Theoretical Study of Geometry of Quinazoline Derivatives and Their Antibacterial Activities

 

Ramandeep Kaur, Monika Bansal and Balbir Kaur*

Department of Chemistry, Punjabi University, Patiala 147002, Punjab, India

*Corresponding Author E-mail: aries_balbir@yahoo.co.in

 

ABSTRACT:

Quinazolines are a pharmacologically very attractive class of compounds. In the preliminary communication, 4-substituted phenyl-3,4,5,6-tetrahydrobenzo[h]quinazoline-2(1H)-thiones and their S-alkyl/aralkyl derivatives were synthesized. Through the Gaussian 03 studies, the expected stereochemistry of the synthesized compounds was checked. Also, the compounds were tested for antibacterial activities against Staphylococcus aureus, Pseudomonas fluorescence.

 

KEYWORDS: Quinazolines, Gaussian studies, Stereochemistry, Antibacterial activities

 


 

1.  INTRODUCTION:

Fused pyrimidines1 are found in a broad variety of natural products, used in medicines, possess antimalarial activities4 and other important biological properties2,3,5,6. Recently, 1,2,3,4,5,6,7,8-octahydroquinazoline-2,5-dione derivatives have been reported to exhibit potent calcium antagonist activities7 and have also attracted considerable attention owing to their potential antibacterial activity against Staphylococcus aureus and Pseudomonas fluorescence.

 

In line with the work on quinazoline derivatives, earlier, we have reported8 the synthesis of 4-substituted phenyl-3,4,5,6-tetrahydrobenzo[h]quinazoline-2(1H)-thiones through one-pot multicomponent reactions and then these quinazolinethiones were converted to S-alkyl/aryl quinazoline derivatives. The synthesized compounds were characterized on the basis of IR, NMR and mass spectral data. The present paper describes the study of expected geometries of these fused pyrimidine derivatives on the basis of Guassian 03 series of programs. Also, the quinazoline derivatives were tested for antibacterial effects. As a result, it was established that 2-ethylthio-4-(4-

hydroxy-3-methoxyphenyl)-1,4,5,6-tetrahydrobenzo [h]quinazoline was the most effective compound, which has caused growth inhibition of Staphylococcus aureus and Pseudomonas fluorescence (Table 7).

 

2.      COMPUTATIONAL STUDIES:

The crystals suitable for X-ray analysis were not obtained. Therefore, the synthesized compounds were characterized through IR, NMR and Mass spectral values. The expected geometry, as per the literature, was obtained with computational studies by using Gaussian 03 series of programs. Bond lengths, Bond angles and dihedral angles were calculated from the geometries optimized with semiempirical methods. The X-ray study of the reference compound 1 taken, shows the boat shaped structure of pyrimidine ring and the substituted aryl ring is positioned axially, perpendicular to, and bisecting the boat like dihydropyrimidine ring, with the 4-aryl substituent (Z) adopting a synperiplanar orientation relative to C4-H (Figure 1).

 

Reference compound 1

 

Figure 1

 

It is clear from the AM1, MNDO, PM3 and PM3MM values of the prepared compounds that pyrimidine ring has taken somewhat elongated shape and 4-aryl ring is also not in the same plane as pyrimidine ring as is clear from the dihedral angle and bond angle values (Table 2, 3, 4, 5, 6) when compared with the reference compound 1 (Table 1). Therefore, it is expected that synthesized compounds (DHPMs) may exist in the expected boat confirmation as given in the literature9-13.

 

Already, studies have shown that as the solid state structure of dihydropyrimidine analogous can adopt a molecular conformation which is similar to the reported conformation of dihyhdropyridine calcium channel blockers. i. e. why dihydropyrimidines represent a heterocyclic system with remarkable pharmacological efficiency like that of dihydropyridine calcium channel blockers.

