2- and 4- (5'nitrofuryl) quinoline derivatives which may be variously substituted on the quinoline nucleus have been found to possess excellent antibacterial and antifungal activity. Procedures for their manufacture are disclosed.

The invention will be illustrated by the following Examples without being 
limited by them. All temperatures are indicated herein in degrees 
Centigrade. All melting points are uncorrected. 
EXAMPLE 1 
5.91 g (0.03 mole) of 1-(5'-nitrofuryl)-butane-1,3-dione and 2.8 g (0.03 
mole) of freshly distilled aniline were heated together at 120.degree. 
with a catalytic amount of ZnCl.sub.2. A clear melt was obtained and after 
15 minutes the whole mass solidified. The melt was kept for a further 10 
minutes at 120.degree.. Thereafter it was cooled and recrystallised from 
methanol to yield 7.4 g of crystaline 
1-(5'-nitro-2'-furo)-butanone-3-phenyl-imino of m.p. 
127.5.degree.-128.5.degree.. Yield 87.5%. 
Then, 5.6 g (0.02 mole) of the above Schiff base were dissolved at about 
5.degree. in 30 g of concentrated sulfuric acid. The clear solution 
obtained was allowed to reach room temperature, was thereafter heated for 
10 minutes to 100.degree.-110.degree. and then poured on ice water. 
An olivegreen precipitate was obtained which was filtered off and suspended 
in water. Ammonia was added to the suspension until the pH was slightly 
alkaline. The suspension was cooled and the precipitate obtained was 
filtered off to yield 2.4 g of 2-methyl-4-[2'-(5'-nitrofuryl)] quinoline, 
m.p.-127.degree.-130.degree.. Further ammonia was added to the mother 
liquor to yield a further 0.3 g of the above compound. 
An analytical sample was obtained by recrystallisation from 
isopropanol/water; m.p. 138.degree.-139.degree.. The analysis was 
calculated for C.sub.14 H.sub.10 N.sub.3 O.sub.3 : 
Calculated: C: 66.14%; H: 3.96%; N: 11.02%; Found: C: 66.08%; H: 4.10%, N: 
10.98%. 
2.7 g of the above quinoline derivative were dissolved with heating in 70 
ml of glacial acetic acid, 2 ml of 30% hydrogen peroxide were added at 
once to the solution obtained, which was kept at 70.degree. for 3 hours. 
The water was added and the resulting precipitate was filtered off to 
yield 2.4 g of 2-methyl-4-[2'-(5'-nitrofuryl)] quinoline N-oxide, m.p. 
207.degree.. 
An analytical sample was prepared by recrystallisation from isopropanol and 
nitromethane; m.p. 226.degree.-227.degree.. The analysis was calculated 
for C.sub.14 H.sub.10 N.sub.2 O.sub.4 : 
Calculated: C: 62.22%; H: 3.73%; N: 10.37%; Found: C: 62.47%; H: 3.69%; N: 
10.29%. 
The hydrochloride of 2-methyl-4-[2'-(5'-nitrofuryl)] quinoline has a m.p. 
of 190.degree.-191.5.degree.. The corresponding hydrobromide has a m.p. of 
230.5.degree.-231.degree.. 
EXAMPLE 2 
3 g (0.02 mole) of 5-nitrofuryl methyl ketone and 2.7 g (0.02 mole) of 
o-amino acetophenone were heated together with a catalytic amount of 
ZnCl.sub.2 at 150.degree., The clear melt obtained was heated for 1 hour 
at 140.degree.-150.degree., then cooled and dissolved in isopropanol. The 
solution was filtered through charcoal. The filtrate was concentrated and 
cooled to yield 1.53 g (30%) of 2-[2'-(5'-nitrofuryl)]-4-methyl quinoline, 
m.p. 148.degree.-162.degree.. 
An analytical sample was obtained by consecutive recrystallisation from 
acetone, isopropanol and benzene/petrol-ether; m.p. 
167.degree.-168.degree.. The analysis was calculated for C.sub.14 H.sub.10 
N.sub.2 O.sub.3 : 
Calculated: C: 66.14%; H: 3.96%; N: 11.02%; Found: C: 65.94%; H: 4.14%; N: 
10.98%. 
The N-oxide has a m.p. of 210.degree.-212.degree.. 
EXAMPLE 3 
5.91 g (0.03 mole) of 1-(5'-nitrofuryl)-2,4-butanedione and 3.82 g (0.03 
mole) of m-chloroaniline were melted together with a catalytic amount of 
ZnCl.sub.2 in an open vessel at 110.degree.-120.degree.. After 10 minutes 
the heating was stopped, the mixture was cooled and dissolved in 
nitromethane. The solution obtained was filtered hot and the filtrate 
yielded after cooling 8.9 g (97% yield) of crystalline 
1-(5'-nitro-2'-furo) butanone-3-(m-chlorophenyl) imino, m.p. 
161.degree.-162.degree.. 
6 g of the above enamine are added gradually with cooling to 18 ml of 
cooled concentrated sulfuric acid. The mixture was allowed to reach room 
temperature and then heated for 10 minutes to 100.degree.-110.degree.. The 
mixture was then cooled and poured on ice-water. The amorphous precipitate 
obtained was filtered off, washed with water, re-suspended in water and 
the suspension was made alkaline with ammonia to yield 5.5 g (yield 97%) 
of 2-methyl-4-[2'-(5'-nitrofuryl)]-7-chloro quinoline. 
An analytical sample was prepared by recrystallisation from isopropanol and 
acetone/water; m.p. 146.degree.. The analysis was calculated for C.sub.14 
H.sub.9 N.sub.3 O.sub.3 Cl: 
Calculated: C: 58.23%; H: 3.14%; N: 9.70%; Cl: 12.30%; Found: C: 58.33%; H: 
3.08%; N: 9.53%; Cl: 12.26%. 
1.2 g of the above quinoline derivative were dissolved with heating in 25 
ml of glacial acetic acid. 2 ml of 30% hydrogen peroxide were added to the 
solution which was kept for 5 hours at 70.degree.. Water was added and the 
precipitate obtained was filtered off to yield 1.15 g (yield 91%) of 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-chloro-quinoline N-oxide, m.p. 
