Section-II Present Work - Information and Library Network …shodhganga.inflibnet.ac.in/bitstream/10603/3032/8/08... · · 2015-12-04Section-II Present Work ... it was thought interesting

Section-II: Experimental

Section-II: Experimental 46

Section-II

Present Work

In view of encouraging reports about technical applications of some of the

novel reactive dyes, it was thought interesting to undertake synthesis and study of the

dyeing properties of the dyes based on,

Series-1 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichlorophenyl}-6-

bromo-2-phenylquinazolin-4(3H)-one

Series-2 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-

phenylquinazolin-4(3H)-one

Series-3 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-

carboxyphenyl}-6-iodo-2-phenylquinazolin-4(3H)-one

Series-4 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluorophenyl}-6-nitro-

2-phenylquinazolin-4(3H)-one

The work is divided in four series.

In Series-1, the hot brand reactive dyes based on the following structure were

prepared.

Where R = various m-nitro anilino cyanurated coupling components.

One mole of diazotized 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-

dichlorophenyl}-6-bromo-2-phenylquinazolin-4(3H)-one was condensing with one

mole of various m-nitro anilino cyanurated coupling components to obtain different

reactive dyes.




prepared.

Where R = various p-chloro anilino cyanurated coupling components.

One mole of diazotized 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-

chloro-2-phenylquinazolin-4(3H)-one was condense with one mole of various

p-chloro anilino cyanurated coupling components to obtain different reactive dyes.


prepared.

Where R = various p-nitro anilino cyanurated coupling components.

One mole of diazotised 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-

2-carboxyphenyl}-6-iodo-2-phenylquinazolin-4(3H)-one was condensing with one

mole of various p-nitro anilino cyanurated coupling components to obtain different

reactive dyes.


prepared.



Where R = various o-chloro-p-nitro anilino cyanurated coupling components.

One mole of diazotised 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-

difluorophenyl}-6-nitro-2-phenylquinazolin-4(3H)-one was condensing with one

mole of various o-chloro-p-nitro anilino cyanurated coupling components to obtain

different reactive dyes.

The procedure followed in connection with each reactive dye is as follows:

1. The reactive dyes are prepared under proper experimental conditions and

purified. The thin layer chromatography was employed to ascertain purity of

the dyes.

2. Each dye is characterized by IR, 1H NMR Spectral Characteristics and C, H, N

elemental analysis.

3. Absorbance maxima (λmax) of each dye in UV Spectrum were recorded.

4. Application of these dyes on silk, wool and cotton fabrics has been

investigated.

5. Colorimetric data (CIELAB values L*, a*, b*, c*, H* and K/S value) have

been determined.

6. Light fastness has been measured by the standard methods of testing

(BS: 1006-1978). The wash fastness has been measured in accordance with

IS: 765-1979. The rubbing fastness test was carried out with a crockmeter

(Atlas) in accordance with AATCC-1961.

7. Antimicrobial activity data of all the dyes were evaluated.

8. Thermogravimetric analysis (TGA) data were also evaluated.



Experimental

Series-1: Hot brand reactive dyes

Step-1: Synthesis of 4,4'-methylene bis(2,5-dichloro aniline)[1,2]

(1)

2,5-Dichloro aniline (16.2 g, 0.1 mol) was dissolved in water (125 ml) and

36.5% hydrochloric acid (25 ml) at 50°C. The reaction mixture was then reacted with

3% aqueous formaldehyde (35 ml) solution at 60°C with stirring for 1 hour and

neutralized with 10% sodium hydroxide solution. The white precipitates obtained

were filtered, washed with hot water, dried and recrystallized from acetic acid, yield

75%, m.p. 115-118°C. Rf = 0.75 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

: 3395, 3315

(N-H), 2995 (C-H), 1595 (N-H bend.), 785 (C-Cl). 1H NMR (DMSO-d6) δ ppm: 2.92

(2H, s, CH2), 6.25 (4H, s, NH2), 6.63-7.12 (4H, m, Ar-H). Anal. Calcd. for

C13H10Cl4N2 (336.04): C, 46.46%; H, 3.00%; N, 8.34%. Found: C, 46.41%; H, 2.92%;

N, 8.26%.

