solid is 
filtered, dried, and recrystallized from a mixture of methanol (sparingly 
soluble) and acetonitrile yielding 470 mg of 63 as an orange crystalline 
solid. NMR: .sup.1 H (400 MHz, DMSO-d.sub.6) .delta. 3.27 (s, 6H), 7.68 
(m, 2H), 7.81 (m, 1H), 7.99 (m, 3H), 8.21 (m, 3H), 8.86 (m, 2H), 8.98 (m, 
1H). .sup.13 C NMR (400 MHz, DMSO-d.sub.6, DEPT (90) correlations) .delta. 
38.36 (CH.sub.3), 109.15 (C), 116.94 (CH), 118.62 (CH), 119.29(CH), 121.75 
(CH), 121.83 (C), 122.65(C), 123.45 (CH), 125.08 (CH), 126.75 (CH), 129.01 
(CH), 129.10 (CH), 129.20 (CH), 131.65 (C), 136.45 (C), 137.26 (CH), 
147.96 (CH), 150.75 (C), 153.14 (C). FABMS Calcd. for C.sub.21 H.sub.18 
N.sub.5 =340.40. Found: 340.24. 
EXAMPLE 8 
A. Preparation of Quin dimer 
6,13-bis-(dimethylamino)-Bispyrido1',2':3,4!imidazo1,5-a:5'1'-c!quinoxal 
in-5,12-diium diperchlorate 64 
##STR52## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 500 mg (1.76 mmole) of 
2,3-dipyridylquinoxaline 60, and the mixture stirred for 5 minutes. 
Dimethyl formamide (514 mg, 7.0 mmole) is added over a period of 20 
minutes, and the orange solution stirred for 30 minutes. The thionyl 
chloride is removed under reduced pressure (.about.0.1 torr, 25.degree. 
C.). The resulting red solid is dissolved in 150 mL of water, and 
precipitated by the addition of 3 g of ammonium hexafluorphosphate. The 
resulting yellow solid is filtered, and recrystallized from a mixture of 
methanol (sparingly soluble) and acetonitrile (soluble), yielding 700 mg 
of 64 as a red crystalline solid. NMR: .sup.1 H (400 MHz, DMSO-d.sub.6) 
.delta. 3.22 (s, 12H), 7.41 (dd, J=7.0, 6.8 Hz, 2H), 7.55 (dd, J=9.5, 6.8 
Hz, 2H), 8.00 (dd, J=6.5, 3.5 Hz, 2H), 8.43 (dd, J=6.5, 3.5 Hz, 2H), 8.47 
(d, J=9.5 Hz, 2H), 8.65 (d, J=7.0 Hz, 2H). .sup.13 C NMR (75 MHz, 
DMSO-d.sub.6, DEPT (90) correlations) .delta. 38.38 (CH.sub.3), 110.26 
(C), 121.43 (CH), 121.73 (CH), 123.13 (CH), 123.52 (C), 126.36 (CH), 
127.07 (C), 129.92 (CH), 133.62 (CH), 138.66 (C). FABMS Calcd. for 
C.sub.24 H.sub.24 N.sub.6 =396.49. Found=396.30. 
B. Preparation of .beta.-azo-dpp dimer 65 
The preparation of 65 is identical to that of 64 (above), using 
2,3-di(2-pyridyl)-1,4,9-triazanapthalene giving 450 mg of 65 as a red 
solid. 
C. Preparation of .alpha.-azo-dpp dimer 66 
The preparation of 65 is identical to that of 64 (above), using 
2,3-di(2-pyridinyl)-1,4,8-triazanaphthalene giving 600 mg of 66 as a red 
solid. 