198.degree.-204.degree.. 
An analytical sample was prepared by recrystallisation from nitromethane; 
m.p. 205.degree.-206.degree.. The analysis was calculated for C.sub.14 
H.sub.9 N.sub.2 O.sub.4 Cl: 
Calculated: C: 55.20%; H: 2.98%; N: 9.19%; Found: C: 55.15%; H: 3.09%; N: 
9.13%. 
EXAMPLE 4 
5.91 g (0.03 mole) of 1-(5'-nitrofuryl)-2,4-butanedione and 3.9 g (0.03 
mole) of m-aminophenol were heated together with a catalytic amount of 
ZnCl.sub.2 at 90.degree.. The clear melt so obtained was heated for 10 
minutes at 100.degree.-110.degree., then cooled and recrystallised from 
methanol to yield 6.1 g of 
1-(5'-nitro-2'-furo)-butanone-3-(m-hydroxy-phenyl)imino; m.p. 
190.5.degree.-192.degree.. 
6 g of the above Schiff base were dissolved in 36 g of sulfuric acid at 
about 5.degree.. The reaction mixture was kept for 5 days at room 
temperature and then poured on ice-water. The obtained aqueous suspension 
was neutralised with ammonia and the precipitated crystals were filtered 
off and recrystallised from ethanol to yield bright-yellow crystals of 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-hydroxy quinoline; m.p. 259.degree.. 
An analytical sample was obtained by repeated recrystallisation from 
ethanol and nitromethane; m.p. 272.degree. (decomp.). The analysis was 
calculated for C.sub.14 H.sub.10 N.sub.2 O.sub.4 : 
Calculated: C: 62.22%; H: 3.73%; N: 10.37%; Found: C: 62.03%; H: 3.92%; N: 
10.20%. 
2-Methyl-4-[2'-(5'-nitrofuryl)]-7-hydroxy quinoline N-oxide was prepared by 
oxidation of the above compound with H.sub.2 O.sub.2 (30%) in glacial 
acetic acid. M.p. 293.degree. (decomp). The analysis was calculated for 
C.sub.14 H.sub.10 N.sub.2 O.sub.5 : 
Calculated: C: 58.75%; H: 3.52%; N: 9.79%; Found: C: 58.88%; H: 3.59%; N: 
9.80%. 
When the 2-methyl-4-[2'-(5'-nitrofuryl)]-7-hydroxy quinoline was 
O-alkylated with n-butyl bromide dissolved in acetone there was obtained 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-n-butoxy quinoline; m.p. 
69.degree.-70.degree.. 
When the O-alkylation is performed with iso-butyl bromide there is obtained 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-i-butoxy quinoline, m.p. 
65.degree.-70.degree.. 
When the O-alkylation is performed with propyl bromide there is obtained 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-propyl quinoline, m.p. 
132.degree.-134.degree.. 
EXAMPLE 5 
2 g of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as described in 
Example 1, were dissolved with heating in 20 ml of glacial acetic acid. 
4.0 g of anhydrous sodium acetate and thereafter 1.25 ml of bromine 
dissolved in some acetic acid were added at 70.degree.-75.degree.. The 
reaction mixture was then heated for 90.degree.-95.degree., then cooled 
and the precipitate obtained was filtered off to yield 3.6 g (yield 92%) 
of yellow crystals of 2-tribromomethyl-4-[2'-(5'-nitrofuryl)]quinoline; 
m.p. 154.degree.-155.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol; 
m.p. 158.degree.-160.degree.. The analysis was calculated for C.sub.14 
H.sub.7 N.sub.2 O.sub.3 Br.sub.3 : 
Calculated: C: 34.25%; H: 1.44%; N: 5.70%; Br: 48.83%; Found: C: 34.38%; H: 
1.45%; N: 5.90%; Br: 49.03%. 
EXAMPLE 6 
1.5 g of 2-tribromomethyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as 
described in Example 5, were dissolved in 50 ml of 50% sulfuric acid. 
Catalytic quantities of FeCl.sub.3 were added to the solution obtained, 
which was then kept for 20 hours at 110-130.degree.. The clear solution 
was cooled, water was added and the precipitate obtained was filtered off 
to yield 0.4 g of 2-carboxy-4-[2'-(5'-nitrofuryl)]quinoline; m.p. 
190.degree.-193.degree.. 
An analytical sample was obtained by recrystallisation from glacial acetic 
acid; m.p. 200.degree.. The analysis was calculated for C.sub.14 H.sub.8 
N.sub.2 O.sub.5 : 
Calculated: C: 59.16%; H: 2.84%; N: 9.86%; Found: C: 59.21%; H: 2.85%; N: 
9.52%. 
EXAMPLE 7 
5.91 g (0.03 mole) of 1-(5'-nitrofuryl)-2,4-butanedione and 3.7 g (0.03 
mole) of m-anisine were heated together with a catalytic amount of 
ZnCl.sub.2 for 10 minutes at 110.degree.. After cooling and 
recrystallisation from methanol, 
1-[5'-nitro-2'-furo)-butanone-3-(m-methoxy-phenyl)imino was obtained, 
yield 81%; m.p. 137.degree.. 
The above enamine was subjected to a ring closure treatment similar to that 
described in Example 1 to yield 2-methyl-4-[2'-(5'-nitrofuryl)]-7-methoxy 
quinoline, yield 54%; m.p. 146.degree.-148.5.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol; 
m.p. 156.degree.-157.degree.. The analysis was calculated for C.sub.15 
H.sub.12 N.sub.2 O.sub.4 : 
Calculated: C: 63.38%; H: 4.25%; N: 9.85%; Found: C: 63.25%; H: 4.38%; N: 
9.83%. 
The N-oxide was prepared by oxidation with H.sub.2 O.sub.2 ; m.p. 
207.degree.-208.degree.. 