Step-2: Synthesis of 6-bromo-2-phenyl-4H-benzo[1,3]oxazine-4-one[3]

(2)

To a stirred solution of 5-bromo anthranilic acid (2.16 g, 0.01 mol) in pyridine

(60 ml), Benzoyl chloride (1.16 ml, 0.01 mol) was added dropwise, maintaining the

temperature near 0-5°C for 1 hour. The reaction mixture was stirred for another

2 hours at room temperature until a solid product was formed. The reaction mixture

was neutralized with saturated sodium bicarbonate solution. Yellow solid which

separated was filtered, washed with water and recrystallized from ethanol. Yield 78%,

m.p. 175-178°C. Rf = 0.65 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

: 3066 (C-H), 1615

(C=N), 1755 (C=O), 1058 (C-O-C), 1182 (C-O), 536 (C-Br). 1H NMR (DMSO-d6) δ

ppm: 7.55-8.14 (8H, m, Ar-H). Anal. Calcd. for C14H8O2NBr (302.12): C, 55.66%;

H, 2.67%; N, 4.64%. Found: C, 55.60%; H, 2.61%; N, 4.56%.

Step-3: Synthesis of 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichlorophenyl}-6-

bromo-2-phenylquinazolin-4(3H)-one[4]

(3)

4,4'-Methylene bis(2,5-dichloro aniline) (1.68 g, 0.005 mol) and 6-bromo-2-

phenyl-4H-benzo[1,3]oxazine-4-one (1.51 g, 0.005 mol) were dissolved in pyridine

(40 ml) and heated under reflux for 6 hours under anhydrous reaction conditions and

then allowed to cool at room temperature. The reaction mixture was then treated with

ice cooled dilute hydrochloric acid and stirred. A solid separated out which was



filtered off and washed with water to remove any adhered pyridine. The crude

quinazolinone thus obtained was dried under vacuum and recrystallized from ethanol.

Yield 70%, m.p. 125-128°C. Rf = 0.60 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

: 3404,

3365 (N-H) 3028 (C-H), 1596 (C=N), 1666 (C=O), 1507 (C-N), 786 (C-Cl), 550

(C-Br). 1H NMR (DMSO-d6) δ ppm: 2.65 (2H, s, CH2), 6.18 (2H, s, NH2), 7.45-8.05

(12H, m, Ar-H). Anal. Calcd. for C27H16ON3Cl4Br (620.15): C, 52.29%; H, 2.60%;

N, 6.78%. Found: C, 52.22%; H, 2.54%; N, 6.71%.

Step-4: Diazotization of 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichlorophenyl}-

6-bromo-2-phenylquinazolin-4(3H)-one (4)

Concentrated hydrochloric acid (1.88 ml, 0.015 mol) was added to a well

stirred suspension of 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichlorophenyl}-6-

bromo-2-phenylquinazolin-4(3H)-one (3.10 g, 0.005 mol) in water (25 ml) and the

mixture was heated up to 70°C and maintained at that temperature till a clear solution

obtained. After cooling the solution to 0-5°C in an ice bath, a solution of sodium

nitrite (0.35 g, 0.005 mol) in water (10 ml) was added dropwise over a period of 10

minutes with stirring. The reaction was stirred at a temperature below 5°C for an hour.

The excess of nitrous acid (tested for using starch iodide paper) was removed by

adding required amount of sulphamic acid solution (10% w/v). The clear diazonium

salt solution (4) thus obtained was used immediately in the coupling reaction.

