WO2017109795A1

WO2017109795A1 - Novel compounds useful as potential insect antifeedant and a process for the preparation thereof

Info

Publication number: WO2017109795A1
Application number: PCT/IN2016/050451
Authority: WO
Inventors: Vadla RAMESH; Pathipati Usha RANI; Vaidya Jayathirtha Rao
Original assignee: Council Of Scientific & Industrial Research
Priority date: 2015-12-21
Filing date: 2016-12-21
Publication date: 2017-06-29

Abstract

The present invention relates to novel compounds of general formula A: Particularly, the present invention relates to compounds which are useful as antifeedant against the major agricultural pest Spodoptera litura and thus useful as potential insect antifeedants. Further, the present invention relates to a process for the preparation of novel compounds of general formula A having insect antifeedant activity.

Description

NOVEL COMPOUNDS USEFUL AS POTENTIAL INSECT ANTIFEEDANT AND A PROCESS FOR THE PREPARATION THEREOF

FIELD OF THE INVENTION

The present invention relates to novel compounds of general formula A

Formula A

Where in R = X, Y

X= substituted phenyl,

Y= substituted 2-Chloro Quinoline,

n = 1, 2.

R6=R7=R₈=R₉= alkyl, Ethyl, iPr, Bromo, halo,

R!=R2= R₃= R4=R₅= alkyl, iPr, Bromo,

N0₂, alkoxy, Ar, Bu, -OCH₂0- halo, dihalo, CN, CF₃

Particularly, the present invention relates to a compounds are antifeedant against the major agricultural pest Spodoptera litura and useful as potential insect. More particularly, the present invention also relates to the process for the preparation of general formula A having insect Antifeedant activity.

The structural formula of these compounds is given below.

13a-q, 14a-q

R₁=R₂=R₃=R₄=R₅= alkyl, iPr, Bromo, alkyl, Ethyl, iPr, Bromo, halo, N0₂,

halo, dihalo, CN, CF₃ alkoxy, Ar, Bu, - OCH₂0- BACKGROUND AND PRIOR ART OF THE INVENTION

Heterocyclic ketene aminals (HKAs), also known as cyclic 1,1-enediamines, are powerful and versatile starting materials for the syntheses of a wide variety of heterocycles. la-d,2a-d Since both the a-carbon and the secondary amino group in ketene aminals could be involved in the reactions with electrophiles, HKAs have been used as bisnucleophiles to construct fused azaheterocycles.^{3a c}'^{4a d} These fused heterocyclic structures are frequently found in pesticides and play important roles in discovery of herbicides, some HKAs and their compounds might be used as pesticides, ^{5a c} antibacterial agents,^{6 b} antianxiety agents,^{7a c} antileishmanial agents⁸ and anticancer agents.⁹ Bicyclic pyridones are of general interest within medicinal chemistry, and a series of substituted variants of have been reported as a basis for analgesics and antiinflammatory agents.^{10a c} However, the range of variation available using these strategies is restricted as the diversity (i.e., substitution pattern) is set very early in the synthetic sequence. This, in turn, places limitations on the flexibility and subsequent applications of this chemistry.

OBJECTIVES OF THE INVENTION

The main objective of the present invention is to provides novel compounds of general formula A

Formula A

Where in R = X, Y

X= substituted phenyl,

Y= substituted 2-Chloro Qulnollne,

R8=R9= alkyl, Ethyl, iPr, Bromo, halo,

R-,=R₂= R₃= R =R₅= alkyl, iPr, Bromo,

N0₂, alkoxy, Ar, Bu, -OCH₂0- halo, dlhalo, CN, CF₃ Another object of the present invention relates to a compounds are antifeedant against the major agricultural pest Spodoptera litura and useful as potential insect.

In another object of the present invention is to provide the process for the preparation of general formula A having insect Antifeedant activity.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides novel compounds of general formula A.

Formula A

in R = X, Y

d phenyl,

d

R₆=R₇=R₈=R₉= alkyl, Ethyl, iPr, Bromo, halo,

R-,=R₂= R₃= R₄=R₅= alkyl, iPr, Bromo,

N0₂, alkoxy, Ar, Bu, -OCH₂0- halo, dihalo, CN, CF₃

In an embodiment of the present invention, wherein the compounds of general formula A is represented by the following compounds of general formula 13a-q, 14a-r, 15a-r, 16a-r.

R₁=R₂=R₃=R₄=R₅= alkyl, iPr, Bromo, R₆=R₇=R₈=R₉= alkyl, Ethyl, iPr, Bromo, halo, N0₂,

halo, dihalo, CN, CF₃ alkoxy, Ar, Bu, - OCH₂0-

In another embodiment of the present invention, wherein the representative compounds of general formula 1 comprise: 6-benzyl-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13a), 6-(2-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13b), 6-(3-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one (13c), 6-(4-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one (13d), 6-(2-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13e), 6-(3-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13f), 6-(4-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13g), 6-(2,6-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13h), 6-(3,4-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13i), 6-(3-bromobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13j ), 6-(4-bromobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13k), 6-(2-(trifluoromethyl)benzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (131), 4-((8-nitro-5-oxo- 1 ,2,3,5-tetrahydroimidazo[ 1 ,2-a]pyridin-6-yl)methyl)benzonitrile (13m),

8-nitro-6-(3-nitrobenzyl)-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13n),

8-nitro-6-(4-nitrobenzyl)-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13o),

6-(4-isopropylbenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13p),

6- (naphthalen-2-ylmethyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13q),

7- (2-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14b), 7-(3-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14c), 7-(2-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14d), 7-(3-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14e), 7-(4-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14f), 7-(2,6-dichlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14g),

7-(3,4-dichlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14h),

7-(3-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14i), 7-(4-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14j), 9-nitro-7-(2-(trifluoromethyl)benzyl)-3,4-dihydro- lH-pyrido[ 1 ,2-a]pyrimidin-6(2H)- one (14k),

4-((9-nitro-6-oxo-2,3,4,6-tetrahydro-lH-pyrido[ l,2-a]pyrimidin-7- yl)methyl)benzonitrile (141),

9-nitro-7-(3-nitrobenzyl)-3,4-dihydro-lH-pyrido[ l,2-a]pyrimidin-6(2H)-one (14m), 9-nitro-7-(4-nitrobenzyl)-3,4-dihydro-lH-pyrido[ l,2-a]pyrimidin-6(2H)-one (14n), 7-(4-methylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l ,2-a]pyrimidin-6(2H)-one (14o), 7-(4-ethylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14p), 7-(4-isopropylbenzyl)-9-nitro-3,4-dihydro- lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14q):

7-(naphthalen-2-ylmethyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14r),

6-((2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin-5(lH)- one (15a),

6-((2-chloro-8-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin 5(lH)-one (15b),

6-((2-chloro-8-ethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin- 5(lH)-one (15c),

6-((2-chloro-7-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin 5(lH)-one (15d),

6-((2-chloro-6-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin 5(lH)-one (15e),

6-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin-5(lH)-one ( 15f),

6-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin-5(lH)-one ( 15g),

6-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3- dihydroimidazo[ 1 ,2 ]pyridin-5( lH)-one ( 15h), 6-((2-chloro-6-isopropylquinolin-3-yl) methyl)-8-nitro-2, 3-dihydroimidazo [ 1, 2-a] pyridin-5(lH)-one (15i),

6-((6-butyl-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2-a]pyridin- 5(lH)-one (15j),

6-((2-chlorobenzo[h]quinolin-3-yl) methyl)-8-nitro-2, 3-dihydroimidazo [ 1, 2-a] pyridin-5(lH)-one (15k),

6-((2-chloro-6-methoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin-5(lH)-one ( 151),

6-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin-5(lH)-one ( 15m),

6-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-8-nitro-2,3- dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 15n),

6-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin-5(lH)-one ( 15o),

6-((6-chloro-[l,3]dioxolo[4,5-g]quinolin-7-yl)methyl)-8-nitro-2,3-dihydroimidazo[l ,2- a]pyridin-5(lH)-one (15p),

6-((2-chloro-7-fluoroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin- 5(lH)-one (15q),

6- ((6-bromo-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l ,2- ]pyridin- 5(lH)-one (15r),

7- ((2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin- 6(2H)-one (16a),

7-((2-chloro-8-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one,( 16b),

7-((2-chloro-8-ethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16c),

7-((2-chloro-7-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16d), 7-((2-chloro-6-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16e),

7-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16f),

7-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16g),

7-((2-chloro-5 , 8-dimethylquinolin-3 -yl)methyl)-9-nitro-3 ,4-dihydro- 1 H-pyrido [1,2- a]pyrimidin-6(2H)-one (16h),

7-((2-chloro-6-isopropylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16i),

7-((6-butyl-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16j),

7-((2-chlorobenzo[h]quinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16k),

7-((2-chloro-6-methoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (161),

7-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2 a]pyrimidin-6(2H)-one (16m),

7-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a] pyrimidin-6(2H)-one (16n),

7-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2 a]pyrimidin-6(2H)-one (16o),

7-((6-chloro-[l,3]dioxolo[4,5-g]quinolin-7-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a] pyrimidin-6(2H)-one (16p),

7-((2-chloro-7-fluoroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16q),

7-((6-bromo-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro- lH-pyrido[ 1 ,2- a]pyrimidin-6(2H)-one (16r) In a preferred embodiment of the present invention, wherein the compounds of general formula A are useful as insect Antifeedant compounds.

In yet another embodiment of the present invention, wherein a process for the preparation of novel compounds of general formula A comprising the steps of:

i. refluxing the mixture of acetylated Baylis-Hillman adducts 6(a-r) or 12(a-r) with solution of 2a 2-(nitromethylene)imidazolidine or 2b 2- (nitromethylene)hexahydropyrimidine in presence of a solvent and base at the temperature ranging between 110 °C for a period of time in the range of 2-3 h following by cooling and pouring into water at room temperature ranging between 25- 35 °C , filtering and washing with water subsequently recrystallizing with ethanol to get imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine based compounds of general formula A.

In still another embodiment of the present invention, wherein the solvent is selected from the group consisting of 1,4-dioxan, 20 ml.

In another embodiment of the present invention, wherein the base is selected from the group consisting of triethylamine(Et₃N) 3ml.

In yet another embodiment of the present invention, wherein the molar ratio of triethylamine(Et₃N) is 3 (1 : 12) in respect of acetylated Baylis-Hillman adducts 6(a-r) or 12(a-r) .

In a preferred embodiment of the present invention, wherein acetylated Baylis-Hillman adducts is selected from the group consisting of 6(a-r) or 12(a-r)

In another embodiment of the present invention, wherein yield of the compounds of general formula A is in the range of 55-81%. DETAILED DESCRIPTION OF THE INVENTION

The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated. The present invention is directed towards the synthesis of a imidazo[l,2- ] pyridine and pyrido[l,2- ]pyrimidine based analogues of general formula A and having excellent insect Antifeedant activity.

Formula A

in R = X, Y

X= substituted phenyl,

Y= substituted 2-Chloro Quinoline,

n = 1 , 2.

R₆=R₇=F?8=R₉= alkyl, Ethyl, iPr, Bromo, halo,

^R1 =^R ₂= ^R3= R4=^R5= alkyl, iPr, Bromo,

N0₂, alkoxy, Ar, Bu, -OCH₂0- halo, dihalo, CN, CF₃

In an embodiment of the present invention the a imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine based analogues are represented by the following compounds of general formula.