EXAMPLE 8 
19.7 g (0.1 mole) of 1-(5'-nitrofuryl)-2,4-butanedione and 10.7 g (0.1 
mole) of p-toluidine were heated together with a catalytic amount of 
ZnCl.sub.2 at 120.degree.. After 10 minutes of further heating and working 
up as described in Example 1, 
1-(5'-nitro-2'-furo)-butanone-3-(p-methyl-phenyl)imino was obtained, yield 
98%, m.p. 145.degree.-146.degree.. 
The above enamine was subjected to a ring closure treatment similar to that 
described in Example 1 to yield 2-methyl-4-[2'-(5'-nitrofuryl)]-6-methyl 
quinoline, yield 97%; m.p. 146.degree.-148.degree.. 
An analytical sample was prepared by recrystallisation from isopropanol; 
m.p. 151.degree.. The analysis was calculated for C.sub.15 H.sub.12 
N.sub.2 O.sub.3 : 
Calculated: C: 67.12%; H: 4.51%; N: 10.44%; Found: C: 67.08%; H: 4.57%; N: 
10.57%. 
The N-oxide was prepared by oxidation with H.sub.2 O.sub.2 ; m.p. 
227.degree.-229.degree. (after recrystallisation). The analysis was 
calculated for C.sub.15 H.sub.12 N.sub.2 O.sub.4 : 
Calculated: C: 63.38%; H: 4.25%; N: 9.85%; Found: C: 63.60%; H: 4.41%; N: 
9.74%. 
EXAMPLE 9 
2.8 g (0.01 mole) of 2-methyl-4-[2'-(5'-nitrofuryl)]-7-chloro quinoline, 
prepared as described in Example 3, were added gradually with cooling to 8 
ml of concentrated sulfuric acid, the temperature being maintained below 
0.degree.. 0.6 ml of nitric acid (100%) was added in one portion to the 
mixture at said temperature. The mixture was then allowed to reach room 
temperature, kept at said temperature for 3 hours and then poured on 
ice-water. The amorphous precipitate obtained was filtered off, washed 
with water and dissolved in ethanol. The solution so obtained was filtered 
with charcoal, concentrated and cooled to yield 1.1 g of 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-chloro-8-nitro quinoline; m.p. 
198.degree.-202.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol and 
nitromethane; m.p. 207.degree.-208.degree.. The analysis was calculated 
for C.sub.14 H.sub.8 N.sub.3 O.sub.5 Cl: 
Calculated: C: 50.39%; H: 2.42%; Cl: 10.63%; Found: C: 50.15%; H: 2.51%; 
Cl: 10.43%. 
There was similarly prepared 
2,8-dimethyl-4-[2'-(5'-nitrofuryl]-5-nitroquinoline, m.p. 
229.degree.-232.degree.. 
EXAMPLE 10 
Performing the process as described in Example 8, but replacing the 
p-toluidine by o-toluidine, 
1-(5'-nitro-2'-furo)-butanone-3-(o-methyl-phenyl)imino was obtained; yield 
91.5%; m.p. 127.degree.-129.degree.. 
The enamine was subjected to a ring closure treatment similar to that 
described in Example 1 to yield 
2,8-dimethyl-4-[2'-(5'-nitrofuryl)]quinoline, yield 82%; m.p. 
147.degree.-149.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol and 
nitromethane; m.p. 157.degree.-158.5.degree.. The analysis was calculated 
for C.sub.15 H.sub.12 N.sub.2 O.sub.3 : 
Calculated: C: 67.12%; H: 4.51%; N: 10.44%; Found: C: 67.05%; H: 4.36%; N: 
10.52%. 
The N-oxide of the above compound was prepared by oxidation with peracetic 
acid in glacial acetic acid. The melting point of the crude compound was 
149.degree.-151.degree.. 
An analytical sample was prepared by recrystallisations from isopropanol, 
yielding a compound melting at 158.degree.-160.degree.. 
The analysis was calculated for C.sub.15 H.sub.12 N.sub.2 O.sub.4 : 
Calculated: C: 63.38%; H: 4.25%; Found: C: 63.59%; H: 4.43%. 
EXAMPLE 11 
Performing the process as described in Example 8, but replacing the 
p-toluidine by m-toluidine, 
1-(5'-nitro-2'-furo)-butanone-3-(m-methyl-phenyl)imino was obtained; yield 
90.5%; m.p. 146.degree.-147.5.degree.. 
The enamine was subjected to a ring closure treatment similar to that 
described in Example 1 to yield 
2,7-dimethyl-4-[2'-(5'-nitrofuryl)]quinoline, yield 75%; m.p. 
142.degree.-145.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol and 
nitromethane; m.p. 145.degree.-146.degree.. The analysis was calculated 
for C.sub.15 H.sub.12 N.sub.2 O.sub.3 : 
Calculated: C: 67.12%; H: 4.51%; N: 10.44%; Found: C: 67.04%; H: 4.45%; N: 
10.67%. 
The N-oxide of the above compound was prepared by an oxidation reaction 
with H.sub.2 O.sub.2 in glacial acetic acid. Yield 92%, m.p. 
210.degree.-212.degree.. 
An analytical sample was prepared by recrystallisation from ethoxy ethanol 
and nitromethane; m.p. 217.degree.-218.5.degree.. The analysis was 
calculated for C.sub.15 H.sub.12 N.sub.2 O.sub.4 : 
Calculated: C: 63.38%; H: 4.25%; N: 9.85%; Found: C: 63.22%; H: 4.41%; N: 
10.07%. 
EXAMPLE 12 
1.27 g of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as described 
in Example 1, was dissolved in 13 ml of hot acetic acid. 0.45 g of 
anhydrous sodium acetate was added to the solution and then 0.8 g of 
bromine dissolved in 2 ml of acetic acid was added dropwise in the course 
of 15 minutes. The reaction mixture was then cooled and the crystals 
obtained filtered off. Thin layer chromatography showed that the material 
obtained was a mixture of 2-dibromo- and 
2-tri-bromo-methyl-4-[2'-(5'-nitrofuryl)]quinoline. 