EXAMPLE 9 
Preparation of diaza Anthracene monomer: 
13-(dimethylamino)-7-(2-pyridinyl)-benzog!-pyrido1',2':3,4!imidazo1,5-a 
!quinoxalin-12-ium perchlorate 68 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 664 mg (2.0 mmole) of 
2,3-dipyridinyl-benzog!quinoxaline 67, and the mixture stirred for 5 
minutes. Dimethyl formamide (146 mg, 2.0 mmole) is added to the flask 
dropwise over a period of 20 minutes, and the red solution stirred for 30 
minutes. The thionyl chloride is removed under reduced pressure 
(.about.0.1 torr, 25.degree. C.). The resulting red solid is dissolved in 
a minimum amount of water, and precipitated by the addition of 3 g of 
ammonium hexafluorophosphate. The resulting red/orange solid is filtered, 
dried, and recrystallized from a mixture of methanol and acetonitrile 
yielding 620 mg of 68 as an red crystalline solid. NMR: .sup.13 C NMR (75 
MHz, DMSO-d.sub.6, DEPT (90) correlations) .delta. 123.727, 124.131, 
127.694, 127.851, 128.896, 134.281, 137.282, 148.388, 148.388, 153.441, 
157.456. FABMS Calcd. for C.sub.25 H.sub.20 N.sub.5 =390.1719 
Found=390.24. 
EXAMPLE 10 
Preparation of diaza Anthracene dimer: 
7,18-bis(dimethylamino)-benzog!bispyrido1',2':3,4!imidazo1,5-a:5',1'-c! 
quinoxaline-6,17-diium bishexafluorophosphate 69 
##STR53## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 664 mg (2.0 mmole) of 67, and the mixture 
stirred for 5 minutes. Dimethyl formamide (514 mg, 7.0 mmole) is added 
over a period of 20 minutes, and the orange solution stirred for 30 
minutes. The thionyl chloride is removed under reduced pressure 
(.about.0.1 torr, 25.degree. C.). The resulting red solid is dissolved in 
a minimum amount of water, and precipitated by the addition of 3 g of 
ammonium hexafluorphosphate. The resulting red solid is filtered, and 
recrystallized from a mixture of methanol (sparingly soluble) and 
acetonitrile (soluble), yielding 740 mg of 69 as a red crystalline solid. 
NMR: .sup.13 C NMR (100 MHz, DMSO-d.sub.6. 
EXAMPLE 11 
Preparation of 
6-(dimethylamino)-3,4-diphenyl-pyrido1',2';3,4!imidazo5,1-c!-1,2,4-triaz 
ine-5-ium perchlorate 71 (or 72) 
##STR54## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 620 mg (2.0 mmole) of 
3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine 70, and the mixture stirred for 
5 minutes. Dimethyl formamide (514 mg, 7.0 mmole) is added in a single 
portion, and the orange/red solution stirred for 30 minutes. The thionyl 
chloride is removed under reduced pressure (.about.0.1 torr, 25.degree. 
C.). The resulting red solid is dissolved in a minimum amount of water, 
and precipitated by the addition of 3 g of ammonium hexafluorphosphate. 
The resulting red solid is filtered, and recrystallized from a mixture of 
methanol (sparingly soluble) and acetonitrile (soluble), yielding 690 mg 
of 71 or 72 as a red crystalline solid. 
6-(dimethylamino)-3,4-pyrdio1',2':3,4!imidazo5,1-c!1,2,4!triazine-5-ium 
, diphenyl-perchlorate: .sup.1 H (300 MHz, DMSO-d6) .delta. 3.5 (s, 3H), 
7.1 (m, 10H), 7.3 (m, 2H), 8.8 (m, 1H). .sup.13 C NMR (75 MHz, 
DMSO-d.sub.6, DEPT (90) correlations) .delta. 40.77, 118.25, 1218.44, 
118.68, 120.40, 120.96, 122.56, 126.08, 128.75, 129.03, 129.54, 129.76, 
130.09, 130.47, 131.19, 134.27, 136.13, 146.71, 154.39. 
EXAMPLE 12 
A. Preparation of 3-(dimethylamino)-imidazo1,5-a!pyridin-1-ol 
monoperchlorate salt 75 
##STR55## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 800 mg (6.6 mmole) of 2-pyridine 73, and the 
mixture stirred for 5 minutes. Dimethyl formamide (1.02 g, 14 mmole) is 
added in a single portion, and the blue solution stirred for 90 minutes. 