13a-q, 14a-q 15a-r, 16a-r

halo, dihalo, CN, CF₃ alkoxy, Ar, Bu, - OCH₂0-

In yet another embodiment the compounds of formula lare represented by the group of the following compounds:

6-benzyl-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13a),

6-(2-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13b), 6-(3-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one (13c), 6-(4-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one (13d), 6-(2-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13e), 6-(3-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13f), 6-(4-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13g), 6-(2,6-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13h), 6-(3,4-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13i), 6-(3-bromobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13j ), 6-(4-bromobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( 1 H)-one ( 13k), 6-(2-(trifluoromethyl)benzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (131), 4-((8-nitro-5-oxo- 1 ,2,3,5-tetrahydroimidazo[ 1 ,2-a]pyridin-6-yl)methyl)benzonitrile (13m),

8-nitro-6-(3-nitrobenzyl)-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13n),

8- nitro-6-(4-nitrobenzyl)-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13o),

6-(4-isopropylbenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13p),

7-(3-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14i), 7-(4-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14j),

9- nitro-7-(2-(trifluoromethyl)benzyl)-3,4-dihydro- lH-pyrido[ 1 ,2-a]pyrimidin-6(2H)- one (14k), 4-((9-nitro-6-oxo-2,3,4,6-tetrahydro-lH-pyrido[ l,2-a]pyrimidin-7- yl)methyl)benzonitrile (141),

6-((2-chloro-8-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin- 5(lH)-one (15b),

6-((2-chloro-7-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin- 5(lH)-one (15d),

6-((2-chloro-6-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin- 5(lH)-one (15e),

6-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3- dihydroimidazo[ 1 ,2 ]pyridin-5( lH)-one ( 15h),

6-((2-chloro-6-isopropylquinolin-3-yl) methyl)-8-nitro-2, 3-dihydroimidazo [ 1, 2-a] pyridin-5(lH)-one (15i), 6-((6-butyl-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2-a]pyridin- 5(lH)-one (15j),

7-((2-chloro-7-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16d),

7-((2-chloro-6-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16e), 7-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16f),

7-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16m),

7-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16o),

7-((6-bromo-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro- lH-pyrido[ 1 ,2- a]pyrimidin-6(2H)-one (16r)

The present invention further provides a process for preparation of a imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine based analogues of formula (13a-q, 14a-r, 15a-r, 16a-r) which comprises reactions of precursor activated olefine (4) as starting material with substituted aromatic aldehydes (3a-q), or (lOa-r) using base DABCO (diazabicyclo [2.2.2] octane) has been the catalyst of choice, various other tertiary amine catalysts such as quinuclidine 3-HQD (3-hydroxy quinuclidine), 3- quinuclidone, DBU, pyrrocoline, DMAP (dimethylaminopyridine), TMPDA (N^N^N^tetramethyl-l^-propanediamine), imidazole, TMG (tetramethyl guanidine) and triethyl amine have also been employed to perform the Baylis-Hillman reaction in certain cases. Several non-tertiary amine catalysts such as dimethyl sulfide/TiC , TiCL_t, trialkylphosphines, RhH(PPh₃)4, have been used as catalysts for coupling of various activated alkenes with aldehydes to obtain (5a-r), (lla-r) and further to acetylated Baylis-Hillman adducts 6a-r, 12a-r by using pyridine, Ac₂0/AcCl. Thus prepared 6a-r, 12a-r were reacted with (Z)-ethyl 2-(pyrrolidin-2- ylidene) acetate (2a, 2b) using base like Et₃N in organic solvents (1, 4 dioxine) in different reaction conditions resulting in the formation of final compounds imidazo[l,2- ] pyridine and pyrido[l,2- ]pyrimidine based analogues of formula (13a- q, 14a-r, 15 -r, 16a-r).

13a-q, 14a-q 15a-r, 16a-r

The precursor substituted aromatic aldehydes (3a-r), (lOa-r), activated olefines (4) and l,4-diazabicyclo[2.2.2]octane (DABCO) are commercially available and imidazo[l,2- ] pyridine and pyrido[l,2- ]pyrimidine s (13a-q, 14a-r, 15a-r, 16a-r), of formula have been prepared as illustrated in the Schemes (1-6).

The substituted aromatic aldehydes (3a-r), (lOa-r), reacted with the activated olefins (4) using DABCO at rt for 10-12 h to obtian desired Baylis-Hillman adducts (5a-r), (lla-r).

To a solution of Baylis-Hillman adducts (5a-r), (lla-r) in dichloromethane at 0 °C, under argon atmosphere was added pyridine after 10 min acetyl chloride was added and allow it to stir at room temperature for 2 h to obtain desired acetylated Baylis- Hillman addcuts (6a-r), (12a-r).

All the imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine based compounds have been synthesized and were purified by recrysatlization from ethanol. Procedure of imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine formation: To a solution of methyl 2-(acetoxy (phenyl) methyl) acrylate (6a-r), (12a-r), (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene) imidazohdine 2a, or 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to room temperature and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products.

These new analogues of imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine based compounds were screened for their and found as potential insect Antifeedant activity. The synthesized molecules presented here are of immense biological significance.

Scheme 1

Scheme 2

Scheme 3

Scheme 6

General procedure for the preparation Baylis-Hillman adducts (5a-r), (lla-r):

Substituted aromatic aldehydes (3a-r), (lOa-r) (10 mmol), activated olefin (4) (20 mmol) and DABCO (30 mol% with respect to aldehyde) were mixed and allowed to stir at room temperature until completion of the reaction, TLC (10-12 h). After completion, the reaction mixture was diluted with water (15 mL) and extracted with ether (3 x 25 mL). The combined organic layers were dried over Na₂S0₄, solvent was removed under reduced pressure and purified by column chromatography using 10% EtOAc in hexane as eluent to afford pure Baylis-Hillman adducts (5a-r), (lla-r) in 80- 90% yield.

General procedure for the preparation of acetylated Baylis-Hillman adducts (6a- r), (12a-r):

To a well stirred solution of Baylis-Hillman adduct (5a-r), (lla-r) (10 mmol) in dichloromethane (30 mL) at 0 °C under argon atmosphere was added slowly pyridine (11 mmol) and stirred for 10 min. Then acetyl chloride (11 mmol) was added slowly and allowed to stir at room temperature until the reaction completed, TLC (1-2 h). After completion of the reaction, diluted the reaction with water (15 mL) and extracted with dichloromethane (2 x 25 mL). The combined organic layers were washed with sat. CuS0₄ solution until pyridine removed, then the layers were sepaerated and dried over Na₂S0_4i solvent was removed under reduced pressure. The resulting residue was subjected to column chromatography using 5% EtOAc in hexane as eluent to afford pure compounds acetylated Baylis-Hillman adducts (6a-r), (12a-r) in 85-90% yield. General Preparation of 2-(nitromethylene) imidazolidine or 2-(nitromethylene) hexahydropyrimidine:

To a Stirred mixture of nitro methane (10 ml, 1.84 mol) and carbon disulfide (11.13ml, 1.84 mol) in dry methanol (10 ml) under a blanket of dry N₂ at 0 °C was slowly added a solution of KOH (23g, 4.14 mol) by using a pressure equalized funnel and the mixture was vigorously stirred at 0 °C for 3h. The reddish salt formed in the reaction was filtered and washed with methanol (15 ml) followed by dry diethyl ether (15 ml) to furnish (17.6 g) of dipotassium 2-nitro 1, 1 ethylenedithiate (45%) as a dry reddish powder. The salt was used for next step immediately.

To the stirred suspension of the salt (17.6 g, 82.6 mmol) in dry hexane (50 ml) and dry toluene (5 ml) was added drop wise freshly distilled dimethyl sulphate (10.4 g, 82.6 mmol) in 10 ml of dry toluene through a pressure equalize funnel at 0 °C during 30 min and the reaction mixture was vigorously stirred for 2 h at the same temp to furnish (2-nitroethene-l,l-diyl) bis(methylsulfane). The crude product 2-(nitromethylene) hexahydropyrimidine / 2-(nitromethylene) imidazolidine was filtered and recrystlized (ethanol) to get the light yellow crystals (11.58 g, 85%) mp.127-129 °C.

The following examples are given by way of illustration.

Example 1

6-benzyl-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13a):

To a solution of methyl 2-(acetoxy(phenyl)methyl)acrylate 6a (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 212-215°C. ^XH NMR (300 MHz, CDC1₃): δ 7.77 (s, 1H), 7.30-7.27(m, 3H), 4.31 (t, 2H, = 9.46 Hz), 4.04 (t, 2H, = 9.46 Hz), 3.76 (s, 2H); MS(LCMS) m z (%): 272[M+H]⁺.

Example 2

6-(2-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13b): To a solution of methyl 2-(acetoxy(2-fluorophenyl)methyl)acrylate 6b (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 216-218°C. 1H NMR (300 MHz, CDC1₃): δ 7.76 (s, 1H), 7.30 (t, 1H, = 7.47 Hz), 7.08 (t, 1H, = 7.47 Hz), 7.05 (d, 1H, / = 8.24 Hz), 7.03 (d, 1H, = 8.24 Hz), 4.31 (t, 2H, = 9.76 Hz), 4.04 (t, 2H, = 9.76 Hz), 3.79 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 155.51, 151.38, 141.44, 132.57, 129.90, 124.54, 121.26, 120.61, 115.84, 115.63, 113.29, 44.41, 43.15, 35.15; MS(LCMS) m/z (%): 312[M+Na]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₄H₁₂FN₃0₃: 290.09355; found: 290.09287.

Example 3

6-(3-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13c): To a solution of methyl 2-(acetoxy(3-fluorophenyl)methyl)acrylate, 6c (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 196-198 °C. ^XH NMR (300 Hz, CDC1₃): δ 7.80 (s, 1H), 7.05 (d, 1H, = 7.55 Hz), 6.99-6.89 (m, 3H), 4.32 (t, 2H, = 9.63 Hz), 4.05 (t, 2H, = 9.63 Hz), 3.74 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 155.51, 151.38, 141.44, 132.57, 129.90, 124.54, 121.26, 120.61, 115.84, 115.63, 113.29, 44.41, 43.15, 35.15; MS(ESI) m/z (%): 312[M+Na]⁺. HRMS(ESI): [M+H]⁺ Calcd for C14H12FN3O3: 290.09355; found: 290.09275.

Example 4

6-(4-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13d): To a solution of 2-(acetoxy(4-fluorophenyl)methyl)acrylate 6d (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 192-194 °C. 1H NMR (300 MHz, CDC1₃): δ 8.17 (s, 1H), 7.63 (d, 1H, = 8.85 Hz), 7.34 (d, 1H, = 8.85 Hz), 4.32 (t, 2H, = 9.76 Hz), 4.07 (t, 2H, = 9.76 Hz), 4.01 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 155.51, 151.38, 141.44, 132.57, 129.90, 124.54, 121.26, 120.61, 115.84, 115.63, 113.29, 44.41, 43.15, 35.15; MS(ESI) m/z (%): 290[M+H]⁺.

Example 5

6-(2-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13e):

To a solution of methyl 2-(acetoxy(2-chlorophenyl)methyl)acrylate 6e (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp. 198-200°C. 1H NMR (300 MHz, CDC1₃): δ 7.68 (s, 1H), 7.38 (d, 1H, = 7.32 Hz), 7.34 (d, 1H, = 6.86 Hz), 7.23 - 7.20 (m, 2H), 4.33 (t, 2H, = 9.61 Hz), 4.05 (t, 2H, 7 = 9.61 Hz), 3.88 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.61, 151.25, 136.15, 134.26, 132.48, 131.47, 129.68, 128.16, 126.91, 126.44, 119.34, 44.41, 43.14, 32.90; MS(LCMS): m/z (%): 328[M+Na]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₄Hi₂ClN₃0₃Na: 328.04594; found: 328.04490.

Example 6

6-(3-chlorobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13f):

To a solution ofmethyl 2-(acetoxy(3-chlorophenyl)methyl)acrylate 6f (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp: 195-197°C. 1H NMR (300 MHz, CDC1₃): δ 7.81 (s, 1H), 7.24 (s, 1H), 7.22 (d, 1H, =7.47 Hz), 7.20 (t, 1H, = 3.32 Hz), 7.16 (d, 1H, = 7.32 Hz), 4.31 (t, 2H, = 9.61 Hz), 4.05 (t, 2H, = 9.61 Hz), 3.72 (s, 2H); MS(LCMS) m/z (%): 304[M-H]⁺.