The material was recrystallised in succession from ethanol, isopropanol, 
cellosolve and again isopropanol, to yield the dibromo-compound only; m.p. 
187.5.degree.-189.degree.. The analysis was calculated for C.sub.14 
H.sub.8 N.sub.2 O.sub.3 Br.sub.2 : 
Calculated: C: 40.80%; H: 1.95%; N: 6.80%; Br: 38.90%; Found: C: 40.60%; H: 
2.20%; N: 6.63%; Br: 38.64%. 
EXAMPLE 13 
2.54 g (0.01 mole) of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as 
described in Example 1, and 1.5 g of sodium carbonate were suspended in 80 
ml of benzene. The mixture was heated to 70.degree. and chlorine gas was 
bubbled therethrough in the course of 3 hours. After cooling, some 
unreacted starting material was filtered off and the filtrate was 
concentrated to yield 2-trichloromethyl-4-[2'-(5'-nitrofuryl)]quinoline; 
m.p. 142.degree.-144.degree.. 
An analytical sample was obtained by recrystallisation from isopropanol and 
nitromethane; m.p. 145.degree.-146.degree.. The analysis was calculated 
for C.sub.14 H.sub.7 N.sub.2 O.sub.3 Cl.sub.3 : 
Calculated: C: 47.02%; H: 1.98%; N: 7.83%; Cl: 29.73%; Found: C: 47.03%; H: 
2.13%; N: 7.70%; Cl: 29.51%. 
EXAMPLE 14 
1.97 g (0.01 mole) of 1-(5'-nitrofuryl)-2,4-butanedione and 1.43 g (0.01 
mole) of B-naphthylamine were heated together with a catalytic amount of 
ZnCl.sub.2 for 10 minutes at 100.degree.-110.degree.. After cooling and 
recrystallisation 2.65 g (yield 82.5%) of 
1-(5'-nitro-2'-furo)-butanone-3-naphthyl imino were obtained; m.p. 
184.degree.-186.5.degree.. 
The enamine obtained was heated with 6 times its weight of concentrated 
sulfuric acid for 10 minutes at 110.degree.. After cooling the reaction 
mixture was poured on ice-water, neutralised and the precipitate obtained 
filtered off to yield 2-methyl-4-[2'-(5'-nitrofuryl)]-6,7-benzoquinoline; 
m.p. 221.degree.. 
An analytical sample was obtained by recrystallisation from nitromethane; 
m.p. 228.degree.. The analysis was calculated for C.sub.18 H.sub.12 
N.sub.2 O.sub.3 : 
Calculated: C: 71.05%; H: 3.97%; N: 9.21%; Found: C: 71.21%; H: 3.96%; N: 
8.98%. 
The N-oxide was prepared by oxidation with H.sub.2 O.sub.2 in glacial 
acetic acid, yield 98%, m.p. 230.degree.-235.degree.. 
As analytical sample was prepared by recrystallisation from nitromethane, 
m.p. 241.degree.-243.degree.. The analysis was calculated for C.sub.18 
H.sub.12 N.sub.2 O.sub.4. 
Calculated: C: 67.50%; H: 3.78%; N: 8.75%; Found: C: 67.33%; H: 3.94%; N: 
8.76%. 
EXAMPLE 15 
2.7 g (0.01 mole) of 2-methyl-4-[2'-(5'-nitrofuryl)]-6-methyl quinoline, 
prepared as described in Example 8, were dissolved in 35 ml of acetic acid 
at 70.degree.. At the same temperature were added 5.4 g of anhydrous 
sodium acetate and thereafter in the course of 25 minutes also 2.4 g of 
bromine dissolved in 5 ml of glacial acetic acid. The mixture was then 
heated for 1 hour at 90.degree.-95.degree., then cooled and the formed 
precipitate was filtered off to yield 2.7 g of yellow-green crystals of 
2-tribromomethyl-4-[2'-(5'-nitrofuryl)]-6-methyl quinoline; m.p. 
191.5.degree.-193.degree.. 
An analytical sample was obtained by recrystallisations from isopropanol, 
dioxane and nitromethane; m.p. 193.degree.-195.degree.. The analysis was 
calculated for C.sub.15 H.sub.9 N.sub.2 O.sub.3 Br.sub.3 : 
Calculated: C: 35.60%; H: 1.78%; N: 5.54%; Br: 47.52%; Found: C: 35.74%; H: 
2.03%; N: 5.35%; Br: 47.55%. 
EXAMPLE 16 
Performing the process as described in Example 2, but replacing the o-amino 
acetophenone with o-amino benzadehyde, 2-[2'-(5'-nitrofuryl)]quinoline was 
obtained; m.p. 137.degree.-147.degree.. 
An analytical sample was obtained by consecutive recrystallisation from 
methanol, isopropanol and ethoxy-ethanol; m.p. 196.degree.-198.degree.. 
The analysis was calculated for C.sub.13 H.sub.8 N.sub.2 O.sub.3 : 
Calculated: C: 65.00%; H: 3.36%; N: 11.66%; Found: C: 64.82%; H: 3.32%; N: 
11.92%. 
The N-oxide had a m.p. of 215.degree.-216.degree.. 
EXAMPLE 17 
Performing the process as described in Example 2 but utilising as starting 
materials 5-nitrofuryl ethyl ketone and o-amino benzaldehyde, 
2-[2'-(5'-nitrofuryl)]-3-methyl quinoline was obtained; m.p. 
175.degree.-196.degree.. 
EXAMPLE 18 
2.54 g (0.01 mole) of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as 
described in Example 1, were added gradually with cooling to 8 ml of 
concentrated sulfuric acid, the temperature being maintained below 
0.degree.. 0.6 ml of nitric acid (100%) was added at said temperature in 
one portion. The mixture was then allowed to reach room temperature, kept 
at that temperature for 3 hours and then poured on ice-water. The 
precipitate obtained was filtered off, washed with water to yield 1.8 g of 
yellow crystals, m.p. 121.degree.-157.degree.. 