Step-5: Cyanuration of H-acid (5)

Cyanuric chloride (1.85 gm, 0.01 mol) was stirred in acetone (25 ml) at a

temperature below 5ºC for a period of an hour. A neutral solution of H acid (3.19 g,

0.01 mol) in aqueous sodium carbonate solution (10% w/v) was then added in small

amount in about an hour. The pH was maintained neutral by simultaneous addition of

sodium carbonate solution (1% w/v). The reaction mass was stirred at 0-5°C for

further 4 hours then clear solution was obtained. The resultant solution was used for

condensation reaction with m-nitro aniline.

Step-6: Condensation with m-nitro aniline (Synthesis of m-nitro anilino

cyanurated H-acid) (6)

The temperature of ice-cooled well stirred solution of cyanurated H-acid (4.67

g, 0.01 mol) was gradually raised to 45°C for half an hour. To this cyanurated H-acid



the m-nitro aniline (1.38 g, 0.01 mol) was added dropwise at same temperature,

during a period of 30 minutes, maintaining the pH neutral by simultaneous addition of

sodium bicarbonate (1% w/v). After the addition was completed, stirring was

continued for further 3 hours. The m-nitro anilino cyanurated H-acid solution thus

obtained was subsequently used for further coupling reaction.

Step-7: Synthesis of reactive dyes D1

To an icecold and stirred solution of m-nitro anilino cyanurated H-acid (2.83

g, 0.005 mol), a freshly prepared diazo solution (4) (3.34 g, 0.005 mol) was added

dropwise over a period of 10-15 minutes. The pH was maintained at 7.5 to 8.5 by

simultaneous addition of sodium carbonate solution (10% w/v). During coupling the

purple solution was formed. The stirring was continued for 3-4 hours to maintain the

temperature below 5°C. The reaction mixture was heated up to 60oC and sodium

chloride (12 g) added until the coloring material was precipitated. Further stirred for

an hour, filtered and washed with a small amount of sodium chloride solution (5%

w/v). The solid was dried at 80-90oC and extracted with DMF. The dye was

precipitated by diluting the DMF-extract with excess of chloroform. A violet dye was

then filtered, washed with chloroform and dried at 60oC.

Same procedure was followed for other reactive dyes D2 to D10 were

synthesized using m-nitro anilino cyanurated coupling components such as J-acid,

N-methyl-J-acid, N-phenyl-J-acid, Bronner acid, Gamma acid, Tobias acid, Sulpho

Tobias acid, Peri acid and Koch acid.

Characterizations of all the dyes are recorded in Table-1.



Step-1: Synthesis of 4,4'-methylene bis(2,5-dichloro aniline) (1)

Step-2: Synthesis of 6-bromo-2-phenyl-4H-benzo[1,3]oxazine-4-one (2)

Step-3: Synthesis of 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichloro phenyl}-6-

bromo-2-phenylquinazolin-4(3H)-one (3)



Step-4: Diazotization of 3-{4-[4-amino-2,5-dichlorobenzyl]-2,5-dichloro phenyl}-

6-bromo-2-phenylquinazolin-4(3H)-one (4)


Step-6: Condensation with m-nitro aniline

(Preparation of m-nitro anilino cyanurated H-acid) (6)






Chart-1: Coupling components used in the preparation of reactive dyes

(Arrow indicates the coupling position)

Final structure of reactive dyes (D1 to D10)










Step-1: Synthesis of 4,4'-methylene bis(m-nitro aniline)[1,2]

(7)

m-Nitro aniline (13.8 g, 0.1 mol) was dissolved in water (125 ml) and 36.5%

hydrochloric acid (25 ml) at 50°C. The reaction mixture was then reacted with 3%

aqueous formaldehyde (35 ml) solution at 60°C with stirring for 1 hour and

neutralized with 10% sodium hydroxide solution. The reddish precipitates obtained

were filtered, washed with hot water, dried and recrystallized from acetic acid, yield


: 3430, 3385

(N-H), 3097 (C-H), 1625 (N-H bend.), 1523, 1349 (N=O). 1H NMR (DMSO-d6) δ

ppm: 2.38 (2H, s, CH2), 6.28 (4H, s, NH2), 6.95-7.42 (6H, m, Ar-H). Anal. Calcd. for

C13H12O4N4 (288.26): C, 54.17%; H, 4.20%; N, 19.44%. Found: C, 54.11%; H,

4.12%; N, 19.38%.