 

Table- 1-Selected Bond lengths (A0), Bond angles (0), dihedral angle(0)

Bond lenghts

 

Bond angles

 

Dihedral angles

 

N1-C8

1.364

C9-C7-C6

112

C6-C7-C9-C14

-111

N1-C5

1.382

C9-C7-C2

111

C14-C9-C7-N2

+126

N2-C8

1.326

C7-C6-C5

120.1

C6-C7-C9-C10

+65

N2-C7

1.474

N2-C8-C1

116.3

C9-C7-N2-C8

92.1

C5-C6

1.358

N2-C7-C6

108

C9-C7-C6-C5

-98

C8-S1

1.678

N1-C5-C6

119.4

N2-C7-C6-C5

24.5

 

 

C7-N2-C8

124.8

 

 

 

 

C7-C6-C1

119.1

 

 

 

 

N1-C8-S1

120.6

 

 

 

 

N2-C8-S1

123.1

 

 

 

Compound 2

 

Table- 2

Parameters

Compd.2

 

 

 

AM1

MNDO

PM3

PM3MM

Bond lenghts

 

 

 

 

C4-N22

1.3889

1.3917

1.3969

1.3969

C1-N22

1.3959

1.4057

1.4151

1.4151

C4-N21

1.39

1.3934

1.3985

1.3985

C3-N21

1.398

1.4091

1.42

1.4204

C3-C2

1.4359

1.4509

1.419

1.414

C4-S23

1.614

1.5844

1.6548

1.6548

Bond angles

 

 

 

 

C24-C1-C2

123.4746

126.345

124.533

124.533

N22-C1-C24

117.7336

115.7887

116.5597

116.5597

C1-C2-C3

119.0535

119.7613

118.9744

118.9744

N21-C4-C22

117.7718

114.8402

115.7969

115.7969

N22-C1-C2

118.7918

117.8663

118.9073

118.9073

C2-C3-N21

118.3407

116.4323

118.9632

118.9632

C1-N22-C4

122.8139

125.139

123.5417

123.5417

C1-C2-C5

122.0186

122.6018

122.3466

122.3466

N21-C4-S23

120.9942

122.4943

122.0079

122.0079

N22-C4-S23

121.2338

122.6655

122.144

122.144

Dihedral angles

 

 

 

 

C2-C1-C24-C25

-47.7894

-90.1107

-55.1944

-55.1944

N22-C1-C24-C25

132.2036

89.881

124.7289

124.7289

C2-C1-C24-C26

133.7975

90.0937

125.6941

125.6941

C24-C1-N22-C4

-175.7451

179.971

179

179.2425

C24-C1-C2-C3

175.0909

-179.9975

177.2947

177.2947

N22-C1-C2-C3

-4.9019

0.011

-2.627

-2.627

 

Compound 3

 

Table- 3

Parameters

Compd.3

 

 

 

AM1

MNDO

PM3

PM3MM

Bond lenghts

 

 

 

 

C12-N34

1.3339

1.3283

1.3369

1.3369

C11-N34

1.3838

1.376

1.3795

1.3795

C12-N35

1.4159

1.4119

1.4272

1.4272

C8-N35

1.4063

1.4195

1.4267

1.4267

C8-C9

1.4305

1.4467

1.4159

1.4159

C12-S19

1.7297

1.6856

1.7696

1.7696

C9-C11

1.411

1.444

1.4317

1.4317

C11-C23

1.4667

1.4823

1.4632

1.4632

C20-S19

1.7475

1.7292

1.8032

1.8032

Bond angles

 

 

 

 

C23-C11-C9

121.7865

125.0063

123.7229

123.7229

N34-C11-C23

117.4414

114.1965

116.4952

116.4952

C11-C9-C8

119.6381

118.6039

118.4523

118.4523

N35-C12-N34

124.7318

122.7712

120.5005

120.5005

N34-C11-C9

120.7614

120.7959

119.7545

119.7545

C9-C8-N35

118.4099

117.212

118.7794

118.7794

C11-N34-C12

118.4808

120.2026

121.6223

121.6223

C11-C9-C10

125.0995

123.5077

122.6476

122.6476

N35-C12-S19

118.3799

115.3081

116.5717

116.5717

N34-C12-S19

116.8846

121.8403

122.8582

122.8582

Dihedral angles

 