The solvents are removed under reduced pressure to give 75 (1.0 g). 
B. Preparation of Pyrazinamide adduct 76 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 800 mg (6.5 mmole) of pyrazinamide 74, and the 
mixture stirred for 5 minutes. Dimethyl formamide (1.02 g, 14 mmole) is 
added in a single portion, and the blue solution stirred for 90 minutes. 
The solvents are removed under reduced pressure to give 76 (1.0 g). 
EXAMPLE 13 
A. Preparation of 2-Pyridinecarboxylic acid adduct 79 
##STR56## 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 800 mg (6.5 mmole) of 2-pyridinecarboxylic 
acid 77, and the mixture stirred for 5 minutes. Dimethyl formamide (1.02 
g, 14 mmole) is added in a single portion, and the orange/red solution 
stirred for 90 minutes. The solvents are removed under reduced pressure to 
give 79 (0.600 g). 
B. Preparation of 2-Pyrazinecarboxylic acid adduct 80 
Thionyl chloride (10 mL) is added to a 25 mL round bottom flask in an ice 
bath. To the flask is added 800 mg (6.5 mmole) of 2-Pyrazinecarboxylic 
acid 74, and the mixture stirred for 5 minutes. Dimethyl formamide (1.02 g 
mg, 14 mmole) is added in a single portion, and the orange/red solution 
stirred for 90 minutes. The solvents are removed under reduced pressure to 
give 80 (0.900 g). 
EXAMPLE 14 
Preparation of 3-dimethylamino-imidazo 1,5-a!pyridine monoperchlorate 82 
##STR57## 
Thionyl chloride (25 mL) of cold (5.degree. C.) is added to a 50 mL round 
bottom flask in an ice bath. To the flask is added 2.0 g (19.2 mmole) of 
2-cyanopyridine 81, and the mixture stirred for 5 minutes. Dimethyl 
formamide (2.5 mg, 34.2 mmole) is added in a single portion, and the 
purple/blue solution stirred for 60 minutes. The thionyl chloride is 
removed under reduced pressure (.about.0.1 torr, 25.degree. C.). The 
resulting blue solid is dissolved in a minimum amount of water, and 
precipitated by the addition of 7 g of magnesium perchlorate. The 
resulting blue solid is filtered, giving 1.5 g of 82 as a blue crystalline 
solid. 
EXAMPLE 15 
Preparation of 
5-(carboxy)-12-(dimethylamino)-pyrido1',2':3,4!imidazo1,5,a!quinlon-11-i 
umacyl chloride perchlorate 19 using POCl.sub.3 
##STR58## 
Phosphorous oxychloride (25 mL) is placed in a 50 mL round bottomed flask, 
fitted with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. 
While in an ice bath, with stirring, 1.0 g of 5 (4.2 mmol) is added. In a 
single portion, 530 mg (7.2 mmol) of DMF is added, producing an immediate 
color change. The orange solution is allowed to stir in the ice bath for 
15 minutes. The ice bath is then removed and the solution is stirred for 
an additional 30 minutes. The phosphorous oxychloride is removed under 
reduced pressure, and the solid is dissolved in 100 mL of water. The 
solution is filtered, and 2 g of solid ammonium hexafluorphosphate is 
added, producing a bright yellow precipitate. The mixture is cooled to 
5.degree. C., and the solid filtered. The solid can be recrystallized from 
methanol giving the perchlorate salt 19 as a yellow solid (1.8 g). The 
.sup.1 H and .sup.13 C NMR data is exactly the same as the product derived 
from the SOCl.sub.2 reaction. 
EXAMPLE 16 
Preparation of General Procedure of Fluorescent Cinchonic Acid Derivatives 
20 using POCl.sub.3 
Phosphorous oxychloride (25 mL) is placed in a 50 mL round bottomed flask, 
fitted with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. 