Thin layer chromatography showed 2 spots corresponding to 
2-methyl-4-[2'-(5'-nitrofuryl)]-5- and 8-nitro quinoline. 
The recrystallised material had a m.p. of 193.degree.-198.degree.. The 
analysis was calculated for C.sub.14 H.sub.9 N.sub.3 O.sub.5 : 
Calculated: C: 56.19%; H: 3.03%; Found: C: 56.36%; H: 3.04%. 
EXAMPLE 19 
In a manner similar to that described in Example 1 there were prepared: 
a. 2-methyl-4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline. m.p. 
114.degree.-115.degree.. The analysis was calculated for C.sub.16 H.sub.14 
N.sub.2 O.sub.3 : 
Calculated: C: 68.08%; H: 5.00%; N: 9.92%; Found: C: 68.05%; H: 5.16%; N: 
10.24%. 
The corresponding N-oxide was prepared, m.p. 194.degree.-195.degree.. The 
analysis was calculated for C.sub.16 H.sub.14 N.sub.2 O.sub.4 : 
Calculated: C: 64.42%; H: 4.73%; N: 9.39%; Found: C: 64.37%; H: 4.94%; N: 
9.20%. 
b. 2,6,8-trimethyl-4-[2'-(5'-nitrofuryl)]quinoline, m.p. 
143.degree.-143.5.degree.. The analysis was calculated for C.sub.16 
H.sub.14 N.sub.2 O.sub.3 : 
Calculated: C: 68.08%; H: 5.00%; N: 9.92%; Found: C: 67.88%; H: 5.28%; N: 
10.00%. 
c. 2,5,8-trimethyl-4-[2'-(5'-nitrofuryl]quinoline, m.p. 
133.degree.-134.degree.. The analysis was calculated for C.sub.16 H.sub.14 
N.sub.2 O.sub.3 : 
Calculated: C: 68.08%; H: 5.00%; N: 9.92%; Found: C: 68.39%; H: 4.91%; N: 
9.72%. 
d. 2-methyl-4-[2'-(5'-nitrofuryl)]-5,8-dimethoxy quinoline, m.p. 
183.degree.-183.5.degree.. The analysis was calculated for C.sub.16 
H.sub.14 N.sub.2 O.sub.5 : 
Calculated: C: 61.14%; H: 4.49%; N: 8.91%; Found: C: 61.05%; H: 4.63%; N: 
8.73%. 
EXAMPLE 20 
Performing the process as described in Example 1 but replacing the 
1-(5'-nitrofuryl)-butane-1,3-dione with 
1-(5'-nitrofuryl)-pentane-1,3-dione, the following 5-nitrofuryl quinolines 
were prepared: 
a. 2-ethyl-4-[2'-(5'-nitrofuryl)]quinoline m.p. 127.degree.-128.degree.. 
The analysis was calculated for C.sub.15 H.sub.12 N.sub.2 O.sub.3 : 
Calculated: C: 67.16%; H: 4.51%; N: 10.44%; Found: C: 67.42%; H: 4.70%; N: 
10.27%. 
The corresponding N-oxide has a m.p. of 184.5.degree.-195.5.degree. 
b. 2-ethyl-4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline m.p. 
117.5.degree.-118.5.degree.. The analysis was calculated for C.sub.17 
H.sub.16 N.sub.2 O.sub.3 : 
Calculated: C: 68.91%; H: 5.44%; N: 9.45%; Found: C: 69.09%; H: 5.56%; N: 
9.37%. 
The corresponding N-oxide was prepared, m.p. 173.5.degree.-174.5.degree.. 
c. 2-ethyl-4-[2'-(5'-nitrofuryl)]-6-methyl quinoline m.p. 
112.5.degree.-113.5.degree.. The analysis was calculated for C.sub.16 
H.sub.14 N.sub.2 O.sub.3 : 
Calculated: C: 68.08%; H: 5.00%; N: 9.92%; Found: C: 68.21%; H: 5.13%; N: 
10.05%. 
The corresponding N-oxide was prepared, m.p. 158.5.degree.-159.5.degree.. 
Performing the process as described in Example 1 but replacing the 
1-('nitrofuryl)-butane-1,3-dione with 
1-(5'-nitrofuryl)-5-methylpentane-1,3-dione, the following 5-nitrofuryl 
quinolines were prepared: 
a. 2-isopropyl-4-[2'-(5'-nitrofuryl)]-6-methyl quinoline; m.p. 
94.degree.-95.degree.. 
The corresponding N-oxide has a m.p. of 201.degree.-202.degree.. 
b. 2-isopropyl-4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline; m.p. 
108.degree.-109.degree.. 
The corresponding N-oxide has a m.p. of 146.degree.-148.degree.. 
EXAMPLE 21 
A mixture comprising 2 g of 2-methyl-4-[2'-(5'-nitrofuryl)]-7-hydroxy 
quinoline, prepared as described in Example 4, 40 ml of acetic anhydride 
and 1 ml of concentrated sulfuric acid were refluxed for 2 hours, then 
left to cool to room temperature and finally poured on ice water. After 2 
hours of further stirring the brown crystals obtained were filtered off 
and washed throughly with water. 
1.5 g of 2-methyl-4-[2'-5'-nitrofuryl)]-7-acetoxyquinoline were obtained., 
yield 65%. 
An analytical sample was prepared by repeated recrystallisation from 
dioxane, nitromethane and isopropanol, mp. 171.5.degree.-172.5.degree.. 
The analysis was calculated for C.sub.16 H.sub.12 N.sub.2 O.sub.5 : 
Calculated: C: 61.54%; H: 3.87%; N: 8.97%; Found: C: 61.37%; H: 3.83%; N: 
9.01%. 
The N-oxide of the above compound was prepared as described in previous 
examples, m.p. 176.degree.. 
EXAMPLE 22 
19.7 g of 1-(5'-nitrofuryl)-2,4-butanedione and 13.7 g of m-phenetidine 
were heated for 20 minutes together with a catalytic amount of ZnCl.sub.2 
at 110.degree.-120.degree.. The mixture was then cooled and recrystallised 
from methanol to yield 28.5 g of 
1-(5'-nitro-2'-furo)-butanone-3-(m-ethoxy-phenyl)imino, m.p. 