 

 

 

C9-C11-C23-C24

-52.9517

-83.9955

-51.7433

-51.7433

N34-C11-C23-C24

128.2285

96.4335

130.1701

130.1701

C9-C11-C23 -C25

128.0753

97.27

129.6316

129.6316

C23-C11-N34-C12

179.8251

-178.6317

-174.0151

-174.0151

C23-C11-C9 -C8

-177.7174

176.5349

174.3253

174.3253

N34-C11-C9 -C8

1.0637

-3.9206

-7.6472

-7.6472

C9-C11-N34 -C12

0.9926

1.7774

7.8181

7.8181

C9-C8-C35 -C12

11.478

7.9864

19.5368

19.5368

N34-C12-N35-C8

-10.0601

-10.7303

-19.968

-19.968

 

Compound 4

 

Table- 4

Parameters

Compd 4

 

 

 

AM1

MNDO

PM3

PM3MM

Bond lenghts

 

 

 

 

C12-N31

1.3386

1.3282

1.3336

1.3336

C11-N31

1.371

1.3761

1.3839

1.3839

C12-N32

1.4113

1.4124

1.4248

1.4248

C8-N32

1.4044

1.4194

1.4261

1.4261

C8-C9

1.4328

1.4467

1.4181

1.4181

C12-S19

1.7227

1.6856

1.7699

1.7699

C11-C9

1.4419

1.4439

1.434

1.434

C11-C20

1.4649

1.4823

1.4621

1.4621

Bond angles

 

 

 

 

C20-C11-C9

121.3618

125.0006

125.8445

125.8445

N31-C11-C20

117.4693

114.1868

114.8524

114.8524

C11-C9-C8

118.3832

118.5889

118.469

118.469

N32-C12-N31

124.4928

122.7162

120.4585

120.4585

N31-C11-C9

121.1659

120.8111

119.3003

119.3003

C9-C8-N32

118.8723

117.2106

119.2002

119.2002

C11-N31-C12

118.7256

120.2276

122.3254

122.3254

C11-C9-C10

122.5722

123.5194

123.3774

123.3774

N32-C12-S19

114.3444

115.0631

116.5551

116.5551

N31-C12-S19

121.1374

122.1415

122.9194

122.9194

Dihedral angles

 

 

 

 

C9-C11-C20-C21

51.8251

97.2571

41.5696

41.5696

N31-C11-C20-C21

-127.5421

-82.3055

-137.8224

-137.8224

C9-C11-C20-C22

-129.9205

-84.0077

-140.047

-140.047

C20-C11-N31-C12

177.756

-178.6343

-175.7189

-175.7189

C20-C11-C9-C8

-177.4573

176.5354

175.3482

175.3482

N31-C11-C9-C8

1.8866

-3.9292

-5.2845

-5.2845

C9-C11-N31-C12

-1.6125

1.783

4.8463

4.8463

C9-C8-N32-C12

7.4994

7.9837

17.327

17.327

N31-C12-N32-C8

-7.6557

-10.7248

-18.199

-18.199

 

Compound 5

 

Table- 5

Parameters

Compd 5

 

 

 

AM1

MNDO

PM3

PM3MM

Bond lenghts

 

 

 

 

C12-N31

1.3387

1.3281

1.3335

1.3335

C11-N31

1.371

1.3761

1.3839

1.3839

C12-N32

1.4114

1.4124

1.4248

1.4248

C8-N32

1.4044

1.4193

1.4261

1.4261

C8-C9

1.4328

1.4467

1.4181

1.4181

C12-S19

1.7228

1.6855

1.7701

1.7701

C11-C9

1.4419

1.4439

1.434

1.434

C11-C20

1.4649

1.4823

1.4621

1.4621

Bond angles

 