Step-2: Synthesis of 7-chloro-2-phenyl-4H-benzo[1,3]oxazine-4-one[3]

(8)

To a stirred solution of 4-chloro anthranilic acid (1.72 g, 0.01 mol) in pyridine


temperature near 0-5°C for 1 hour. The reaction mixture was stirred for another 2

hours at room temperature until a solid product was formed. The reaction mixture was

neutralized with saturated sodium bicarbonate solution. A white solid which separated

was filtered, washed with water and recrystallized from ethanol. Yield 70%, m.p. 192-

195°C. Rf = 0.68 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

: 3075 (C-H), 1613 (C=N),

1756 (C=O), 1062 (C-O-C), 1177 (C-O), 779 (C-Cl). 1H NMR (DMSO-d6) δ ppm:

7.58-8.10 (8H, m, Ar-H). Anal. Calcd. for C14H8O2NCl (257.67): C, 65.26%; H,

3.13%; N, 5.44%. Found: C, 65.20%; H, 3.05%; N, 5.38%.

Step-3: Synthesis of 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-

phenylquinazolin-4(3H)-one[4]

(9)

4,4'-Methylene bis(m-nitro aniline) (1.44 g, 0.005 mol) and 7-chloro-2-phenyl-

4H-benzo[1,3]oxazine-4-one (1.29 g, 0.005 mol) were dissolved in pyridine (40 ml)

and heated under reflux for 6 hours under anhydrous reaction conditions and then

allowed to cool at room temperature. The reaction mixture was then treated with ice

cooled dilute hydrochloric acid and stirred. A solid separated out which was filtered

off and washed with water to remove any adhered pyridine. The crude quinazolinone

thus obtained was dried under vacuum and recrystallized from ethanol. Yield 72%,




: 3425, 3380 (N-H)

3045 (C-H), 1613 (C=N), 1674 (C=O), 1494 (C-N), 1525, 1350 (N=O), 778 (C-Cl).

1H NMR (DMSO-d6) δ ppm: 2.28 (2H, s, CH2), 6.22 (2H, s, NH2), 7.52-8.10 (14H, m,

Ar-H). Anal. Calcd. for C27H18O5N5Cl (527.92): C, 61.43%; H, 3.44%; N, 13.27%.

Found: C, 61.35%; H, 3.38%; N, 13.20%.

Step-4: Diazotization of 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-

phenylquinazolin-4(3H)-one (10)


stirred suspension of 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-phenyl

quinazolin-4(3H)-one (2.64 g, 0.005 mol) in water (25 ml) and the mixture was heated

up to 70°C and maintained at that temperature till a clear solution obtained. After

cooling the solution to 0-5°C in an ice bath, a solution of sodium nitrite (0.35 g, 0.005

mol) in water (10 ml) was added dropwise over a period of 10 minutes with stirring.

The reaction was stirred at a temperature below 5°C for an hour. The excess of nitrous

acid (tested for using starch iodide paper) was removed by adding required amount of

sulphamic acid solution (10% w/v). The clear diazonium salt solution (10) thus

obtained was used immediately in the coupling reaction.


Cyanuric chloride (1.85 g, 0.01 mol) was stirred in acetone (25 ml) at a

temperature below 5°C for a period of an hour. A neutral solution of H acid (3.19 g,





condensation reaction with p-chloro aniline.