129.degree.-130.degree.. 
2 g of the above Schiff base were mixed with 25 g of polyphosphoric acid at 
about 5.degree. C. The reaction mixture was a viscous mass which was 
heated for 10 minutes at 100.degree., then allowed to cool to room 
temperature and then 100 ml of water were added with external cooling. The 
pH was adjusted to 8, with ammonium hydroxide and the greenish crystals 
obtained were filtered off and washed with water. 1.7 g of the crude 
compound obtained, 2-methyl-4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline, 
were crystallised from ethanol 95%, m.p. 122.5.degree.-123.5.degree.. 
An analytical sample was prepared by successive recrystallisation from 
isopropanol, acetone/water and cellosolve, m.p. 
124.5.degree.-126.5.degree.. 
The N-oxide of the above compound was prepared by oxidation with H.sub.2 
O.sub.2 (30%) in glacial acetic acid. 
An analytical sample was prepared by repeated recrystallisations from 
nitromethane and ethanol, m.p. 201.degree.-202.degree.. The analysis was 
calculated for C.sub.16 H.sub.14 N.sub.2 O.sub.5 : 
Calculated: C: 61.14%; H: 4.49%; N: 8.91%; Found: C: 60.99%; H: 4.61%; N: 
8.84%. 
EXAMPLE 23 
A mixture of 2 g of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline N-oxide, 
prepared as described in Example 1, and 10 g of acetic acid anhydride was 
heated to 120.degree.-130.degree. for 2 hours on an oil bath. The excess 
of acetic acid anhydride was then distilled off under reduced pressure and 
ice-water was added to the residue. Crystals precipitated which were 
separated by filtration and washed with water. 
2.1 g of 2-acetoxymethyl-4-[2'-(5'-nitrofuryl)]quinoline were obtained; 
yield 89% m.p. 125.degree.-130.degree.. After recrystallisation from 
ethanol with charcoal the melting point rose to 135.degree.-136.degree.. 
An analytic sample having a m.p. of 137.degree.-138.degree. was prepared. 
The analysis was calculated for C.sub.16 H.sub.12 N.sub.2 O.sub.5 
Calculated: C: 61.54%; H: 3.87%; N: 8.97%; Found: C: 61.44%; H: 3.92%; N: 
9.00%. 
The N-oxide of the above compound was prepared by oxidation with hydrogen 
peroxide dissolved in glacial acetic acid yielding a compound melting at 
188.degree.-189.5.degree. after recrystallisation from isopropanol. 
2-Hydroxymethyl-4-[2'-(5'-nitrofuryl)]quinoline was prepared by refluxing 
the 2-acetoxy-methyl-4-[2'-(5'-nitrofuryl)]quinoline in a 12% sulfuric 
acid solution. 
EXAMPLE 24 
In the same manner as described in Example 23 there was prepared from 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-hydroxyquinoline N-oxide the 
2-acetoxymethyl-4-[2'-(5'-nitrofuryl)]-7-acetoxy quinoline, m.p. 
151.5.degree.-152.degree.. The analysis was calculated for C.sub.18 
H.sub.14 N.sub.2 O.sub.7 : 
Calculated: C: 58.38%; H: 3.81%; N: 7.56%; Found: C: 58.41%; H: 4.04%; N: 
7.72%. 
EXAMPLE 25 
In a 250 ml three-necked, round-bottomed flask, fitted with stirrer and 
reflux condenser, were placed 20 ml of diozane (90%) and 3.9 g of selenium 
dioxide. The mixture was heated to 50.degree.-60.degree. until the solid 
was dissolved. Then 5 g of 2-methyl-4-[2'-(5'-nitrofuryl)]quinoline 
(prepared as described in Example 1) were added to the solution in one lot 
and the resulting mixture was refluxed for 2 hours with continued 
stirring. The hot solution was then twice filtered with charcoal, and 
concentrated to 1/2 of its initial volume. The precipitated crystals of 
4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde, were then filtered off. 
The crude compound was recrystallised from dioxane, yielding 4.2 g of a 
yellow compound, mp. 185.degree.-187.degree.. 
The following compounds were obtained in a similar manner: 
4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline-2-carboxaldehyde, m.p. 
179.degree.-181.degree.; 
4-[2'-(5'-nitrofuryl)]-7-chloro quinoline-2-carboxaldehyde, m.p. 
148.degree.-151.degree.; 
4-[2'-(5'-nitrofuryl)]-7-methyl quinoline-2-carboxaldehyde, m.p. 
155.degree.-157.degree.; 
4-[2'-(5'-nitrofuryl)]-6-methyl quinoline-2-carboxaldehyde, m.p. 
110.degree.-119.degree.. 
4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline-2-carboxaldehyde m.p. 
157.degree.-161.degree.. 
Similarly from 2-ethyl-4-[2'-(5'-nitrofuryl)]quinoline there was prepared 
4-[2'-(5'-nitrofuryl)]quinoline-2-methyl ketone, m.p. 
209.degree.-211.degree.. 
EXAMPLE 26 
In a 100 ml three-necked, round-bottomed flask fitted with stirrer and 
reflux condenser, were placed 2.7 g of 
4-[2'(5'-nitrofuryl)]quinoline-2-carboxaldehyde and 50 ml of dioxane. The 
mixture was heated to boiling until a clear solution was obtained. Then 
added at once 0.7 g hydroxylamine hydrochloride dissolved in 20 ml water. 
The mixture was refluxed with stirring for 2 hours. The hot solution was 
filtered with charcoal and concentrated to 1/5 of its initial volume. 50 
ml of water were added and the crystaline precipitate was filtered off. 
2.6 g of 4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde oxime were 
obtained. Yield 92%, m.p. 202.5.degree.-204.degree.. 