 

 

 

C20-C11-C9

121.1705

125.0055

125.8576

125.8576

N31-C11-C20

117.4671

114.183

114.8419

114.8419

C11-C9-C8

118.3805

118.5891

118.4682

118.4682

N32-C12-N31

124.4882

122.709

120.4596

120.4596

N31-C11-C9

121.1705

120.81

119.2979

119.2979

C9-C8-N32

118.8728

117.2084

119.208

119.208

C11-N31-C12

118.725

120.2312

122.3361

122.3361

C11-C9-C10

122.5746

123.5183

123.3802

123.3802

N32-C12-S19

114.303

115.0443

116.5177

116.5177

N31-C12-S19

121.183

122.1693

122.952

122.952

Dihedral angles

 

 

 

 

C9-C11-C20-C21

51.8464

97.2873

41.4877

41.4877

N31-C11-C20-C21

-127.5248

-82.2702

-137.9142

-137.9142

C9-C11-C20-C22

-129.8956

-83.9815

-140.1434

-140.1434

C20-C11-N31-C12

177.772

-178.6232

-175.7579

-175.7579

C20-C11-C9-C8

-177.4778

176.5275

175.3996

175.3996

N31-C11-C9-C8

1.8701

-3.9425

-5.2228

-5.2228

C9-C11-N31-C12

-1.6004

1.7989

4.7979

4.7979

C9-C8-N32-C12

7.5218

8.0012

17.2946

17.2946

N31-C12-N32-C8

-7.6837

-10.7402

-18.1498

-18.1498

 

Compound 6

 

Table- 6

Parameters

Compd 6

 

 

 

AM1

MNDO

PM3

PM3MM

Bond lenghts

 

 

 

 

C12-N33

1.3271

1.3283

1.3356

1.3356

C11-N33

1.3898

1.3758

1.3798

1.3798

C12-N34

1.4117

1.4124

1.4261

1.4261

C8-N34

1.4041

1.4187

1.4273

1.4273

C8-C9

1.4365

1.4465

1.4166

1.4166

C12-S19

1.7307

1.6857

1.7693

1.7694

C11-C9

1.4026

1.4439

1.4322

1.4322

C11-C22

1.4677

1.4827

1.4615

1.4616

S19-C20

1.774

1.7438

1.8312

1.8313

C20-C37

1.4781

1.5055

1.4875

1.4875

Bond angles

 

 

 

 

C22-C11-C9

121.8772

124.8936

124.5441

124.5391

N33-C11-C22

117.2937

114.2029

115.8928

115.8936

C11-C9-C8

119.7072

118.5809

118.393

118.3928

N34-C12-N33

124.7898

122.7019

120.2451

120.2473

N33-C11-C9

120.8149

120.9034

119.5077

119.511

C9-C8-N34

117.9195

117.2044

118.9264

118.9257

C11-N33-C12

118.3208

120.2087

121.9862

121.9841

C11-C9-C10

124.8064

123.5344

122.7599

122.759

C12-S19-C20

107.4853

111.9696

105.9124

105.9067

C20-C37-C39

120.274

120.7852

120.0362

120.0388

C20-C37-C38

120.376

121.1215

120.4442

120.4435

N34-C12-S19

113.4991

114.7716

117.1506

117.1523

N33-C12-S19

121.6496

122.3291

122.5304

122.5264

Dihedral angles

 

 

 

 

C9-C11-C22-C23

-56.0118

-92.5341

-47.7965

-47.8589

N33-C11-C22-C23

125.351

87.5703

134.9345

-134.8963

C9-C11-C22-C24

124.8916

88.6246

134.0068

-133.9467

C22-C11-N33-C12

-178.5359

-179.6689

-175.4692

-175.5173

C22-C11-C9-C8

-179.1151

177.6677

174.6098

174.6485

N33-C11-C9-C8

-0.5253

-2.4434

-8.2133

-8.1997

C9-C11-N33-C12

2.8116

0.431

7.1155

7.0905

C9-C8-N34-C12

12.1393

6.9857

19.2286

19.2287

N33-C12-N34-C8

-10.5597

-9.503

-20.8874

-20.8988

S19-C20-C37-C39

78.7907

66.7287

81.2616

81.2499

S19-C20-C37-C38

-102.2602

-114.6461

-100.2235

-100.246

 