Example 7

6-(4-chlorobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13g): To a solution of methyl 2-(acetoxy(4-chlorophenyl)methyl) 6g (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 60%; mp: 187-189 °C. 1H NMR (300 MHz, CDC1₃): δ 7.79 (s, 1H), 7.21 (s, 1H), 7.19 (s, 1H), 4.30 (t, 2H, = 9.61 Hz), 4.04 (t, 2H, = 9.61 Hz), 3.71 (s, 2H): ¹³C NMR (300 MHz, CDC1₃): δ 160.55, 152.54, 142.73, 132.38, 130.84, 130.25, 129.11, 128.64, 120.84, 44.41, 43.16, 34.92; MS(LCMS); m/z (%): 304[M- H]⁺. HRMS(ESI): [M-H]⁺ Calcd for C14H12CIN3O3: 304.04971; found: 304.04835. Example 8

6-(2, 6-dichlorobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13h):

To a solution of methyl 2-(acetoxy(2,6-dichlorophenyl)methyl)acrylate 6h (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 73%; mp: 197-199 °C. 1H NMR (300 MHz, CDC1₃): δ 7.37 (d, 1H, 7 = 7.93 Hz), 7.25 (d, 1H, 7 = 7.93 Hz), 7.24 (s, 1H), 7.17 (t, 1H, 7 = 7.93 Hz), 4.38 (t, 2H, 7 = 8.68 Hz), 4.09 (t, 2H, 7 = 8.68 Hz), 3.68 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.46, 151.26, 136.02, 134.60, 134.05, 133.28, 130.46, 129.26, 128.82, 128.47, 127.77, 44.48, 43.18, 30.41; MS(LCMS) m/z (%): 362[M+H]⁺. HRMS(ESI): [M-H]⁺ Calcd for Ci₄HnCl₂N₃0₃: 340.02435; found: 340.02417.

Example 9

6-(3, 4-dichlorobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13i):

To a solution of methyl 2-(acetoxy(3,4-dichlorophenyl)methyl)acrylate 6i (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 73%; mp: 226-228 °C. 1H NMR (300 MHz, CDC1₃): δ 7.83 (s, 1H), 7.36 (d, 1H, 7 = 5.49 Hz), 7.35 (s, 1H), 7.12 (d, 1H, 7 = 8.24 Hz), 4.31 (t, 2H, 7 = 9.61 Hz), 4.05 (t, 2H, = 9.61 Hz), 3.70 (s, 2H); MS(LCMS) m/z (%): 338[M-H]⁺. HRMS(ESI): [M-H]⁺ Calcd for C₁₄H₁₁CI₂N₃O₃: 340.02435; found: 340.02437.

Example 10

6-(3-bromobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13j): To a solution of methyl 2-(acetoxy(3-bromophenyl)methyl)acrylate 6j (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 194-196 °C. 1H NMR (300 MHz, CDC1₃): δ 7.81 (s, 1H), 7.40 (s, 1H), 7.35 (t, 1H, = 5.49 H z), 7.22 (d, 1H, = 8.08 Hz), 7.17 (d, 1H, = 7.78 Hz), 4.31 (t, 2H, = 9.61 Hz), 4.05 (t, 2H, = 9.61 Hz), 3.72 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.51, 151.41, 141.37, 137.09, 132.65, 131.74, 130.04, 129.60, 128.49, 127.59, 120.41, 44.43, 43.17, 35.13; MS(LCMS); m/z (%): 348[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₄Hi₂BrN₃0₃: 350.01348; found: 350.01403.

Example 11

6-(4-bromobenzyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)-one (13k):

To a solution ofmethyl 2-(acetoxy(4-bromophenyl)methyl)acrylate 6k (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 196-198 °C. 1H NMR (300 MHz, CDC1₃): δ 7.79 (s, 1H), 7.41 (d, 1H, = 5.49 H z), 7.15 (d, 1H, = 8.39 Hz), 7.17 (d, 1H, = 8.39 Hz), 4.30 (t, 2H, = 9.61 Hz), 4.04 (t, 2H, = 9.61 Hz), 3.70 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.54, 151.33, 141.12, 137.97, 133.71, 131.73, 131.55, 130.63, 123.40, 44.38, 43.16, 34.97; MS(ESIR) m/z (%): 350[M+H]⁺. Example 12

8-nitro-6-(2-(trifluoromethyl) benzyl)-2, 3-dihydroimidazo [1, 2-a] pyridin-5(lH)- one (131):

To a solution of methyl 2-(acetoxy(2-(trifluoromethyl)phenyl)methyl)acrylate 61 (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 77%; mp: 197-199 °C. 1H NMR (300 MHz, CDC1₃): δ 7.84 (br, 1H), 7.69 (d, 1H, = 7.78 Hz), 7.49 (t, 1H, = 7.47 Hz), 7.48 (s, 1H), 7.37 (t, 1H, = 7.47 Hz), 7.32 (d, 1H, = 7.78 Hz), 4.35 (t, 2H, = 9.00 Hz), 4.07 (t, 2H, = 9.00 Hz), 3.96 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.29, 149.46, 137.01, 133.21, 131.95, 131.58, 126.81, 126.27, 126.23, 118.03, 113.84, 40.26, 38.82, 32.17, 19.03; MS(LCMS) m/z (%): 338[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅Hi₂F₃N₃0₃: 350.07470; found: 338.07602.

Example 13

4-((8-nitro-5-oxo-l, 2, 3, 5-tetrahydroimidazo[l,2-a]pyridin-6- yl)methyl)benzonitrile (13m):

To a solution of methyl 2-(acetoxy(4-cyanophenyl)methyl)acrylate 6m (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 64%; mp: 237-239 °C. 1H NMR (300 MHz, CDC1₃): δ 7.86 (s, 1H), 7.58 (d, 1H, = 5.49 H z), 7.39 (d, 1H, = 8.24 Hz), 7.17 (d, 1H, = 8.24 Hz), 4.30 (t, 2H, = 9.76 Hz), 4.06 (t, 2H, = 9.76 Hz), 3.79 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 140.13, 139.19, 132.95, 132.30, 132.10, 132.01, 130.43, 129.61, 128.70, 118.30, 52.26, 44.41, 35.80; MS(LCMS) m/z (%): 395[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C15H12N4O3: 297.09822; found: 297.09754.

Example 14

8-nitro-6-(3-nitrobenzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13n): To a solution of methyl 2-(acetoxy(3-nitrophenyl)methyl)acrylate 6n (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 63%; mp: 169-171 °C. 1H NMR (300 MHz, CDC1₃): δ 7.81 (s, 1H), 7.40 (s, 1H), 7.35 (d, 1H, = 7.55 Hz), 7.22 (d, 1H, = 7.55 Hz), 7.19 (t, 1H, = 7.55 Hz), 4.32 (t, 2H, = 9.82 Hz), 4.06 (t, 2H, = 9.82 Hz), 3.72 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 157.37, 151.45, 141.40, 135.62, 132.66, 131.78, 130.64, 130.07, 129.65, 127.61, 120.49, 44.45, 43.18, 35.15; MS(LCMS) m/z (%): 317[M+H]⁺.

Example 15

8-nitro-6-(4-nitrobenzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13o):

To a solution of methyl 2-(acetoxy(4-nitrophenyl)methyl)acrylate (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 63%; mp: 238-240°C. 1H NMR (300 MHz, CDC1₃): δ 8.15 (d, 1H, = 8.68 Hz), 7.89 (s, 1H), 7.82 (br, 1H), 7.45 (d, 1H, =8.68 Hz), 4.31 (t, 2H, = 9.63 Hz), 4.06 (t, 2H, = 9.63 Hz), 3.85 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.53, 151.41, 141.11, 134.26, 132.64, 129.74, 129.46, 128.87, 127.11, 126.69, 120.44, 44.43, 43.19, 35.15; MS(LCMS) m/z (%): 315[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for ^Η₁₂Ν₄0₅: 315.07240; found; 315.07388. Example 16

6-(4-isopropylbenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13p):

To a solution of methyl 2-(acetoxy(4-isopropylphenyl)methyl)acrylate 6p (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 190-192°C. 1H NMR (300 MHz, CDC1₃): δ 7.91 (s, 1H), 7.51 (d, 1H, / = 8. 08 Hz), 7.34 (d, 1H, = 8.08 Hz), 4.21 (t, 2H, = 9.00 Hz), 4.08 (s, 2H), 3.97 (t, 2H, = 9.00 Hz), 2.96 (sp, 1H), 1.28 (s, 3H), 1.27 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 149.79, 148.36, 142.39, 142.26, 130.67, 127.64, 126.51, 126.38, 125.52, 44.36, 43.49, 42.78, 33.72, 23.70; MS(LCMS) m/z (%): 312[M-H]⁺. HRMS(ESI): [M]⁺ Calcd for Ci₇Hi₉N₃0₃: 313.14209; found: 313.14032. Example 17

6-(naphthalen-2-ylmethyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13q):

To a solution of methyl 2-(acetoxy(naphthalen-2-yl)methyl)acrylate 6q (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 65%; mp: 194-196 °C. 1H NMR (300 MHz, CDC1₃): δ 7.81 (s, 1H), 7.40 (s, 1H), 7.35 (d, 1H, = 7.55 Hz), 7.22 (d, 1H, 7 = 7.55 Hz), 7.19 (t, 1H, = 7.55 Hz), 4.32 (t, 2H, = 9.82 Hz), 4.06 (t, 2H, = 9.82 Hz), 3.72 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 144.19, 144.04, 133.32, 130.67, 130.17, 128.72, 127.01, 126.82, 126.29, 125.41, 125.32, 123.11, 112.07, 58.08, 57.66, 56.81 ; MS(LCMS) m/z (%): 322[M+H]⁺. HRMS(ESI): [M]⁺ Calcd for C18H15N3O3: 321.13560; found: 321.13526.

Example 18

7-benzyl-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14a):

To a solution of methyl 2-(acetoxy(phenyl)methyl)acrylate 6a (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 198-200°C. 1H NMR (300 MHz, CDC1₃): δ 7.98 (s, 1H), 7.25 (s, 1H), 7.31-7.27 (m, 5H), 4.07 (t, 2H, = 5.95 Hz), 3.75 (s, 2H), 3.59 (m, 2H), 2.14 (qt, 2H); MS(LCMS) m z (%) 286[M+H]⁺.

Example 19

7-(2-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14b):

To a solution of methyl 2-(acetoxy(2-fluorophenyl)methyl)acrylate 6b (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 198-200°C. 1H NMR (300 MHz, CDC1₃): δ 7.86 (s, 1H), 7.37 (d, 1H, = 6.04 Hz), 7.33 (d, 1H, = 6.04 Hz), 7.21 (m, 2H), 4.09 (t, 2H, = 6.04 Hz), 3.88 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.31, 149.56, 132.95, 131.49, 131.43, 128.47, 128.35, 124.13, 124.07, 115.61, 115.32, 40.20, 38.83, 29.29, 19.05; MS(LCMS) m/z (%) 304[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅H₁₄FN₃0₃: 304.10965; found: 304.10972. Example 20

7-(3-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14c):

To a solution of methyl 2-(acetoxy(3-fluorophenyl)methyl)acrylate 6c (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 1 10 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 74%; mp: 158-160°C. 1H NMR (300 MHz, CDC1₃): δ 8.00 (s, 1H), 7.25 (s, 1H), 7.04-6.89 (m, 1H), 4.07 (t, 2H, = 6.04 Hz), 3.74 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 164.42, 161.22, 149.56, 133.06, 129.89, 124.45, 118.14, 1 15.78, 115.52, 113.42, 1 13.13, 40.17, 38.75, 35.78, 18.90; MS(LCMS) m/z (%): 304 [M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅H₁₄FN₃0₃: 304.10965; found: 304.10996.

Example 21

7-(2-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14d):

To a solution of methyl 2-(acetoxy(2-chlorophenyl)methyl)acrylate 6d (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 1 10 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp: 178-180 °C. 1H NMR (300 MHz, CDC1₃): δ 7.86 (s, 1H), 7.37 (d, 1H, = 6.04 Hz), 7.33 (d, 1H, = 6.04 Hz), 7.21 (m, 2H), 4.09 (t, 2H, = 6.04 Hz), 3.88 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.52, 149.71 , 136.38, 134.54, 133.24, 131.67, 129.88, 128.33, 127.11, 117.20, 114.04, 40.42, 39.03, 33.74, 19.21 ; MS(LCMS) m/z (%): 320[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C15H14CIN3O3: 320.7965; found: 320.08029.

Example 22

7-(3-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14e):

To a solution of methyl 2-(acetoxy(3-chlorophenyl)methyl)acrylate 6e (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp: 160-162°C. 1H NMR (300 MHz, CDC1₃): δ 8.01 (s, 1H), 7.24-7.15 (m, 4H), 4.07 (t, 2H, = 6.04 Hz), 3.72 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.20, 149.59, 141.14, 134.17, 133.14, 129.68, 128.82, 127.08, 126.60, 118.04, 113.70, 40.19, 38.79, 35.80, 18.95; MS(LCMS) m/z (%): 320[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅Hi₄ClN₃0₃: 320.7965; found: 320.08021.