While in an ice bath, with stirring, 1.1 g of 5 (4.2 mmol) is added. In a 
single portion, 530 mg (7.2 mmol) of N,N-dimethyl formamide (DMF) is 
added, producing an immediate color change. The orange solution is allowed 
to stir in the ice bath for 15 minutes. The ice bath is then removed and 
the solution is stirred for an additional 30 minutes. The phosphorous 
oxychloride is removed under reduced pressure, and the solid is dissolved 
in 100 mL of water. The solution is filtered, and 2 g of solid ammonium 
hexafluorphosphate is added, producing a bright yellow precipitate. The 
mixture is cooled to 5.degree. C., and the solid filtered. The solid can 
be recrystallized from methanol giving the perchlorate salt 20 as a yellow 
solid (2.0 g). 
EXAMPLE 17 
Preparation of 3-dimethylamino-imidazo1,5-a!pyridine monoperchlorate Using 
POCl.sub.3 
##STR59## 
Phosphorous oxychloride (25 mL) is added to a 50 mL round bottom flask in 
an ice bath, and cooled to (5.degree. C.). To the flask is added 2.0 g 
(19.2 mmole) of 2-cyanopyridine 81, and the mixture stirred for 5 minutes. 
Dimethyl formamide (2.5 mg, 34.2 mmole) is added in a single portion, and 
the purple/blue solution stirred for 60 minutes. The thionyl chloride is 
removed under reduced pressure (.about.0.1 torr, 25.degree. C.). The 
resulting blue solid is dissolved in a minimum amount of water, and 
precipitated by the addition of 7 g of sodium perchlorate. The resulting 
blue solid is filtered, giving 2.2 g of 82 as a blue crystalline solid. 
EXAMPLE 18 
Preparation of Fluorescent PVA/Cinchonate Polymer 96 
##STR60## 
To a stirred mixture of 1.0 g of polyvinyl alcohol (MW 30,000-70,000) in 
100 mL of acetonitrile is added 1.0 g (2.4 mmol) 19 (as its perchlorate 
salt). The mixture is stirred for 10 minutes, and then refluxed for 2 
hours. The solid is filtered and washed with methanol (2.times.20 mL). The 
material is slightly soluble in hot water, and aqueous solutions can be 
evaporated to yield films of 96. 
EXAMPLE 19 
Preparation of Fluorescent 
5-carboxy-12-(dibutylamino)-pyrido1',2':3,4!-imidazo1,5-a!quinolin-11-iu 
m perchlorate 97 using N,N-dibutylformamide 
##STR61## 
Thionyl chloride (25 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1.0 g of 4 (5.0 mmol) is added. In a single 
portion, 2.5 g (16 mmol) of N,N-dibutylformamide is added, producing an 
immediate color change. The orange solution is allowed to stir in the ice 
bath for 15 minutes. The ice bath is then removed and the solution is 
stirred for an additional 30 minutes. The thionyl chloride is removed 
under reduced pressure, and the solid is dissolved in 100 mL of water. The 
solution is filtered, and 2 g of solid ammonium hexafluorphosphate is 
added, producing a bright yellow precipitate. The mixture is cooled to 
5.degree. C., and the solid filtered. The solid can be recrystallized from 
methanol giving the perchlorate salts 97 as a yellow solid (1.8 g). 1H 
(300 MHz, DMSO-d.sub.6) .delta. 0.78 (t, J=7.3 Hz, 6H), 1.15 (q, J=7.3, 
4H), 1.55 (m, 4H), 3.75 (m, 4H), 7.55 (dd, J=6.8, 6.8 Hz, 1H), 7.60 (dd, 
J=6.8, 6.8 Hz, 1H), 7.85 (dd, J=8.0, 7.3 Hz, 1H), 7.95 (dd, J=7.3, 7.3 Hz 
1H), 8.70 (d, J=6.8 Hz, 1H), 8.78 (d, J=8.6 Hz, 1H), 8.95 (d, J=8.0 Hz, 
1H), 9.02 (s, 1H), 9.05 (d, J=8.6 Hz, 1H). .sup.13 C (DMSO-d.sub.6) 
.delta. 14.00, 20.03, 30.50, 51.68, 116.93, 118.78, 119.21, 120.86, 
122.34, 122.52, 123.46, 124.49, 126.19, 127.87, 129.27, 130.01, 130.33, 
131.13, 166.93. 