An analytical sample was obtained by successive recrystallisation from 
isopropanol, nitromethane and acetone, m.p. 208.degree.-210.degree.. The 
analysis was calculated for C.sub.14 H.sub.9 N.sub.3 O.sub.4 : 
Calculated: C: 59.37%; H: 3.20%; N: 14.84%; Found: C: 59.23%; H: 3.33%; N: 
14.68%. 
The N-oxide of the above compound was prepared in the usual manner, i.e. by 
oxidation with H.sub.2 O.sub.2 (30%) in glacial acetic acid, m.p. 
201.5.degree.-203.5.degree.. The analysis was calculated for C.sub.14 
H.sub.9 N.sub.3 O.sub.5 : 
Calculated: C: 56.19%; H: 3.03%; N: 14.04%; Found: C: 56.33%; H: 3.17%; N: 
13.94%. 
EXAMPLE 27 
In the same manner as described in Example 26 but replacing the 
hydroxylamine hydrochloride with semicarbazide hydrochloride there was 
obtained 4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde semicarbazone. 
An analytical sample was prepared by successive recrystallisation from 
isopropanol, acetone and dioxane, m.p. 247.degree.-248.degree.. The 
analysis was calculated for C.sub.15 H.sub.11 N.sub.5 O.sub.4 : 
Calculated: C: 55.39%; H: 3.41%; N: 21.53%; Found: C: 55.54%; H: 4.03%; N: 
21.34%. 
In the same manner as described in Example 26, replacing the hydroxylamine 
hydrochloride with hydroxylethyl hydrazine there was obtained 
4-[2'-(5'-nitrofuryl)]-quinoline-2-carboxaldehyde B-hydroxyethyl 
hydrazine; m.p. 143.degree.-145.degree.. 
EXAMPLE 28 
In the same manner as described in Example 26 but replacing the 
hydroxylamine hydrochloride with 1-amino-oxazolidine-2-one there was 
obtained 
4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde-amino-oxazolidone, mp. 
264.degree.-265.5.degree.. The analysis was calculated for C.sub.17 
H.sub.12 N.sub.4 O.sub.5 : 
Calculated: C: 57.96%; H: 3.34%; N: 15.90%, Found: C: 57.83%; H: 3.45%; N: 
15.93%. 
EXAMPLE 29 
In the same manner as described in Example 26 but replacing the 
hydroxylamine hydrochloride with 1-aminohydantoin there was obtained 
4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde aminohydantoin, m.p. 
233.degree.-235.degree.. 
Likewise in the same manner as described in Example 26 but replacing the 
hydroxylamine hydrochloride with acetylhydrazine, phenylhydrazine or 
isonicotinoyl hydrazine there were obtained acetyl hydrazone, 
phenylhydrazone and isonicotinoyl hydrazone, respectively, of the 
4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde. 
EXAMPLE 30 
4-[2'-(5'-nitrofuryl)]quinoline-2-carboxaldehyde prepared as described in 
Example 25 was oxidised with H.sub.2 O.sub.2 -glacial acetic acid to yield 
2-carboxy-4-[2'-(5'-nitrofuryl)]quinoline, yield 85% m.p. crude 
192.degree.-196.degree.; after recrystallisation from isopropanol, 
nitromethane the melting point was 199.5.degree.-200.degree.. 
A mixed melting point determination with the compound prepared in Example 6 
gave no depression. 
The N-oxide was prepared, m.p. 188.degree.-189.degree.. 
The 2-carboxy-4-[2'-(5'-nitrofuryl)]quinoline was treated with thionyl 
chloride (by a method known per se) to yield the corresponding 
acylchloride which in turn was treated with: 
a. Abs.ethanol to yield 2-carbethoxy-4-[2'-(5'-nitrofuryl)]quinoline; m.p. 
183.5.degree.-184.5.degree.. 
b. diethylamine to yield 4-[2'-(5'-nitrofuryl)]quinoline-2-carboxylic acid 
diethylamide, m.p. 141.5.degree.-142.5.degree.. 
c. morpholine to yield 2-carboxylic acid-N-morpholine 
amide-4-[2'-(5'-nitrofuryl)]-quinoline, m.p. 173.5.degree.-177.5.degree.. 
The N-oxide was prepared; m.p. 232.degree.-233.degree.. 
Other aldehydes, prepared as described in Example 25, were oxidized in the 
same manner to yield: 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline, m.p. 
176.degree.-177.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-methyl quinoline, m.p. 
203.degree.-204.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline N-oxide, m.p. 
178.degree.-179.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-chloro quinoline N-oxide, m.p. 
177.degree.-178.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-methyl quinoline N-oxide m.p. 
195.degree.-196.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-6-methyl quinoline N-oxide m.p. 
183.degree.-184.degree.; 
2-carboxy-4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline N-oxide m.p. 
169.degree.-170.degree.. 
EXAMPLE 31 
A mixture of 
______________________________________ 
Polyethylene glycol 4000 
200 g 
Polyethylene glycol 1500 
200 g 
Polyethylene glycol 300 
250 g 
Propylene glycol 125 g 
Cety alcohol 20 g 
______________________________________ 
was heated on a steam bath. 2-3 g of 
2-methyl-4-[2'-(5'-nitrofuryl)]quinoline, prepared as described in Example 
1, were added to the melt with efficient stirring. After cooling the mass 
obtained was passed through an ointment roller to produce an ointment. 
EXAMPLE 32 
16 g of 4-methyl-2-[2'-(5'-nitrofuryl)]quinoline, prepared as described in 
Example 2, and 25 g of lactose were mixed together. A starch mucilage 
binder was added in an amount sufficient to produce a proper mass for 
granulation. The mass obtained was passed through a sieve, dried at 
70.degree.-80.degree. and then again passed through a sieve. A small 
quantity of talcum and starch powder was added and tablets were pressed in 
a tabletting machine. 
EXAMPLE 33 
A mixture of 1 g of 2-methyl-4-[2'-(5'-nitrofuryl)]-7-methoxy quinoline 
N-oxide, prepared as described in Example 7, 4 g of lactose, 6 g of 
calcium carbonate and 50 g of soyabean meal were mixed in a Fisher-Kendall 
mixer to be utilised as premix for animal feedstuffs. 