3.      ANTIBACTERIAL STUDIES:

3. 1 Micro-organisms:

Two different bacterial strains were collected as test organisms to check the antimicrobial activity of organic compounds. The microbial cultures were procured from the IMTECH, Chandigarh.

These seven indicator test bacteria were:

 

Strain                                                  MTCC No.

1. Pseudomonas fluorescence             103

2. Staphylococcus aureus                    1740

 

The bacteria were sub cultured in nutrient agar medium and the culture of each bacterium was preserved on the same medium at 40 C. The cultures were sub cultured periodically on the same medium at 370 C ± 20C.

3. 2 Composition of nutrient agar medium (NA)

Components                        Amount

NaCl                                     8g

Peptone                               5g

Beef extract                         3g

Agar                                     15g

Distilled water                     1 lt.

pH                                        7

 

3. 3 Procedure for making medium:

NaCl (8g), Peptone (5g) and Beef extract (3g) were mixed in distilled water and made the final volume 1lt. pH was adjusted to 7. Finally, agar-agar powder (15 g) was added.

 

3. 4 Preparation of inoculums:

One loopful of 24 h old culture of bacteria was inoculated into 50 ml nutrient broth in 50ml Erlenmeyer flasks. Flasks were kept on rotary shaker (100 rpm) at 370 C±20 C for 24h.

 

3. 5 Method used for antibacterial activities

The antibacterial activity was checked using well plate assay. The details are given below:

 

Stock solutions:

The stock solutions of extracts and antibiotics were prepared. The stock solutions (2 mg/ml) were diluted in alcohol (organic extracts), distilled water (aq. Extracts) and in slightly warm water (antibiotics) to the desired concentrations i. e. 1000, 700, 500, 300, 100 and 30 µg. Six different concentrations were tested for antimicrobial activity.

 

 

Well plate assay:

Nutrient agar medium plates were prepared by pouring approximately 15 ml nutrient agar into the sterilized plates. A lawn of test bacteria was made with 5 ml of the molten agar (450 C) inoculated with 1 ml of inoculum consisting of 106 cells/ml after proper mixing on cyclomixer. After solidification, wells from agar plates were punched out with a sterile borer of 8mm diameter. Six different concentrations i. e. 1000µg, 700µg, 500µg, 300µg, 100µg and 30µg of extracts were poured into the wells with the help of micropipette under sterilized conditions. DMSO was employed as control. The plates were then incubated at 370 C±20 C. The zone of inhibition (ZI) around the wells was measured in mm after 24h incubation.

 

3. 6 Antibiotics:

Standard antibacterial antibiotics were used along with the selected best antimicrobial organic extracts. The antibacterial efficacy of the most effective extracts was compared with those of existing standard antibacterial antibiotics. viz. Tetracycline and Chloramphenicol.

 

3. 7 COMPOUNDS TO BE TESTED FOR ANTI-BACTERIAL ACTIVITY:

The following compounds were evaluated for antibacterial activity.

 

 

1

 

2

 

3

 

4

 

5

 

6

 

7

 

8

 

9

 

10

 

11

 

12

 

3. 8 OBSERVATIONS:

The following observations were made during the anti-bacterial activities of above mentioned compounds. These compounds were screened for anti-bacterial activity against Staphylococcus aureus and Pseudomonas fluorescence. The concentration of the compounds taken was 500 µg/ml for this screening (Table 7).

 

Table 7 : Antibacterial activity

Compound

Staphylococcus aureus

Pseudomonas fluorescence

1.

-----

-----

2.

-----

-----

3.

+

-----

4.

-----

-----

5.