Example 23

7-(4-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14f):

To a solution of methyl 2-(acetoxy(4-chlorophenyl)methyl)acrylate 6f (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp: 146-148 °C. ^XH NMR (300 MHz, CDC1₃): δ 7.99 (s, 1H), 7.25 (d, 2H, = 8.39 Hz), 7.20 (d, 2H, = 8.39 Hz), 4.06 (t, 2H, = 5.79 Hz), 3.71 (s, 2H), 3.59 (m, 2H), 2.14 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 149.53, 145.89, 140.33, 137.48, 132.86, 130.21, 128.52, 118.40, 113.63, 40.14, 38.75, 35.52, 18.90; MS(LCMS) m/z (%): 320[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C15H14CIN3O3: 320.7965; found: 320.08036.

Example 24

7-(2,6-dichlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14g):

To a solution of methyl 2-(acetoxy(2,6-dichlorophenyl)methyl)acrylate 6g (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 73%; mp: 208-210 °C. 1H NMR (300 MHz, CDC1₃): δ 7.41 (s, 1H), 7.36 (d, 2H, = 8.08 Hz), 7.20 (t, 2H, = 8.08 Hz), 4.15 (t, 2H, = 5.95 Hz), 4.09 (s, 2H), 3.61 (m, 2H), 2.18 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.35, 157.91, 149.41, 136.20, 133.76, 130.94, 128.79, 128.44, 115.52, 40.26, 38.80, 30.92, 18.96; MS(LCMS) m/z (%): 352[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅Hi₃Cl₂N₃0₃: 354.04067; found: 354.04160.

Example 25

7-(3,4-dichlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14h):

To a solution of methyl 2-(acetoxy(3,4-dichlorophenyl)methyl)acrylate 6h (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 73%; mp: 172-174 °C. 1H NMR (300 MHz, CDC1₃): δ 8.04 (s, 1H), 7.36 (s, 1H), 7.34 (d, 2H, = 8.24 Hz), 7.12 (d, 2H, = 8.24 Hz), 4.06 (t, 2H, = 5.95 Hz), 3.69 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃) δ: 161.13, 149.63, 139.45, 133.25, 132.28, 130.62, 130.37, 130.30, 128.31, 117.52, 113.67, 40.20, 38.81, 35.45, 18.93; MS(LCMS) m/z (%): 354[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for CisHisCbNsOs: 354.04067; found: 354.04153.

Example 26

7-(3-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14i):

To a solution of methyl 2-(acetoxy(3-bromophenyl)methyl)acrylate 6i (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 167-169 °C. 1H NMR (300 MHz, CDC1₃): δ 8.01 (s, 1H), 7.24-7.15 (m, 4H), 4.07 (t, 2H, = 6.04 Hz), 3.72 (s, 2H), 3.60 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.18, 149.59, 141.46, 133.14, 131.69, 129.98, 129.51, 127.56, 122.47, 118.00, 113.69, 40.19, 38.79, 35.78, 18.94; MS(LCMS) m/z (%): 364[M+H]⁺.

Example 27

7-(4-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14j):

To a solution of methyl 2-(acetoxy(4-bromophenyl)methyl)acrylate 6j (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystalhzed by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 158-160 °C. 1H NMR (300 MHz, CDC1₃): δ 8.00 (s, 1H), 7.41 (d, 2H, = 8.30 Hz), 7.15 (d, 2H, = 8.30 Hz), 4.06 (t, 2H, = 6.04 Hz), 3.69 (s, 2H), 3.59 (m, 2H), 2.14 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.22, 149.56, 138.06, 132.94, 131.52, 130.63, 120.28, 118.32, 113.70, 40.17, 38.80, 35.66, 18.97; MS(LCMS) m/z (%): 364[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for CisHwBrNsOs: 364.02913; found: 364.02937.

Example 28

9-nitro-7-(2-(trifluoromethyl)benzyl)-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin- 6(2H)-one (14k):

To a solution of methyl 2-(acetoxy(2-(trifluoromethyl)phenyl)methyl)acrylate 6k (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 77%; mp; 262-264 °C. 1H NMR (300 MHz, CDC1₃): δ 7.69 (d, 2H, = 7.62 Hz), 7.68 (s, 1H), 7.49 (t, 2H, = 7.62 Hz), 7.36 (t, 2H, = 7.62 Hz), 7.30 (d, 2H, = 7.62 Hz), 4.12 (t, 2H, = 5.95 Hz), 3.96 (s, 2H), 3.61 (m, 2H), 2.17 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.25, 149.42, 137.01, 133.15, 131.91, 131.50, 126.74, 126.15, 125.44, 123.26, 117.84, 113.77, 40.23, 38.77, 32.12, 18.94; MS(LCMS) m/z (%): 354[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₆Hi₄F₃N₃0₃: 354.10600; found: 354.10530.

Example 29

4-((9-nitro-6-oxo-2,3,4,6-tetrahydro-lH-pyrido[l,2-a]pyrimidin-7- yl)methyl)benzonitrile (141):

To a solution of methyl 2-(acetoxy(4-cyanophenyl)methyl)acrylate 6n (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 63%; mp: 230-232 °C. 1H NMR (300 MHz, CDC1₃): δ 8.07 (s, 1H), 7.58 (d, 2H, = 8.24 Hz), 7.39 (d, 2H, = 8.24 Hz), 4.06 (t, 2H, = 5.95 Hz), 3.79 (s, 2H), 3.60 (m, 2H), 2.14 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.15, 149.68, 144.87, 133.50, 132.29, 129.60, 118.91, 117.15, 113.73, 40.24, 38.84, 36.49, 18.98; MS(LCMS) m/z (%): 309[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₆Hi₄N₄0₃: 311.11387; found: 311.11480.

Example 30

9-nitro-7-(3-nitrobenzyl)-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14m):

To a solution of methyl 2-(acetoxy(3-nitrophenyl)methyl)acrylate 61 (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 64%; mp: 172-174 °C. ^XH NMR (300 MHz, CDC1₃): δ 8.11 (s, 1H), 8.09 (s, 1H), 8.08 (d, 1H, = 7.63 Hz), 7.63 (d, 1H, = 7.63 Hz), 7.46 (t, 1H, = 7.63 Hz), 4.06 (t, 2H, = 5.79 Hz), 3.85 (s, 2Hz), 3.61 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.14, 149.69, 148.34, 141.30, 135.14, 133.60, 129.97, 129.29, 123.55, 121.61, 117.06, 40.24, 38.82, 36.03, 18.94; MS(LCMS) m/z (%): 329 [M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₅Hi₄N₄0₅: 331.103; found: 331.10431.

Example 31

9-nitro-7-(4-nitrobenzyl)-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14n): To a solution of methyl 2-(acetoxy(4-nitrophenyl)methyl)acrylate 6m (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 63%; mp: 168-170 °C. 1H NMR (300 MHz, CDC1₃): δ 8.15 (d, 1H, = 8.69 Hz), 8.09 (s, 1H), 7.44 (d, 1H, = 8.69 Hz), 4.06 (t, 2H, = 5.79 Hz), 3.84 (s, 2Hz), 3.61 (m, 2H), 2.15 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.25, 149.42, 137.01, 133.15, 131.91, 131.50, 126.74, 126.15, 125.44, 123.26, 117.84, 113.77, 40.23, 38.77, 32.12, 18.94; MS(LCMS) m/z (%): 329[M-H]⁺.

Example 32

7-(4-methylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14o):

To a solution of methyl 2-(acetoxy(p-tolyl)methyl)acrylate 6o (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 65%; mp: 150-152 °C. 1H NMR (300 MHz, CDC1₃): δ 8.07 (s, 1H), 7.58 (d, 2H, = 8.24 Hz), 7.39 (d, 2H, = 8.24 Hz), 4.06 (t, 2H, = 5.95 Hz), 3.79 (s, 2H), 3.60 (m, 2H), 2.25 (s 3H), 2.14 (qt, 2H); MS(LCMS) m/z (%): 300[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₆Hi₇N₃0₃: 311.13427; found: 300.13478.

Example 33

7-(4-ethylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14p): To a solution of methyl 2-(acetoxy(4-ethylphenyl)methyl)acrylate 6p (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 68%; mp: 145-147 °C. 1H NMR (300 MHz, CDC1₃): δ 8.07 (s, 1H), 7.58 (d, 2H, = 8.24 Hz), 7.39 (d, 2H, = 8.24 Hz), 4.06 (t, 2H, = 5.95 Hz), 3.79 (s, 2H), 3.60 (m, 2H), 2.14 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.34, 149.49, 142.26, 136.08, 132.63, 130.31, 128.83, 127.96, 127.82, 127.70, 126.52, 119.35, 40.13, 38.76, 35.63, 30.86, 28.38, 18.98; MS(LCMS) m z (%): 312[M-H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₇H₁₉N₃0₃: 314.14992; found: 314.15092.

Example 34

7-(4-isopropylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14q):

To a solution of methyl 2-(acetoxy(4-isopropylphenyl)methyl)acrylate 6q (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 70%; mp: 178-180 °C. 1H NMR (300 MHz, CDC1₃): δ 7.99 (s, 1H), 7.19 (d, 1H, = 8.08 Hz), 7.15 (d, 1H, = 8.08 Hz), 4.07 (t, 2H, = 5.79 Hz), 3.71 (s, 2H), 3.58 (m, 2H), 2.87 (sep, 1H), 2.13 (qt, 2H), 1.23 (s, 3H), 1.22 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 161.36, 149.51, 146.86, 136.23, 132.64, 128.79, 126.52, 119.31, 113.72, 40.14, 38.76, 35.60, 33.62, 23.94, 18.97; MS(LCMS) m/z (%): 328[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₈H₂₁N₃0₃: 328.16557; found; 328.16657.

Example 35 7-(naphthalen-2-ylmethyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)- one (14r):

To a solution of methyl 2-(acetoxy(naphthalen-2-yl)methyl)acrylate 6r (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 1 10 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by Ethonal to form the final products, as eluent to obtained. Yellow solid; Yield: 65%; mp: 187-189 °C. 1H NMR (300 MHz, CDC1₃): δ 8.07 (s, 1H), 7.58 (d, 2H, = 8.24 Hz), 7.39 (d, 2H, = 8.24 Hz), 4.06 (t, 2H, = 5.95 Hz), 3.79 (s, 2H), 3.60 (m, 2H), 2.14 (qt, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 154.47, 142.81, 133.27, 129.02, 128.47, 127.88, 126.81, 126.37, 126.31, 125.85, 125.61, 125.29, 123.96, 123.32, 110.05, 38.83, 38.48, 34.38, 19.31 ; MS(LCMS): m/z (%): 336[M+H]⁺. HRMS(ESI): [M]⁺ Calcd for Ci₉Hi₇N₃0₃: 335.14965; found: 335.14950. Example 36

6-((2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin- 5(lH)-one (15a):

To a solution of methyl 2-(acetoxy(2-chloroquinolin-3-yl)methyl)acrylate 12a (0.0025 mol) was taken in round bottom flask added to 2-(nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 56 %; mp: 272-274 °C. 1H NMR (300 MHz, CDC1₃): δ 8.16 (s, 1H), 8.00 (d, 1H, = 8.39 Hz), 7.92 (s, H), 7.80 (d, 1H, = 8.39 Hz), 7.70 (t, 1H = 8.08 Hz ) 7.55 (t, 1H, = 8.08 Hz), 4.33 (t, 2H, = 9.61 Hz), 4.07 (t, 2H, = 9.61 Hz), 4.03 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 166.1, 159.09, 140.65, 136.16, 134.33, 130.95, 130.66, 129.97, 128.73, 127.52, 96.92, 52.70, 48.48, 42.22; IR (neat, cm^"1): 3398, 2920, 2358, 1734, 1716, 1602, 1388, 1338, 1199, 1029, 754; MS (LCMS) m/z (%): 356 [M-H]⁺.