EXAMPLE 20 
Preparation of 
5-carboxy-12-(diethylamino)-pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchloate 98 using N,N-diethylformamide 
##STR62## 
Thionyl chloride (25 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1.0 g of 4 (5.0 mmol) is added. In a single 
portion, 1.6 g (16 mmol) of N,N-diethylformamide is added, producing an 
immediate color change. The orange solution is allowed to stir in the ice 
bath for 15 minutes. The ice bath is then removed and the solution is 
stirred for an additional 30 minutes. The thionyl chloride is removed 
under reduced pressure, and the solid is dissolved in 100 mL of water. The 
solution is filtered, and 2 g of solid ammonium hexafluorphosphate is 
added, producing a bright yellow precipitate. The mixture is cooled to 
5.degree. C., and the solid filtered. The solid can be recrystallized from 
methanol giving the perchlorate salts 98 as a yellow solid (1.8 g). .sup.1 
H (300 MHz, DMSO-d.sub.6) .delta. 1.14 (t, J=7.1 Hz, 6H), 3.6 (m, 4H), 
7.65 (dd, J=6.8, 6.8 Hz, 1H), 7.65 (dd, J=6.8, 6.8 Hz, 1H), 7.85 (dd, 
J=7.6, 7.6 Hz, 1H) 7.95 (dd, J=7.6, 7.6 Hz, 1H), 8.8 (d,J=6.8 Hz, 1H), 
8.88 (d, J=8.6 Hz, 1H), 9.1 (s, 1H), 9.15 (d, J=8.6 Hz, 1H). .sup.13 C 
(DMSO-d.sub.6) .delta. 13.91, 45.89, 117.05, 118.63, 119.32, 120.94, 
122.43, 122.66, 123.57, 124.50, 126.29, 127.98, 129.33, 130.08, 130.36, 
130.78, 166.91. 
EXAMPLE 21 
Preparation of Fluorescent 
5-carboxy-12-(4-morpholinyl)pyrido1',2':3,4!imidazo1,5-a!quinolin-11-ium 
perchlorate 
##STR63## 
Thionyl chloride (25 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1.0 g of 4 (5.0 mmol) is added. In a single 
portion, 1.84 g (16 mmol) of 1-Morpholinecarboxyaldehyde is added 
producing an immediate color change. The orange solution is allowed to 
stir in the ice bath for 15 minutes. The ice bath is then removed and the 
solution is stirred for an additional 30 minutes. The thionyl chloride is 
removed under reduced pressure, and the solid is dissolved in 100 mL of 
water. The solution is filtered, and 2 g of solid ammonium 
hexafluorphosphate is added, producing a bright yellow precipitate. The 
mixture is cooled to 5.degree. C., and the solid filtered. The solid can 
be recrystallized from methanol giving the perchlorate salts 99 as a 
yellow solid (1.4 g). 