EXAMPLE 34 
9.85 g (0.05 moles) of 1-(5'-nitrofuryl)-butane-1,3 dione and 9 g (0.05 
mole) of 4-amino-2-methoxy-acetanilide were heated together at 110.degree. 
C. with a pinch of ZnCl.sub.2 as catalyst. A melt was obtained and after 
20 minutes the whole mass solidified. It was kept a further 10 minutes at 
110.degree.-120.degree.. After cooling and recrystallization from 
methanol, 16 g of crystalline Schiff base, 
1-(5'-nitro-2'-furo)-butanone-3-(3"-methoxy-4"-acetylamino-phenyl) imino 
were obtained; m.p. 207.degree.-210.degree., yield 89%. 
7 g of the above Schiff base were admixed with 85 g of polyphosphoric acid 
at room temperature. The reaction mixture was a viscous mass which was 
heated for 40 minutes at 110.degree.--110.degree., then allowed to cool to 
room temperature and then 300 ml of water were added with external 
cooling. The pH was adjusted with ammonium-hydroxide to 8 and the 
dark-colored crystals obtained were filtered off and washed with water. 
6.25 g of the crude compound were obtained, 
2-methyl-4-[2'-(5'-nitrofuryl)]-6-acetylamino-7-methoxy-quinoline; m.p. 
210.degree.-216.degree.. 
An analytical sample was prepared by repeated crystallisations from 
isopropanol, benzene and nitromethane; m.p. 239.degree.-240.5.degree.. The 
analysis was calculated for C.sub.17 H.sub.17 N.sub.3 O.sub.5 : 
Calculated: C: 59.47%; H: 4.99%; N: 12.24%; Found: C: 59.80%; H: 4.80%; N: 
12.23%. 
The N-oxide was prepared; m.p. 253.degree.-256.degree.. 
EXAMPLE 35 
7 g of 
1-(5'-nitro-2'-furo)-butanone-3-(3"-methoxy-4"-acetylamino-phenyl)imino 
prepared as described in Example 34 were dissolved at about 5.degree. in 
20 ml of concentrated sulfuric acid. The clear solution was allowed to 
reach room temperature and was afterwards heated to 
100.degree.-110.degree. for 10 minutes and then poured on ice water and 
neutralised with ammonia. 
A red precipitate was obtained which was filtered off. 5 g of a crude 
compound were obtained, 
2-methyl-4-[2'-(5'-nitrofuryl)]-6-amino-7-methoxy-quinoline. 
An analytical sample was prepared by repeated recrystallisations from 
isopropanol, benzene, and nitro-methane; m.p. 216.degree.-217.degree.. The 
analysis was calculated for C.sub.15 H.sub.15 N.sub.3 O.sub.4 : 
Calculated: C: 59.80%; H: 5.02%; N: 13.95%; Found: C: 59.85%; H: 4.71%; N: 
13.99%. 
The N-oxide was prepared, m.p. 229.degree.-230.degree.. 
EXAMPLE 36 
In the same manner as described in Example 34, replacing the 
4-amino-2-methoxy-acetanilide with 2,6-diaminotoluene there was prepared 
2,6-dimethyl-4-[2'-(5'-nitrofuryl)]-7-amino-quinoline; m.p. 
176.degree.-177.degree.. 
This compound was acetylated to yield 
2,6-dimethyl-4-[2'-(5'-nitrofuryl)]-7-acetylaminoquinoline; m.p. 
257.degree.-258.5.degree.. 
By another acetylation there was obtained 
2,6-dimethyl-4-[2'-(5'-nitrofuryl)]-7-trifluoro-acetylamino quinoline; 
m.p. 211.degree.-211.5.degree.. 
EXAMPLE 37 
2-carboxy-4-[2'-(5'-nitrofuryl)]quinoline, obtained as described in Example 
6 or 30, was heated in a high boiling solvent, diphenyl ether, to 
175.degree.-180.degree. for 5 hours. After cooling the solution was poured 
on water, the precipitate was filtered off and dried to yield 
4-[2'-(5'-nitrofuryl)]quinoline, m.p. 176.degree.-177.degree.. The N-oxide 
was prepared, m.p. 185.degree.-186.degree.. 
EXAMPLE 38 
In the same manner as described in Example 25 there was prepared from 
2-methyl-4-[2'-(5'-nitrofuryl)]-7-methoxy-quinoline the 
4-[2'-(5'-nitrofuryl)]-7-methoxy quinoline-2-carboxaldehyde, m.p. 
203.5.degree.-204.5.degree.. 
The compound obtained was oxidised, in the same manner as described in 
Example 30, with H.sub.2 O.sub.2 in glacial acetic acid to yield 
2-carboxy-4-[2'-(5'-nitrofuryl)]-7-methoxy quinoline N-oxide; m.p. 
192.degree.-193.degree.. 
The compound obtained was heated in 50 ml of boiling DMF for 30 minutes and 
then treated as described in Example 30 to yield 
4-[2'-(5'-nitrofuryl)]-7-methoxy quinoline N-oxide; m.p. 
209.degree.-210.degree.. 
Following the procedure of Example 37, and utilising as starting materials 
the carboxy compounds of Example 30, the following compounds were 
prepared: 
4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline, m.p. 142.degree.-144.degree.; 
4-[2'-(5'-nitrofuryl)]-7-ethoxy quinoline N-oxide, m.p. 
185.degree.-187.degree.; 
4-[2'-(5'-nitrofuryl)]-7-chloro quinoline N-oxide, m.p. 
220.degree.-221.degree.; 
4-[2'-(5'-nitrofuryl)]-7-methyl quinoline N-oxide, m.p. 
194.degree.-195.degree.; 
4-[2'-(5'-nitrofuryl)]-6-methyl quinoline N-oxide, m.p. 
183.degree.-184.degree.; 
4-[2'-(5'-nitrofuryl)]-6-ethyl quinoline N-oxide, m.p. 
185.degree.-186.degree..