Example 37

6-((2-chloro-8-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15b):

To a solution of methyl 2-(acetoxy(2-chloro-8-methylquinolin-3-yl)methyl)acrylate 12b (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 60 %; mp: 268-270 °C. 1H NMR (300 MHz, CDC1₃): δ 8.10 (s, 1H), 7.88 (s, H), 7.79 (brs, 1H), 7.63 (d, 1H, = 7.74 Hz), 7.54 (d, 1H, = 7.74 Hz), 7.42 (t, 1H, = 7.74 Hz), 4.33 (t, 2H, = 10.00 Hz), 4.06 (t, 2H, = 10.00 Hz), 4.03 (s, 2H), 2.76 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 159.9, 159.0, 157.5, 156.1, 152.4, 150.6, 147.4, 138.5, 135.2, 132.7, 130.0, 126.7, 126.2, 124.7, 43.5, 42.8, 32.1, 28.8; IR (neat, cm^"1): 3365, 2918, 2848, 2358, 2330, 1734, 1668, 1604, 1394, 1338, 1201 , 1010, 921, 761 ; HRMS (ESI): [M+H]⁺ (m/z) calcd for Ci₈Hi₅ClN₄0₃: 371.09054, found: 371.091 19.

Example 38

6-((2-chloro-8-ethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15c):

To a solution of methyl 2-(acetoxy(2-chloro-8-ethylquinolin-3-yl)methyl)acrylate 12c (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65 %, mp: 210-212 °C. 1H NMR (300 MHz, CDC1₃): δ 8.10 (s, 1H), 7.89 (s, H), 7.81(brs, 1H), 7.63 (d, 1H, = 7.74 Hz), 7.54 (d, 1H, = 7.74 Hz), 7.46 (t, 1H, = 7.74 Hz), 4.32 (t, 2H, = 9.63 Hz), 4.06 (t, 2H, = 9.63 Hz), 4.02 (s, 2H), 3.24 (q, 2H, = 7.55 Hz), 1.36 (t, 3H, 7 = 7.55 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 160.50, 155.56, 151.39, 150.05, 145.38, 142.12, 139.44, 133.30, 129.89, 128.34, 126.92, 126.89, 125.09, 1 18.21, 44.44, 43.16, 33.02, 24.17, 14.83; IR (neat, cm^"1): 3383, 2970, 2358, 2341 , 1747, 1616, 1602, 1388, 1338, 1288, 1197, 1029, 927, 761 ; HRMS (ESI): [M+H]⁺ (m/z) Calcd for Ci₉Hi₇ClN₄0₃: 385.10726; found: 385.10619.

Example 39

6-((2-chloro-7-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15d).

To a solution of methyl 2-(acetoxy(2-chloro-7-methylquinolin-3-yl)methyl)acrylate 12d (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 61 %; mp: 268-270 °C. 1H NMR (300 MHz, CDC1₃): δ 8.10 (s, 1H), 7.89 (s, 1H), 7.77 (s, H), 7.80 (brs, 1H), 7.68 (d, 1H, = 8.39 Hz) 7.37 (d, 1H, = 8.39 Hz), 7.70 (t, 1H = 8.08 Hz ), 7.55 (t, 1H, = 8.08 Hz), 4.32 (t, 2H, = 9.61 Hz), 4.06 (t, 2H, = 9.61 Hz), 4.00 (s, 2H), 2.54 (s, 3H); ¹³C NMR (300 MHz, CDC1₃) δ: IR (neat, cm^"1): 3398, 2920, 2358, 2330, 1734, 1716, 1602, 1388, 1338, 1199, 1029, 754. HRMS (ESI): [M+H]⁺ (m/z) calcd for Ci₈Hi₅ClN₄0₃: 393.06305, found: 393.06220.

Example 40

6-((2-chloro-6-methylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15e):

To a solution of methyl 2-(acetoxy(2-chloro-6-methylquinolin-3-yl)methyl)acrylate 12e (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 61 %; mp: 228-230 °C. 1H NMR (300 MHz, CDC1₃): δ 8.10 (s, 1H), 7.87 (s, H), 7.81(br, 1H), 7.63 (d, 1H, = 7.93 Hz), 7.54 (d, 1H, = 7.93 Hz),7.43 (s, 1H), 4.33 (t, 2H, = 10.00 Hz), 4.06 (t, 2H, = 10.00 Hz), 4.03 (s, 2H), 2.75 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 160.49, 157.41 , 151.32, 146.02, 139.42, 137.86, 136.34, 133.21, 130.09, 129.95, 126.78, 125.17, 118.18, 98.23, 44.42, 43.15, 33.00, 29.67; IR (neat, cm^"1): 3365, 2970, 2358, 2330, 1734, 1716, 1541, 1338, 1203, 1083, 1012, 763; HRMS (ESI): [M-H]⁺ (m/z) Calcd for Ci₈H₁₅ClN₄0₃: 369.07489, found: 369.07573.

Example 41

6-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ] pyridin-5(lH)-one (15f):

To a solution of methyl 2-(acetoxy(2-chloro-7,8-dimethylquinolin-3- yl)methyl)acrylate 12f (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65 %; mp: 208-210 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.04 (s, 1H), 7.84 (s, H), 7.79(br, 1H), 7.53 (d, 1H, = 8.39 Hz), 7.35 (d, 1H, = 8.24 Hz), 4.31 (t, 2H, = 9.76 Hz), 4.05 (t, 2H, = 9.76 Hz), 4.00 (s, 2H), 2.69 (s, 3H), 2.48 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 160.52, 151.37, 150.04, 146.02, 139.32, 137.94, 133.65, 133.10, 129.87, 128.71 , 125.77, 124.12, 118.48, 112.93, 44.45, 43.15, 32.87, 20.66, 13.32; IR (neat, cm^"1): 3365, 2970, 2358, 2330, 1734, 1616, 1600, 1338, 1199, 1033, 927, 761 ; HRMS (ESI): m z Calcd for Ci₉H₁₇ClN₄0₃: [M-H]⁺ 383.09054; found:383.09165. Example 42

6-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15g):

To a solution of methyl 2-(acetoxy(2-chloro-6,8-dimethylquinolin-3- yl)methyl)acrylate 12g (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 66 %; mp: 223-225 °C. ^XH NMR (300 MHz, CDC1₃) δ: 8.00 (s, 1H), 7.83 (s, H), 7.81(brs, 1H), 7.38 (s, 1H), 7.37 (s, 1H), 4.31 (t, 2H, = 9.63 Hz), 4.04 (t, 2H, = 9.63 Hz), 4.00 (s, 2H), 2.71 (s, 3H), 2.46 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 160.49, 151.34, 149.21 , 144.64, 138.79, 136.64, 135.86, 133.1 1, 132.41 , 129.80, 127.51, 124.03, 118.36, 1 12.91, 44.43, 43.15, 32.97, 21.53, 17.66; IR (neat, cm^"1): 3365, 2970, 2358, 2330, 1734, 1616, 1600, 1338, 1199, 1033, 927, 761 ; HRMS(ESI): (m/z) calcd for Ci₉Hi₇ClN₄0₃ : [M-H]⁺ 383.09054; found: 383.09157.

Example 43

6-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2 a]pyridin-5(lH)-one (15h):

To a solution of methyl 2-(acetoxy(2-chloro-5,8-dimethylquinolin-3- yl)methyl)acrylate 12h (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 66 %; mp: 218-220 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.30 (s, 1H), 7.81 (s, H), 7.80 (brs, 1H), 7.42 (d, 1H, = 7.17 Hz), 7.25 (d, 1H, = 7.17 Hz), 4.32 (t, 2H, = 9.06 Hz), 4.06 (t, 2H, = 9.06 Hz), 4.04 (s, 2H), 2.70 (s, 3H), 2.63 (s, 3H); ^liC NMR (300 MHz, CDC1₃): δ 160.49, 151.31, 149.73, 146.39, 136.49, 134.16, 132.89, 131.93, 129.83, 129.19, 127.26, 126.82, 118.52, 1 12.89, 44.42, 43.13, 33.27, 18.61, 17.74; IR (neat, cm^"1): 3336, 2924, 2358, 2328, 1647, 1614, 1595, 1386, 1328, 1201 , 1087, 759; HRMS (ESI): [M+Na]⁺ calcd for Ci₉Hi₇ClN₄0₃Na= 407.08855; found= 407.08814.

Example 44

6-((2-chloro-6-isopropylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15i):

To a solution of methyl 2-(acetoxy(2-chloro-6-isopropylquinolin-3-yl)methyl)acrylate 12i (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 70 %; mp: 268-270 °C. 1H NMR (300 MHz, CDC1₃): δ 8.10 (s, 1H), 7.90 (s, H), 7.79(br, 1H), 7.92 (d, 1H, = 8.39 Hz), 7.60 (d, 1H, = 8.24 Hz), 7.59 (s, H), 4.32 (t, 2H, = 9.76 Hz), 4.06 (t, 2H, = 9.76 Hz), 4.01 (s, 2H), 3.07 (sep, 1H), 1.34 (s, 3H), 1.32 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 160.51 , 151.33, 150.25, 147.74, 145.56, 138.89, 133.33, 130.07, 130.04, 127.88, 127.39, 123.38, 117.93, 1 12.86, 44.40, 43.16, 34.03, 29.64, 23.73; IR (neat, cm^"1): 3392, 2956, 2920, 2358, 2343, 1716, 1658, 1602, 1506, 1328, 1197, 1029, 1006, 761 ; HRMS(ESI): (m/z) calcd for C₂₀Hi₉ClN₄O₃ : [M-H]⁺ 397.10619; found: 397.10731.

Example 45

6-((6-butyl-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15j):

To a solution of methyl 2-(acetoxy(6-butyl-2-chloroquinolin-3-yl)methyl)acrylate 12j ( (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 75 %; mp: 229-231 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.07 (s, 1H), 7.91 (d, 1H, = 7.55 Hz), 7.89 (s, H), 7.82(br, 1H), 7.55 (s, H), 7.54 (d, 1H, = 7.55 Hz), 4.33 (t, 2H, = 9.06 Hz), 4.06 (t, 2H, = 9.06 Hz), 4.01 (s, 2H), 2.77 (t, 2H), 1.68 (qt, 2H), 1.38 (sex, 2H), 0.95 (t, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 160.50, 151.41, 150.25, 145.51, 141.96, 138.75, 133.34, 131.68, 130.07, 127.86, 127.41, 125.56, 118.15, 1 12.95, 44.46, 43.17, 35.56, 33.26, 33.10, 22.29, 13.92; IR (neat, cm^"1): 3402, 2927, 2858, 2358, 2330, 1734, 1668, 1602, 1394, 1338, 1197, 1029, 761 ; MS(LCMS) m/z (%): 411 [M-H]⁺. HRMS(ESI): [M-H]⁺ Calcd for Ci₉H₁₇ClN₄0₃: 41 1.12309; found: 411.12184.

Example 46

6-((2-chlorobenzo[h]quinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15k):

To a solution of methyl 2-(acetoxy(2-chlorobenzo[h]quinolin-3-yl)methyl)acrylate 12k (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65 %; mp: 218-220 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.19 (s, 1H), 7.95 (s, H), 7.89 (d, 1H, = 8.00 Hz), 7.81 (d, 1H, = 8.85 Hz), 7.73 (d, 1H = 8.00 Hz), 7.70 (dd, 1H = 7.62 Hz), 7.66 (d, 1H = 8.85 Hz), 4.33 (t, 2H, = 9.15 Hz), 4.06 (t, 2H, = 9.15 Hz), 4.03 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 159.31 , 149.96, 148.65, 143.33, 137.70, 132.25, 132.19, 132.12, 130.30, 128.75, 127.26, 126.55, 125.85, 124.19, 123.31, 122.84, 115.24, 1 11.29, 42.88, 42.14, 31.56; IR(neat, cm^"1): 3292, 2970, 2926, 2358, 2328, 1734, 1593, 1396, 1328, 1199, 1053, 817, 754; HRMS(ESI): [M-H]⁺ Calcd for C₂iHi₅ClN40₃: 405.07489; found: 405.07590.

Example 47

6-((2-chloro-6-methoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (151):

To a solution of methyl 2-(acetoxy(2-chloro-6-methoxyquinolin-3-yl)methyl)acrylate 121 (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 75 %; mp: 263-265 °C. 1H NMR (300 MHz, CDC1₃): δ 8.06 (s, 1H), 7.92 (s, H), 7.89 (d, 1H, = 9.03 Hz), 7.80 (brs, 1H), 7.34 (d, 1H, = 9.30 Hz),7.06 (s, 1H), 4.32 (t, 2H, = 9.76 Hz), 4.06 (t, 2H, = 9.76 Hz), 4.0 (s, 2H), 3.91 (s, 3H); ¹³C NMR(300 MHz, CDC1₃): δ 158.55, 156.08, 149.42, 146.28, 140.26, 135.70, 131.49, 129.44, 127.15, 126.67, 120.74, 1 14.38, 110.51, 103.45, 53.76, 42.31, 41.62, 30.75; IR(neat, cm^"1): 3419, 2918, 2848, 2358, 2341, 1734, 1660, 1600, 1392, 1338, 1 197, 1037, 831, 763; MS(LCMS) m/z (%): 385[M-H]⁺. HRMS(ESI): [M-H]⁺ Calcd for C₁₈H₁₅CIN₄O₄: 387.08553; found: 387.08546.