EXAMPLE 22 
Preparation of 
5-carboxy-12-(1-pyrrolidinyl)pyrido1',2':3,4!imidazo1,5-a!quinolin-11-iu 
m perchlorate 100 using 1-pyrrolidinecarboxaldehyde 
##STR64## 
Thionyl chloride (25 mL) is placed in a 50 mL round bottomed flask, fitted 
with a magnetic stirring bar, and cooled to 5.degree.-10.degree. C. While 
in an ice bath, with stirring, 1.0 g of 4 (5.0 mmol) is added. In a single 
portion, 1.6 g (16 mmol) of 1-Pyrrolidinecarboxaldehyde is added, 
producing an immediate color change. The orange solution is allowed to 
stir in the ice bath for 15 minutes. The ice bath is then removed and the 
solution is stirred for an additional 30 minutes. The thionyl chloride is 
removed under reduced pressure, and the solid is dissolved in 100 mL of 
water. The solution is filtered, and 2 g of solid ammonium 
hexafluorphosphate is added, producing a bright yellow precipitate. The 
mixture is cooled to 5.degree. C., and the solid filtered. The solid can 
be recrystallized from methanol giving the perchlorate salts 100 as a 
yellow solid (1.4 g). NMR: .sup.1 H (300 MHz, DMSO-d.sub.6) 1.90 (m, 4H), 
3.0 (m, 4H), 4.0 (s, 3H), 7.65 (m, 2H), 7.70 (t, J=?, 1H), 8.05 (t, J=?, 
1H), 8.10 (t, J=?, 1H), 8.55 (d, J=?, 1H), 8.60 (d, J=?, 1H), 8.65 (m, 
1H), 8.70 (s, 1H). .sup.13 C (DMSO-d.sub.6) .delta. 24.02, 45.21, 53.44, 
119.85, 123.06, 124.69, 125.65, 126.49, 129.72, 130.27, 131.27, 136.66, 
141.51, 147.54, 148.18, 153.0, 153.5, 148.18, 166.27. 
EXAMPLE 23 
##STR65## 
A 50-ml, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.78 mmol) of 
(4-carboxymethyl-2-(2-pyridyl)quinoline 5), and 5 Ml of toluene was added 
then cooled in ice water bath to 0.degree. C. To this solution 10 
equivalents (2.76 h, 2.972 mL, 37.8 mmol) of cold thionyl chloride is 
added and the cold solution immediately becomes yellow/orange. The 
solution is stirred in a well ventilated hood for an hour and allowed to 
warm to room temperature. The contents of the flask is then poured into a 
100 mL beaker and placed in the well ventilated hood where the thionyyl 
chloride is allowed to evaporate overnight. The resulting red solid is 
dissolved in 50 mL of water and allowed to precipitate by the addition of 
3 g (24.5 mmol) of sodium perchlorate. The resulting yellow solid was 
filtered and 1.,2 g (75.6%) of the fluorescent product is obtained. The 
compound can be recrystallized from acetonitrile or a mixture of methanol 
and acetonitrile. The .sup.1 H and .sup.13 C NMR spectra are identical to 
the product 21 obtained in Example 2. 
EXAMPLE 24 
##STR66## 
A 50-mL, one neck, round bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.78 mmol) of 
4-carboxymethyl-2-(2-pyridyl)quinoline 5) and 5 mL of toluene was added 
then cooled in an ice water bath at 0.degree. C. To this solution 10 
equivalents (2.76 g, 2.972 mL, 37.8 mmol) of dimethyl formamide is added. 
To this mixture, ice cold 5 equivalents (3.93 g, 1.38 mL, 18.9 mmol) of 
cold thionyl bromide is added and the cold solution immediately becomes 
dark red and a precipatate forms. The solution is stirred in a well 
ventilated hood for an hour and allowed to warm at room temperature. The 
contents of the flask is then poured into a 100 mL beaker and placed in 
the well ventilated hood where the excess thionyl bromide is allowed to 
evaporate overnight. The resulting red solid is dissolved in 50 mL of 
water and allowed to precipitate by the addition of 3 g (24.5 mmol) of 
sodium perchlorate. The resulting yellow solid was filtered and 0.8 g 
(50%) of two compounds is obtained. After performing an alumina column on 
the mixture we obtained the fluorescent product 20, similarly obtained in 
Example 2. The 1H and .sup.13 C NMR sspectra are identical to the product 
obtained in Example 2. 
EXAMPLE 25 
##STR67## 
A 50-mL, one neck, round bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.78 mmol) of 
(4-carboxymethyl-2-(2-pyridyl)quinoline 5) and 5 mL of toluene was then 
added, cooled in an ice water bath to 0.degree. C. To this solution 10 
equivalents (2.76 g, 2.927 mL, 37.8 mmol) of dimethyl formamide is added. 