-----

-----

6.

+

-----

7.

+

-----

8.

+

-----

9.

-----

-----

10.

-----

-----

11.

-----

-----

12.

+

+

‘+’ indicates that these compounds acted as antibacterial agents.

 

The compounds 1, 2, 4, 5, 9, 10, 11 didn’t show any antibacterial activity against both of these bacterial strains.

The compound 12 which have shown antibacterial activity against both of these bacterial strains, was tested for the Minimal Inhibitory Concentration (MIC) using different concentrations.

 

The zones of inhibition (mm) of the compound 12 are compared with those of the standard drugs Tetracycline and Chloramphenicol. For calculating the MIC value of compound 12, the whole procedure of testing antibacterial activity was repeated using different concentrations (Table 8 and 9).


Table 8: Bacterial Strain- Staphylococcus aureus

Concentrations  of Compound 12 (µg)

Zone of inhibition of compound 12 (mm)

Zones of inhibition (mm)

Tetracycline

Chloramphenicol

1000

43

-----

------

700

31

-----

------

500

23

49

40

300

13

 25. 5

18

100

3. 10

12. 6

8. 0

30

-----

5. 3

3. 0

 

Table 9: Bacterial Strain- Pseudomonas fluorescence

Concentrations

Of Compound 12 (µg)

Zone of inhibition of compound 12 (mm)

Zones of inhibition (mm)

Tetracycline

Chloramphenicol

1000

37

------

------

700

24

------

------

500

19

46

48

300

6. 0

23

23

100

1. 0

9. 1

11

30

--------

2. 1

5. 3

 

 


4.   RESULTS AND DISCUSSIONS:

1. The compounds 1, 2, 4, 5, 9, 10, 11 are inactive against both of the bacterial strains taken. viz. Staphylococcus aureus and Pseudomonas fluorescence.

 

2. The compound 12 is active towards both of the bacterial strains.

 

3. The results show that all the Quinazolinethiones screened for antibacterial activity, the thiones in which hydroxyl group has been present in the 4-phenyl ring (i. e. compound 12) show an increase in the antibacterial action as compared to compound 3, which has only 4-methoxy group in phenyl ring.

 

4. Also, S-ethyl derivative (compound 12) is most potent as S-Ethyl moiety is present on the right side of the expected boat shaped structure. This again shows that we cannot ignore the structural details of right hand side.

 

5. The result 3and4 leads to the conclusion that the S-Me or S-Et derivatives synthesized from vanillin are much more potent than other derivatives against anti-bacterial activities. Thus, the stereochemistry between the aryl group and the dihydropyrimidine ring was found to be one of the factors having a pronounced effect on biological activity. It was proposed that in receptor bound conformation of DHPMs, the substituted aryl ring is positioned axially, perpendicular to, and bisecting the boat like dihydropyridine/ dihydropyrimidine ring with the 4-arylsubstituted Z adopting a synperiplanar (relative to C4-H) orientation. Also, it was verified from the results discussed, that right hand side cannot be neglected in receptor bound theory.

 

5.      REFERENCES:

1.       Brown, D. J. : Qunazolines, Supplement I ( The Chemistry of Heterocyclic Compounds Vol. 55), John Wiley and Sons: Chichester (U. K. ), 1996.

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10.     Jauk, B., Pernat, T. and Kappe, C. O. : Molecules, 2000, 5, 227.

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12.     Fossheim, R. : J. Med. Chem., 1986, 29, 305.

13.     Rovnyak, G. C., Kimball, S. D., Beyer, B., Cucinotta G., DiMarco, J. D., Gougoutas, J., Hedberg, A., Malley, M., McCarthy, J. P., Zhang, R. And Moreland, S. : J. Med. Chem., 1995, 38, 119.

 

 

 

Received on 22.10.2010        Modified on 06.11.2010

Accepted on 28.11.2010        © AJRC All right reserved

Asian J. Research Chem. 4(4): April 2011; Page 560-566