Example 48

6-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15m):

To a solution of methyl 2-(acetoxy(2-chloro-6,7-dimethoxyquinolin-3- yl)methyl)acrylate 12m (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 77 %; mp: 244-246 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.01 (s, 1H), 7.89 (s, H), 7.82(br, 1H), 7.32 (s, 1H), 7.02 (s, 1H), 7.43 (s, 1H), 4.32 (t, 2H, = 9.76 Hz), 4.05 (t, 2H, = 9.76 Hz), 4.00 (s, 2H), 3.99 (s, 3H), 3.97 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.10, 152.52, 151.01, 149.71, 142.82, 136.83, 132.66, 128.32, 122.65, 116.26, 106.30, 105.1 1, 95.58, 55.66, 55.58, 43.88, 43.21 , 31.93; IR (neat, cm^"1): 2970, 2358, 2341 , 1716, 1651, 1606, 1506, 1327, 1234, 1217, 1143, 1035, 1006, 848, 759; HRMS(ESI): [M+H]⁺ (m/z) calcd for Ci₉Hi₇ClN₄0₅: 417.09602; found: 417.09533.

Example 49

6-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-8-nitro-2,3- dihydroimidazo[l,2-a]pyridin-5(lH)-one (15n):

To a solution of methyl 2-(acetoxy(2-chloro-6,7-dimethoxy-8-nitroquinolin-3- yl)methyl)acrylate 12m (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 75 %; mp: 238-240 °C. 1H NMR (300 MHz, CDC1₃): δ 7.93 (s, 1H), 7.81 (s, H), 7.51 (s, 1H), 4.32 (t, 2H, = 9.76 Hz), 4.08 (t, 2H, = 9.76 Hz), 4.06 (s, 3H), 4.04 (s, 2H) 3.98 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 160.31, 154.90, 151.97, 151.49, 143.36, 142.92, 139.99, 133.42, 132.64, 130.79, 117.26, 1 14.87, 1 12.87, 1 10.55, 62.60, 56.59, 44.46, 43.20, 33.16; IR (neat, cm^"1): 2970, 2358, 2341 , 1716, 1651, 1606, 1506, 1327, 1234, 1217, 1143, 1035, 1006, 848, 759; HRMS(ESI): [M+Na]⁺ (m/z) calcd for CigHieClNsOyNa: 484.06305; found: 484.06220.

Example 50

6-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15o): To a solution of methyl 2-(acetoxy(2-chloro-6,7-dimethoxyquinolin-3- yl)methyl)acrylate 12n (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 75 %; mp: 268-270 °C. 1H NMR (300 MHz, CDC1₃) : δ 8.48 (s, 1H), 7.79 (brs, 1H), 7.75 (s, H), 6.92 (d, 1H, = 8.54 Hz), 6.76 (d, 1H, = 8.54 Hz),7.43 (s, 1H), 4.33 (t, 2H, = 9.76 Hz), 4.05 (t, 2H, = 9.76 Hz), 4.03 (s, 2H), 4.01 (s, 3H), 3.95 (s, 3H). ¹³C NMR (300 MHz, CDC1₃): δ 158.29, 149.15, 148.20, 146.18, 133.61, 131.84, 130.79, 128.65, 1 18.19, 114.35, 11 1.58, 1 10.10, 107.06, 103.25, 54.26, 53.98, 42.13, 41.46, 30.62; IR (neat, cm^"1): 2998, 2885, 2358, 2330, 1716, 1647, 1506, 1334, 1323, 1203, 11 14, 1035, 931, 761 ; HRMS(ESI): [M+Na]⁺ (m/z) calcd for Ci₉Hi₇ClN₄0₅: 439.07788; found: 439.07797.

Example 51

6-((6-chloro-[l,3]dioxolo[4,5]quinolin-7-yl)methyl)-8-nitro-2,3- dihydroimidazo[l,2-a]pyridin-5(lH)-one (15p):

To a solution of methyl 2-(acetoxy(6-chloro-[ l,3]dioxolo[4,5-g]quinolin-7- yl)methyl)acrylate 12p (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 70 %; mp: 220-222 °C. ^XH NMR (300 MHz, CDC1₃): δ 7.96 (s, 1H), 7.88 (s, H), 7.82(br, 1H), 7.28 (s, 1H), 7.02 (s, 1H), 6.10 (s, 2H), 4.33 (t, 2H, = 9.76 Hz), 4.06 (t, 2H, = 9.76 Hz), 3.95 (s, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 152.37, 148.24, 146.49, 137.84, 134.85, 133.26, 122.48, 122.33, 110.11 , 108.55, 105.24, 104.90, 102.22, 101.90, 101.64, 44.44, 43.16, 29.67; IR (neat, cm^"1): 3749, 2970, 2358, 2330, 1716, 1647, 1541, 1506, 1338, 1217, 1033, 933, 848, 759; HRMS (ESI): [M+H]⁺ (m/z) calcd for C18H13CIN4O5: 401.06472; found: 401.06396.

Example 52

6-((2-chloro-7-fluoroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15q):

To a solution of methyl 2-(acetoxy(2-chloro-6-fluoroquinolin-3-yl)methyl)acrylate 12p (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65 %; mp: 266-268 °C. 1H NMR (300 MHz, CDC1₃): δ 8.17 (s, 1H), 7.95 (s, H), 7.81 (d, 1H, = 8.68 Hz), 7.77(br, 1H), 7.63 (d, 1H, = 8.68 Hz), 7.33 (s, 1H), 4.32 (t, 2H, = 9.23 Hz), 4.06 (t, 2H, = 9.23 Hz), 4.01 (s, 2H); HRMS(ESI): [M+H]⁺ (m/z) calcd for CI₇HI₂C1FN₄0₃: 375.06488; found: 375.06488.

Example 53

6-((6-bromo-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- a]pyridin-5(lH)-one (15r):

To a solution of methyl 2-(acetoxy(6-bromo-2-chloroquinolin-3-yl)methyl)acrylate 12r (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)imidazolidine 2a (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 68 %; mp: 270-272 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 7.97 (s, 1H), 7.96 (s, 1H), 7.86 (d, 1H, = 9.00 Hz), 7.81 (brs, 1H), 7.76 (d, 1H, = 9.00 Hz), 4.32 (t, 2H, = 9.76 Hz), 4.07 (t, 2H, = 9.76 Hz), 4.02 (s, 2H), 3.99 (s, 3H), 3.97 (s, 2H); IR (neat, cm^"1): 2970, 2358, 2341, 1716, 1651, 1606, 1506, 1327, 1234, 1217, 1143, 1035, 1006, 848, 759; MS(LCMS) m/z (%): 433[M-H]⁺. HRMS(ESI): [M+H]⁺ (m/z) calcd for Ci₇H₁₂ClBrN₄0₃: 435.08912; found: 435.08941.

Example 54

7-((2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin- 6(2H)-one(16a):

To a solution of methyl 2-(acetoxy(2-chloroquinolin-3-yl)methyl)acrylate 12a (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1 ,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 57%; mp: 268-270 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 7.77 (s, 1H), 7.68 - 7.37 (m, 4H), 4.08 (t, 2H, = 6.04 Hz), 4.00 (s, 2H), 3.60 (t, 2H, = 6.30 Hz ), 2.55 (s, 3H), 2.15 (m, 2H); MS(LCMS) m/z (%): 371 [M+H]⁺. HRMS(ESI): [M-H]⁺ Calcd for Ci₈Hi₅ClN₄0₃: 371.09054; found: 371.09158.

Example 55

7-((2-chloro-8-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16b):

To a solution of methyl 2-(acetoxy(2-chloro-8-methylquinolin-3-yl)methyl)acrylate 12b (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1 ,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 61 %; mp: 258-260 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 7.77 (t, 1H, = 8.30 Hz), 7.68 (d, 1H, = 8.30 Hz), 7.37 (d, 1H, = 8.30 Hz), 4.08 (t, 2H, = 6.04 Hz), 4.00 (s, 2H), 3.60 (t, 2H, = 6.30 Hz ), 2.55 (s, 3H), 2.15 (m, 2H); MS(LCMS) m/z (%): 383[M-H]⁺.

Example 56

7-((2-chloro-8-ethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16c):

To a solution of methyl 2-(acetoxy(2-chloro-8-ethylquinolin-3-yl)methyl)acrylate 12c (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid: Yield: 66%; mp: 246-248 °C. 1H NMR (300 MHz, CDC1₃): δ 8.09 (s, 1H), 8.09 (s, 1H), 7.62 (d, 1H, = 7.01 Hz), 7.54 (d, 1H, = 7.93 Hz), 7.46 (t, 2H, = 7.93 Hz), 4.08 (t, 2H, = 5.95 Hz), 4.01 (s, 2H), 3.60 (m, 2H), 3.24 (q, 3H, = 7.62 Hz), 2.15 (t, 2H, = 5.95 Hz), 1.36 (s, 3H, t, 2H, = 7.62 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 161.20, 150.13, 149.58, 145.35, 142.10, 139.35, 133.82, 129.94, 128.27, 127.48, 126.86, 125.08, 115.82, 113.82, 40.22, 38.80, 25.33, 24.16, 18.96, 14.82; MS(LCMS) m/z (%): 397[M- H]⁺. HRMS(ESI): [M-H]⁺ Calcd for C₂oH₁₉ClN₄0₃: 399.12184; found: 399.12240. Example 57

7-((2-chloro-7-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16d):

To a solution of methyl 2-(acetoxy(2-chloro-7-methylquinolin-3-yl)methyl)acrylate 12d (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 61%; mp: 258-260 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 8.08 (s, 1H), 7.77 (s, 1H), 7.68 (d, 1H, = 8.30 Hz), 7.37 (d, 1H, = 8.30 Hz), 4.08 (t, 2H, = 6.04 Hz), 4.00 (s, 2H), 3.60 (t, 2H, = 6.30 Hz ), 2.55 (s, 3H), 2.15 (m, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.20, 158.87, 155.38, 151.19, 149.57, 140.48, 138.84, 133.86, 129.34, 129.22, 127.16, 126.87, 126.41, 125.41, 40.23, 38.81, 33.65, 18.96; MS(LCMS) m/z (%): 383[M-H]⁺. HRMS(ESI): [M-H]⁺ Calcd for Ci₉H₁₇ClN₄0₃: 385.10619; found: 385.10690.

Example 58

7-((2-chloro-6-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16e):

To a solution of methyl 2-(acetoxy(2-chloro-6-methylquinolin-3-yl)methyl)acrylate 12e (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 61%; mp: 258-260 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 8.07 (s, 1H), 7.63 (d, 1H, J = 1.11 Hz), 7.53 (d, 1H, 7 = 7.17 Hz), 7.42 (s, 1H), 4.08 (t, 2H, = 5.95 Hz), 4.02 (s, 2H), 3.61 (t, 2H, = 5.95 Hz ), 2.75 (s, 3H), 2.15 (m, 2H); MS(LCMS) m/z (%): 385[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₉Hi₇ClN₄0₃: 385.10619; found: 385.10601.

Example 59

7-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyridofl ,2-a]pyrimidin-6(2H)-one (16f) :

To a solution of methyl 2-(acetoxy(2-chloro-7,8-dimethylquinolin-3- yl)methyl)acrylate 12f (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 66%; mp: 228-230 °C. 1H NMR (300 MHz, CDC1₃): δ 8.04 (s, 1H), 8.02 (s, 1H), 7.53 (d, 1H, = 8.24 Hz), 7.35 (d, 1H, = 8.24 Hz), 4.08 (t, 2H, = 5.79 Hz), 4.00 (s, 2H), 3.60 (m, 2H), 2.69 (s, 3H), 2.48 (s, 3H), 2.15 (m, 2H); ¹³C NMR (300 MHz, CDC1₃): δ 161.20, 150.12, 149.55, 145.99, 139.24, 137.84, 133.64, 129.81, 128.76, 125.76, 124.10, 116.04, 113.83, 40.21, 38.80, 33.49, 20.64, 18.97, 13.30; IR (neat, cm^"1): 3734, 2953, 2358, 2330, 1716, 1541, 1506, 1338, 1213, 1031, 933, 756; MS(LCMS) m z (%): 399[M+H]⁺. HRMS(ESI): [M-H]⁺ Calcd for C₂oHi₉ClN₄0₃: 397.10812; found: 397.10619.