To this mixture ice cold 1.5 equivalents (0.720 g, 0.487 mL, 5.67 mmol) of 
oxalyl chloride is added and the cold solution immediately becomes 
yellow/orange and a precipitate immediately forms at the bottom of the 
flask. The solution is stirred in a well ventilated hood for an hour and 
allowed to warm to room temperature. The remaining solution is then poured 
off and 5 mL of toluene is added and subsequently removed. The resulting 
red solid is dissolved in 50 mL of water and allowed to precipitate by the 
addition of 3 g (24.5 mmol) of sodium perchlorate. The .sup.1 H and 
.sup.13 C NMR spectra are identical to the product 21 obtained in Example 
2. 
EXAMPLE 26 
##STR68## 
A 50-mL, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.78 mmol) of 
(4-carboxymethyl-2-(2-pyridyl)quinoline 5) and 5 mL of toluene was added, 
then cooled in an ice water bath to 0.degree. C. To this solution 10 
equivalents (2.76 g, 2.927 mL, 37.8 mmol) of dimethyl formamide is added. 
To this mixture ice cold 1.5 equivalents (0.4346 g, 0.288 mL, 5.67 mmol) 
of thiophosgene is added and the cold solution immediately becomes 
yellow/orange and a precipitate immediately forms at the bottom of the 
flask. The solution is stirred in a well ventilated hood for an hour and 
allowed to warm to room temperature. The remaining solution is then poured 
off, and 5 mL of toluene is added and subsequently decanted. The resulting 
solid is then dissolved in 20 mL of water and allowed to precipitate by 
the addition of 3 g (24.5 mmol) of sodium perchlorate. The .sup.1 H and 
.sup.13 C NMR spectra are identical to the product 21 obtained in Example 
2. 
EXAMPLE 27 
##STR69## 
A 50-mL, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.78 mmol) of 
(4-carboxymethyl-2-(2-pyridyl)quinoline 5), and 5 mL of toulene was added, 
then cooled in an ice water bath to 0.degree. C. To this solution 10 
equivalents (2.76 g, 2.927 mL, 37.8 mmol) of dimethyl formamide is added. 
To this mixture ice cold 1.5 equivalents (0.4346 g, 0.288 mL, 5.67 mmol) 
of thiophosgene is added, and the cold solution immediately becomes 
yellow/orange and a precipitate immediately forms at the bottom of the 
flask. The solution is stirred in a well ventilated hood for an hour, and 
allowed to warm to room temperature. The remaining solution is then poured 
off and 5 mL of toluene is added and subsequently decanted. The resulting 
solid is then dissolved in 20 mL of water and allowed to precipitate by 
the addition of 3 g (24.5 mmol) of sodium perchlorate. The .sup.1 H and 
.sup.13 C NMR spectra are identical to the product 21 obtained in Example 
2. 
EXAMPLE 28 
##STR70## 
A 50-mL, one neck, round-bottomed flask is equipped with stirring bar. The 
flask is charged with 1.00 g (3.78 mmol) of 
(4-carboxymethyl-2-(2-pyridyl)quinoline 5), and 5 mL of toulene was added, 
then cooled in an ice water bath to 0.degree. C. To this solution 10 
equivalents (2.76 g, 2.927 mL, 37.8 mmol) of dimethyl formamide is added. 
To this mixture ice cold 10 equivalents 4.50 g, 2.76 mL, 37.8 mmol) of 
cold phosphoryl chloride is added and the cold solution immediately 
becomes yellow/orange. The solution is stirred in a well ventilated hood 
for an hour and allowed to warm to room temperature. The contents of the 
flask is then poured into a 100 mL beaker and placed in a well ventilated 
hood where the phosphoryl chloride is allowed to evaporate overnight. The 
resulting red solid is dissolved in 50 mL of water, and allowed to 
precipitate by the addition of 3 g (24.5 mmol) of sodium perchlorate. The 
title product can be recrystalized from acetonitrile or a mixture of 
methanol and acetonitrile. The .sup.1 H and .sup.13 C NMR spectra are 
identical to the product 21 obtained in Example 2. 
EXAMPLE 29 
##STR71## 
A 50-mL, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged 10 mL of toluene to which 1 mL (0.6079 g, 3.965 mmol) 
of phosphoryl chloride, and 5 equivalents (2.48 mL, 2.34 g, 32.0 mmol) of 
dimethyl formamide is then added. After the solution is stirred at room 
temperature for several minutes, 1.00 g (6.40 mmol) of 2,2'-bipyridine 35 
is added and allowed to stir for five minutes. The solution is stirred in 
a well ventilated hood for an hour during which time the solution 
increasingly becomes a deep yellow color. The contents of the flask are 
then poured into a 100 mL beaker and placed in a well ventilated hood 
where the solution is allowed to evaporate overnight. The resulting yellow 
solid 41 that remains in the reaction flask is dissolved in 50 mL of water 
and allowed to precipitate by the addition of 3 g (24.5 mmol) of sodium 
perchlorate. The resulting yellow solid 41 was filtered and the NMR of 
this material confirmed the exclusive formation of the desired 
6-(dimethylamino)dipyrido1,2-c:2',1'-e!imidazol-5-ium-perchlorate (41) 
fluorescent adduct as previously shown in Example 4. 
EXAMPLE 30 
##STR72## 
A 50-mL, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (6.40 mmol) of 2,2'-bipyridine, and 
cooled in an ice water bath, to which 2 equivalents (0.99 mL, 0.9360 g, 
12.8 mmol) of ice cold oxalyl bromide is added and with the formation of a 
precipitate and a release of a gas is observed. The solution is stirred in 
a well ventilated hood for an hour. The contents of the flask are then 
filtered. The resulting brown solid is dissolved in 50 mL of water and 
allowed to precipitate by the addition of 3 g (24.5 mmol) of sodium 
perchlorate. The resulting yellow solid was filtered and the NMR of this 
material confirmed the formation of the desired 
dipyrido1,2-c:2',1'-e!imidazol-5-ium, 6-(dimethylamino),-perchlorate (41) 
fluorescent adduct as previously shown in Example 4. 
EXAMPLE 31 
##STR73## 
A 50-mL, one neck, round-bottomed flask is equipped with a stirring bar. 
The flask is charged with 1.00 g (3.20 mmol) of the substrate 
2,3-dipyridyl-6,7-dimethyl-1,4,5-triazanaphthalene which is dissolved in 
10 mL of toluene and cooled in an ice water bath, to which 5 equivalents 
(1.24 mL, 1.17 g, 16.0 mmol) of dimethyl formamide is added. The solution 
is allowed to cool, and 3 equivalentsdd (0.826 mL, 1.22 g, 9.60 mmol) of 
ice cold oxalyl chloride are then added and allowed stir for five minutes. 
When oxalyl chloride is added an immediate red precipitate is observed and 
a vigorous release of a gas is observed. The solution is stirred in a well 
ventilated hood for an hour. The solution of the flask is then poured into 
a 100 mL beaker and placed in a well ventilated hood where the solution is 
allowed to evaporate overnight. The resulting red solid is dissolved in 50 
mL of water and is precipitated by the addition of 3 g (24.5 mmol) of 
sodium perchlorate. The resulting orange solid is filtered, and 
recrystalized from acetonitrile, yielding 1.25 g (63%) of one compound 
exclusively. 
.sup.1 H (300 MHz, DMSO-d.sub.6) .delta. 2.55(s, 6H), 3,25 (s, 12H), 7.39 
(dd, J=7.0, 7.0 Hz, 2H), 7.53 (dd, J=9.5, 7.0 Hz, 2H), 8.06 (s, 2H), 8.45 
(d, J=9.5 Hz, 1H), 8.63 (d, J=7.0 Hz, 1H). .sup.13 C NMR (75 MHz, 
DMSO-d.sub.6, DEPT (90) correlations) .delta. 20.47 (CH.sub.2), 40.13 
(CH.sub.3), 107.69 (C), 118.78 (CH), 1119.11 (CH), 120.08 (CH), 120.91 
(C), 122.18 (C), 123.52 (CH), 127.07 (CH), 135.21 (C), 140.19 (C).