Example 60

7-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a]pyrimidin-6(2H)-one (16g):

To a solution of methyl 2-(acetoxy(2-chloro-6,8-dimethylquinolin-3- yl)methyl)acrylate 12g (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 66%; mp: 212-214 °C. 1H NMR (300 MHz, CDC1₃): δ 8.04 (s, 1H), 7.99 (s, 1H), 7.38 (s, 1H), 7.37 (s, 1H), 4.07 (t, 2H, = 5.95 Hz), 3.99 (s, 2H), 3.60 (m, 2H), 2.71 (s, 3H), 2.46 (s, 3H), 2.15 (t, 2H, = 5.95 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 160.50, 148.99, 148.52, 143.68, 137.90, 135.95, 134.79, 132.91, 131.73, 129.70, 126.85, 123.55, 114.54, 112.98, 38.59, 38.32, 32.79, 20.87, 18.17, 16.97; MS(LCMS) m/z (%): 399[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₂₀H₁₉ClN₄O₃: 399.12184; found: 399.12259. Example 61

7-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyridofl ,2-a]pyrimidin-6(2H)-one (16h) :

To a solution of methyl 2-(acetoxy(2-chloro-5,8-dimethylquinolin-3- yl)methyl)acrylate 12h (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 66%; mp: 212-214 °C. 1H NMR (300 MHz, CDC1₃): δ 8.28 (s, 1H), 8.01 (s, 1H), 7.41 (d, 1H, / = 7.17 Hz), 7.25 (d, 1H, = 7.17 Hz), 4.08 (t, 2H, = 5.95 Hz), 4.04 (s, H), 3.60 (m, 2H), 2.71 (s, 3H), 2.63 (s, 3H), 2.15 (t, 2H, = 5.95 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 161.19, 150.33, 149.58, 145.47, 141.89, 138.64, 133.88, 131.59, 130.16, 127.84, 127.40, 125.53, 115.70, 113.82, 40.22, 38.81, 35.54, 22.28, 18.97, 13.90; IR (neat, cm^"1): 3734, 2953, 2358, 2330, 1716, 1541, 1506, 1338, 1213, 1031, 933, 756; MS(LCMS) m/z (%): 399[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₂oHi₉ClN₄0₃: 399.12184; found: 399.12131.

Example 62

7-((2-chloro-6-isopropylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16i):

To a solution of methyl 2-(acetoxy(2-chloro-6-isopropylquinolin-3-yl)methyl)acrylate 12i (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained . Yellow solid; Yield: 71%; mp: 200-202 °C. 1H NMR (300 MHz, CDC1₃): δ 7.98 (s, 1H), 7.20 (d, 1H, = 6.79 Hz), 7.18 (s, 1H), 7.16 (s, 1H), 7.15 (d, 1H, = 6.79 Hz), 4.07 (t, 2H, = 5.95 Hz), 3.71 (s, 2H), 3.58 (m, 2H), 2.87 (sep, 1H), 2.15 (t, 2H, = 5.95 Hz), 1.24 (s, 3H), 1.22 (s, 3H); ¹³C NMR (300 MHz, CDC1₃): δ 161.36, 149.51, 146.86, 136.23, 132.65, 128.80, 126.53, 119.31, 113.72, 40.14, 38.76, 35.60, 33.63, 23.94, 23.70, 18.97; MS(LCMS) m z (%): 451 [M+K]⁺.

Example 63

7-((6-butyl-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16j):

To a solution of methyl 2-(acetoxy(6-butyl-2-chloroquinolin-3-yl)methyl)acrylate 12j (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 77%; mp: 208-210 °C. 1H NMR (300 MHz, CDC1₃): δ 8.08 (s, 1H), 8.05 (s, 1H), 7.90(d, 1H, = 8.39 Hz), 7.55 (s, 1H), 7.54 (d, 1H, = 8.39 Hz), 4.08 (t, 2H, = 5.95 Hz), 4.00 (s, 2H), 3.60 (m, 2H), 2.77 (t, 2H, = 7.78 Hz), 2.15 (t, 2H, = 5.95 Hz), 1.68 (pt, 2H, = 7.62 Hz), 1.38 (q, 2H, = 7.47 Hz), 0.94 (s, 3H, = 7.32 Hz); ¹³C NMR (300 MHz, CDC1₃) δ: 161.12, 149.77, 149.45, 146.32, 136.42, 134.09, 133.32, 131.88, 129.73, 129.20, 127.18, 126.78, 116.10, 113.74, 40.17, 38.75, 33.82, 30.87, 29.62, 18.89, 18.58, 17.71; IR(neat, cm^"1): 3734, 2947, 2358, 2341, 1716, 1541, 1506, 1336, 1213, 1157, 1091, 997, 758; MS(ESI) m/z (%): 425[M-H]⁺.

Example 64

7-((2-chlorobenzo[h]quinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16k):

To a solution of methyl 2-(acetoxy(2-chlorobenzo[h]quinolin-3-yl)methyl)acrylate 12k (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65%; mp: 240-242 °C. 1H NMR (300 MHz, CDC1₃): δ 8.17 (s, 1H), 7.14 (s, 1H), 7.89(d, 1H, = 7.32 Hz), 7.81(d, 1H, = 8.85 Hz), 7.73(d, 1H, = 7.32 Hz), 7.71(d, 1H, = 7.17 Hz), 7.70(d, 1H, = 7.17 Hz), 7.66(d, 1H, = 8.85 Hz), 4.07 (t, 2H, = 5.95 Hz), 4.06 (s, 2H), 3.60 (m, 2H), 2.15 (t, 2H, = 5.95 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 149.62, 139.14, 133.96, 130.94, 128.47, 128.17, 127.74, 127.24, 125.53, 124.57, 124.48, 115.69, 38.83, 33.77, 29.70, 18.96; IR(neat, cm^"1): 3734, 2945, 2358, 2341, 1716, 1595, 1541, 1375, 1328, 1207, 1192, 114, 1097, 810, 758; MS(LCMS) m/z (%): 421 [M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₂₂H₁₇C1N₄0₃: 421.10619; found: 421.10751.

Example 65

7-((2-chloro-6-methoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (161):

To a solution of methyl 2-(acetoxy(2-chloro-6-methoxyquinolin-3-yl)methyl)acrylate 121 (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1 ,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 76%; mp: 228-230 °C. 1H NMR (300 MHz, CDC1₃): δ 8.1 1 (s, 1H), 8.04 (s, 1H), 7.88 (d, 1H, = 9.30 Hz), 7.34(d, 1H, = 9.30 Hz), 7.06 (s, 1H), 4.08 (t, 2H, = 5.95 Hz), 4.00 (s, 2H), 3.92 (s, 3H), 3.60 (m, 2H), 2.77 (t, 2H, = 7.78 Hz), 2.16 (t, 2H, = 5.95 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 166.66, 161.23, 158.24, 158.10, 149.05, 147.95, 143.30, 138.02, 134.00, 132.04, 129.56, 122.68, 119.70, 104.83, 55.55, 40.25, 38.82, 33.73, 29.67; IR(neat, cm^"1): 3734, 2947, 2358, 2341, 1716, 1541 , 1506, 1336, 1213, 1157, 1091, 997, 758; MS(LCMS) m/z (%): 401[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for Ci₉Hi₇ClN₄0₄: 401.10111; found: 401.10219.

Example 66

7-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a]pyrimidin-6(2H)-one (16m):

To a solution of methyl 2-(acetoxy(2-chloro-6,7-dimethoxyquinolin-3- yl)methyl)acrylate 12m (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 77%; mp: 206-208 °C. 1H NMR (300 MHz, CDC1₃): δ 8.47 (s, 1H), 7.94 (s, 1H), 6.93(d, 1H, = 8.54 Hz), 6.75 (d, 1H, = 8.54 Hz), 4.08 (t, 2H, = 5.95 Hz), 4.02 (s, 2H), 4.00 (s, 3H), 3.94 (s, 3H), 3.60 (m, 2H), 2.15 (t, 2H, = 5.95 Hz); MS(LCMS) m/z (%): 431[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₂oHi₉ClN₄0₅: 431.11167; found: 431.11306.

Example 67

7-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a]pyrimidin-6(2H)-one (16o):

To a solution of methyl 2-(acetoxy(2-chloro-6,7-dimethoxy-8-nitroquinolin-3- yl)methyl)acrylate 12m (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 72%; mp: 210-212 °C. 1H NMR (300 MHz, CDC1₃): δ 8.02 (s, 1H), 7.916 (s, 1H), 7.5 l(s, 1H), 4.08 (t, 2H, = 5.95 Hz), 4.06 (s, 3H), 3.03 (s, 3H), 3.98 (s, 2H), 3.60 (m, 2H), 2.15 (t, 2H, = 5.95 Hz); ^UC NMR (300 MHz, CDC1₃): δ 161.28, 152.81, 150.00, 149.53, 148.83, 143.73, 137.58, 133.80, 128.09, 122.93, 115.90, 113.82, 106.93, 104.68, 56.16, 56.04, 40.22, 38.81, 33.57, 18.95; MS(LCMS) m/z (%): 476[M+H]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₂oH₁₈ClN₅0₇: 476.09675; found: 476.09871.

Example 68

7-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyridofl ,2-a]pyrimidin-6(2H)-one (16n) :

To a solution of methyl 2-(acetoxy(2-chloro-5,8-dimethoxyquinolin-3- yl)methyl)acrylate 12m (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 77%; mp: 206-208 °C. 1H NMR (300 MHz, CDC1₃): δ 8.09 (s, 1H), 7.99 (s, 1H), 7.32(S, 1H), 7.02 (s, 1H), 4.08 (t, 2H, = 5.95 Hz), 4.00 (s, 3H), 3.99 (s, 3H), 3.97 (s, 2H), 4.00 (s, 3H), 3.94 (s, 3H), 3.60 (m, 2H), 2.15 (t, 2H, = 5.95 Hz); ¹³C NMR (300 MHz, CDC1₃): δ 161.28, 152.81, 150.00, 149.53, 148.83, 143.73, 137.58, 133.80, 128.09, 122.93, 115.90, 113.82, 106.93, 104.68, 56.16, 56.04, 40.22, 38.81, 33.57, 18.95; MS(LCMS) m/z (%): 431 [M+H]⁺.

Example 69

7-((6-chloro-[l,3]dioxolo[4,5-g]quinolin-7-yl)methyl)-9-nitro-3,4-dihydro-lH- pyridofl ,2-a]pyrimidin-6(2H)-one (16p) :

To a solution of methyl 2-(acetoxy(6-chloro-[l,3]dioxolo[4,5-g]quinolin-7- yl)methyl)acrylate 12p (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 2-3 h at 110 ^UC and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 71%; mp: 212-214 °C. ^XH NMR (300 MHz, CDC1₃): δ 8.07 (s, 1H), 7.94 (s, 1H), 7.28(s, 1H), 7.02 (s, 1H), 6.10 (s, 3H), 4.07 (t, 2H, = 5.95 Hz), 3.94 (s, 2H), 3.60 (m, 2H), 2.15 (t, 2H, / = 5.95 Hz); IR(neat, cm^"1): 3734, 2945, 2358, 1716, 1595, 1541, 1375, 1328, 1207, 1192, 1097, 810, 758; MS(LCMS) m/z (%): 437[M+Na]⁺. HRMS(ESI): [M+H]⁺ Calcd for C₁₉H₁₅CIN₄O₅: 415.07951 ; found: 415.07951.

Example 70

7-((2-chloro-7-fluoroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16q):

To a solution of methyl 2-(acetoxy(2-chloro-6-fluoroquinolin-3-yl)methyl)acrylate 12p 0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1 ,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 68%; mp: 250-252 °C. 1H NMR (300 MHz, CDC1₃): δ 8.15 (s, 1H), 8.14 (s, 1H), 7.79 (d, 1H, = 9.00 Hz), 7.63(d, 1H, J = 9.91 Hz), 7.33(s, 1H), 4.08 (t, 2H, = 5.95 Hz), 4.00 (s, 2H), 3.60 (m, 3H), 2.60 (m, 2H), 2.77 (t, 2H, = 7.78 Hz), 2.16 (t, 2H, = 5.95 Hz); IR(neat, cm^"1): 3734, 2947, 2358, 2341, 1716, 1541, 1506, 1336, 1213, 1 157, 1091, 997, 758; MS(LCMS) m/z (%): 411 [M+Na]⁺.

Example 71

7-((6-bromo-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2- a]pyrimidin-6(2H)-one (16r):

To a solution of methyl 2-(acetoxy(6-bromo-2-chloroquinolin-3-yl)methyl)acrylate 12r (0.0025 mol) was taken in round bottom flask added to 2- (nitromethylene)hexahydropyrimidine 2b (0.0025 mol) in 1 ,4-dioxane solvent (20ml) and to this Et₃N (3ml) was added. The mixture was refluxed for 3 h at 110 °C and cooled to 30 °C and poured into water. The reaction mixture was filtered off, and the residue was washed with H₂0 to give a crude product that was recrystallized by ethanol to form the final products, as eluent to obtained. Yellow solid; Yield: 65%; mp: 254-256 °C. 1H NMR (300 MHz, CDC1₃): δ 8.15 (s, IH), 8.06 (s, IH), 7.96 (s, IH), 7.86 (d, IH, = 9.00 Hz), 7.75(d, IH, = 9.00 Hz), 4.07 (t, 2H, = 5.79 Hz), 4.01 (s, 2H), 3.61 (m, 2H), 2.16 (m, 2H); IR(KBr, cm^"1): 3734, 2947, 2358, 2341 , 1716, 1541 , 1506, 1336, 1213, 1 157, 1091 , 997, 758; MS(LCMS) m/z (%): 449[M+H]⁺.

d

60

a 16g 16m

b 16h 16n

c 16i 16o

Example 72

ENTOMOLOGICAL EVALUTION:

Insect Antifeedant Activity:

Antifeedant activity of the compounds was assessed on tobacco caterpillar, Spodoptera litura (F). The experiments were conducted according to the classical no-choice leaf disk bioassay described earlier method [Akhtar and Isman Entomol. Exp. Appl. 2004, 111, 201-208]. To study the antifeedant activity of the test compounds, a small circular disk of 5 cm diameter was cut from fresh castor leaves. The leaf discs were treated on their upper surface with individual concentrations of the compounds, and one leaf disk each was transferred to each Petri plate of 15 cm diameter containing moist filter paper. Control leaf discs were treated with the same volume of the acetone only. In each Petri dish, prestarved healthy third instar larvae of S. litura were introduced to assess antifeedant activity. Progress of the consumption of the leaf area was measured at 6, 12 and 24 h in both treated and control leaf disks. Areas of control and treated leaf discs consumed were measured after 6 h using a leaf area meter (AM-300, ADC, Bioscientific Limited, England). The antifeedant index was then calculated as (C - T)/(C + T) x 100, where C is the consumption of control leaf discs, and T is consumption of treated leaf discs (Isman et al. J. Agric. Food Chem.1990, 38, 1406-1411). For each concentration, 10 experimental sets were assayed. All tests were replicated three times. The mean of the 10 sets was taken for each compound. Means were subjected to probit analysis [Finney D. J. In Probit Analysis; Cambridge Univer sity Press: London, 1971,68 - 72]. The antifeedant activity was given as percentage for the compounds 13a- q, 14a-r, 15a-r, and 16a-r are included in Table 1.

Tablel. Insect Antifeedant activity of the imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine compounds against Spodoptera litura.

13g 00.00 54.89

13k 52.34 82.98

131 55.74 86.38

13m 33.19 63.83

13q 16.17 46.81

14b 41.70 72.34

14e 67.63 97.47

14g 47.23 77.87

14h 41.70 72.34

14i 41.70 72.34

14k 67.53 97.61

141 54.47 85.11

14m 58.72 89.36

14o 00.00 15.74

14p 4.68 35.32

14r 36.60 67.23

14s 51.49 82.13

15a 00.00 40.43

15d 37.87 68.51

15e 00.00 52.77

15j 00.00 17.87

15m 61.28 91.91

15q 00.00 30.64

15r 40.00 97.87

16c 67.28 97.84

16d 38.30 68.94

16e 4.43 30.21

16f 0.00 37.87 32 16g 0.00 15.96

33 16h 0.00 17.02

34 16i 31.91 62.55

35 16j 0.00 43.83

36 16k 62.98 93.62

37 161 43.40 74.04

38 16m 43.83 74.47

39 16n 52.34 94.89

40 16o 41.70 72.34

41 16p 2.55 33.19

42 16r 36.17 66.81

ADVANTAGES OF THE INVENTION

• The present invention provides the synthesis of new imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine analogues useful as insect Antifeedant compound in agricultural use.

• The present invention provides a process for the preparation of a imidazo[l,2- ]pyridine and pyrido[l,2- ]pyrimidine compounds.

• It is another advantage that Baylis-Hillman adducts used as synthons for the synthesis of targeted compouns.

• It is another advantage that the synthesized compounds are heterocyclic compounds is Heterocyclic compounds.

• It is another advantage that bases utilised for the synthons are simple and base are commercially available.

• It is another advantage that the method used for the synthesis of compounds is a.

Claims

WE CLAIM

1. Novel compounds of general formula A:

Formula A

Where in R = X, Y

X= substituted phenyl,

Y= substituted 2-Chloro Quinoline,

R₆=R₇=R₈=R₉= alkyl, Ethyl, iPr, Bromo, halo,

Ri=R₂= R₃= R₄=R₅= alkyl, iPr, Bromo,

N0₂, alkoxy, Ar, Bu, -OCH₂0- halo, dihalo, CN, CF₃

2. The compounds of general formula A as claimed in claim 1, wherein the compounds are represented b the compounds of general formula 13a-q, 14a-r, 15a-r, 16a-r.

halo, dihalo, CN, CF₃ alkoxy, Ar, Bu, -OCH₂0-

3. The compounds of general formula A as claimed in claim 1, wherein the representative compounds comprise:

6-benzyl-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one (13a),

6-(2-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13b),

6-(3-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13c), 6-(4-fluorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13d),

6-(2-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13e),

6-(3-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13f),

6-(4-chlorobenzyl)-8-nitro-2,3-dihydroimidazo[ 1 ,2-a]pyridin-5( lH)-one ( 13g),

6-(2,6-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13h), 6-(3,4-dichlorobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13i), 6-(3-bromobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13j),

6-(4-bromobenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13k),

6-(2-(trifluoromethyl)benzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (131),

4-((8-nitro-5-oxo- 1 ,2,3 ,5-tetrahydroimidazo[ 1 ,2-a]pyridin-6-yl)methyl)benzonitrile ( 13m), 8-nitro-6-(3-nitrobenzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13n),

8- nitro-6-(4-nitrobenzyl)-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13o),

6-(4-isopropylbenzyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one (13p),

6- (naphthalen-2-ylmethyl)-8-nitro-2,3-dihydroimidazo[l,2-a]pyridin-5(lH)-one(13q),

7- (2-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14b) 7-(3-fluorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14c), 7-(2-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14d), 7-(3-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14e), 7-(4-chlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14f), 7-(2,6-dichlorobenzyl)-9-nitro-3,4-dihydro-lH^yrido[l,2-a]pyrimidin-6(2H)-one (14g), 7-(3,4-dichlorobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14h), 7-(3-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14i), 7-(4-bromobenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14j),

9- nitro-7-(2-(trifluoromethyl)benzyl)-3,4-dihydro- lH-pyrido[ 1 ,2-a]pyrimidin-6(2H)-one (14k),

4-((9-nitro-6-oxo-2,3,4,6-tetrahydro-lH-pyrido[l,2-a]pyrimidin-7-yl)methyl)benzonitrile (141),

9-nitro-7-(3-nitrobenzyl)-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14m), 9-nitro-7-(4-nitrobenzyl)-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14n), 7-(4-methylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14o), 7-(4-ethylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14p), 7-(4-isopropylbenzyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a]pyrimidin-6(2H)-one (14q): 7-(naphthalen-2-ylmethyl)-9-nitro-3,4-dihydro-lH^yrido[l ,2-a]pyrimidin-6(2H)-one (14r),

6-((2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin-5(lH)-one

( 15a),

6-((2-chloro-8-ethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin-5(lH)- one (15c),

6-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin- 5(lH)-one (15f),

6-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin- 5(lH)-one (15g),

6-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2 ]pyridin- 5(lH)-one (15h),

6-((2-chloro-6-isopropylquinolin-3-yl) methyl)-8-nitro-2, 3-dihydroimidazo [1 , 2-a] pyridin 5(lH)-one (15i),

6-((6-butyl-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridin-5(lH)- one (15j),

6-((2-chlorobenzo[h]quinolin-3-yl) methyl)-8-nitro-2, 3-dihydroimidazo [1, 2-a] pyridin 5(lH)-one (15k),

6-((2-chloro-6-methoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- ]pyridi 5(lH)-one (151),

6-((2-cmoro-6,7-dimethoxyquinolin-3-yl)mem^

5(lH)-one (15m),

6-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- a]pyridin-5(lH)-one (15n),

6-((2-chloro-5,8-dimethoxyquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[l,2- ]pyridin 5(lH)-one (15o), 6-((6-chloro-[l,3]dioxolo[4,5-g]quinolin-7-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2- a]pyridin-5(lH)-one (15p),

6-((2-cUoro-7-fluoroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2-a]pyridin- 5(lH)-one (15q),

6- ((6-bromo-2-chloroquinolin-3-yl)methyl)-8-nitro-2,3-dihydroimidazo[ l,2-a]pyridin- 5(lH)-one (15r),

7- ((2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[l,2-a]pyrimidin-6(2H)- one (16a),

7-((2-chloro-8-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[l,2-a]pyrimidin 6(2H)-one,(16b),

7-((2-chloro-8-ethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[ l,2-a]pyrimidin- 6(2H)-one (16c),

7-((2-chloro-7-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro- lH-pyrido[ 1 ,2-a]pyrimidin 6(2H)-one (16d),

7-((2-chloro-6-methylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro- lH-pyrido[ 1 ,2-a]pyrimidin 6(2H)-one (16e),

7-((2-chloro-7,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16f),

7-((2-chloro-6,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16g),

7-((2-chloro-5,8-dimethylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16h),

7-((2-chloro-6-isopropylquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16i),

7-((6-butyl-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[ l,2-a]pyrimidin- 6(2H)-one (16j),

7-((2-chlorobenzo[h]quinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[ l,2-a]pyrimidin- 6(2H)-one (16k),

7-((2-chloro-6-methoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro- lH-pyrido[ 1 ,2- a]pyrimidin-6(2H)-one ( 161),

7-((2-chloro-6,7-dimethoxyquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[ l,2- a]pyrimidin-6(2H)-one ( 16m), 7-((2-chloro-6,7-dimethoxy-8-nitroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH- pyrido[l,2-a] pyrimidin-6(2H)-one (16n),

7-((6-chloro-[l,3]dioxolo[4,5-g]quinolin-7-yl)methyl)-9-nitro-3,4-dihydro-lH-pyrido[l,2-a] pyrimidin-6(2H)-one (16p),

7-((2-chloro-7-fluoroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[l,2-a]pyrimidin- 6(2H)-one (16q),

7-((6-bromo-2-chloroquinolin-3-yl)methyl)-9-nitro-3,4-dihydro-lH^yrido[l,2-a]pyrimidin- 6(2H)-one (16r).

4. The compounds of general formula A as claimed in claim 1 , useful as insect Antifeedant.

5. A process for the preparation of compounds of general formula A as claimed in claim 1, wherein the said process comprising the steps of:

6. The process as claimed in claim 5, wherein the solvent is 1,4-dioxan.

7. The process as claimed in claim 5, wherein the base is triethylamine(Et₃N).

8. The process as claimed in claim 5, wherein the molar ratio of triethylamine (Et₃N) is 3 (1: 12) in respect of acetylated Baylis-Hillman adducts 6(a-r) or 12(a-r).

9. The process as claimed in claim 5, wherein the acetylated Baylis-Hillman adducts is selected from the group consisting of 6(a-r) or 12(a-r).

10. The process as claimed in claim 4, wherein the yield of the compounds of general formula A is in the range of 55-81%.