Step-6: Condensation with p-chloro aniline (Synthesis of p-chloro anilino

cyanurated H-acid) (12)



the p-chloro aniline (1.28 g, 0.01 mol) was added dropwise at same temperature,

during a period of 30 minutes, maintaining the pH neutral by simultaneous addition of




continued for further 3 hours. The p-chloro anilino cyanurated H-acid solution thus



To an ice cold and stirred solution of p-chloro anilino cyanurated H-acid (2.79

g, 0.005 mol), a freshly prepared diazo solution (10) (2.88 g, 0.005 mol) was added




temperature below 5°C. The reaction mixture was heated up to 60oC and sodium







synthesized using p-chloro anilino cyanurated coupling components such as J-acid,






Step-1: Synthesis of 4,4'-methylene bis(m-nitro aniline) (7)

Step-2: Synthesis of 7-chloro-2-phenyl-4H-benzo[1,3]oxazine-4-one (8)

Step-3: Synthesis of 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-




Step-4: Diazotization of 3-{4-[4-amino-2-nitrobenzyl]-3-nitrophenyl}-7-chloro-2-



Step-6: Condensation with p-chloro aniline

(Preparation of p-chloro anilino cyanurated H-acid) (12)














Step-1: Synthesis of 5,5'-methylene bis(2-amino-4-chlorobenzoic acid)[1,2]

(13)

2-Amino-4-chloro benzoic acid (17.2 g, 0.1 mol) was dissolved in water

(125 ml) and 36.5% hydrochloric acid (25 ml) at 50°C. The reaction mixture was then

reacted with 3% aqueous formaldehyde (35 ml) solution at 60°C with stirring for

1 hour and neutralized with 10% sodium hydroxide solution. The reddish precipitates

obtained were filtered, washed with hot water, dried and recrystallized from acetic

acid, yield 72%, m.p. 215-218°C. Rf = 0.76 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

:

3478, 3362 (N-H), 3006 (C-H), 1754 (C=O), 1614 (N-H bend.), 777 (C-Cl). 1H NMR

(DMSO-d6) δ ppm: 2.65 (2H, s, CH2), 6.28 (4H, s, NH2), 11.06 (2H, s, COOH),

6.95-7.32 (4H, m, Ar-H). Anal. Calcd. for C15H12O4N2Cl2 (355.17): C, 50.72%;

H, 3.41%; N, 7.89%. Found: C, 50.65%; H, 3.35%; N, 7.80%.

Step-2: Synthesis of 6-Iodo-2-phenyl-4H-benzo[1,3]oxazine-4-one[3]

(14)

To a stirred solution of 5-Iodo anthranilic acid (2.63 g, 0.01 mol) in pyridine




was neutralized with saturated sodium bicarbonate solution. A yellow solid which



: 3056 (C-H), 1608

(C=N), 1757 (C=O), 1062 (C-O-C), 1182 (C-O), 539 (C-I). 1H NMR (DMSO-d6)

δ ppm: 7.55-7.95 (8H, m, Ar-H). Anal. Calcd. for C14H8O2NI (349.12): C, 48.16%;

H, 2.31%; N, 4.01%. Found: C, 48.09%; H, 2.24%; N, 3.92%.

Step-3: Synthesis of 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-

carboxyphenyl}-6-iodo-2-phenylquinazolin-4(3H)-one[4]

(15)

5,5'-Methylene bis(2-amino-4-chlorobenzoic acid) (1.78 g, 0.005 mol) and

6-Iodo-2-phenyl-4H-benzo[1,3]oxazine-4-one (1.75 g, 0.005 mol) were dissolved in

pyridine (40 ml) and heated under reflux for 6 hours under anhydrous reaction

conditions and then allowed to cool at room temperature. The reaction mixture was

then treated with ice cooled dilute hydrochloric acid and stirred. A solid separated out

which was filtered off and washed with water to remove any adhered pyridine. The

crude quinazolinone thus obtained was dried under vacuum and recrystallized from



ethanol. Yield 76%, m.p. 102-105°C. Rf = 0.56 (PhMe:EtOAc, 3:1 v/v). IR (KBr)

cm-1

: 3425, 3374 (N-H), 3067 (C-H), 1758 (C=O of COOH), 1668 (C=O of

quinazoline), 1578 (C=N), 1511 (C-N), 778 (C-Cl), 531 (C-I). 1H NMR (DMSO-d6) δ

ppm: 2.72 (2H, s, CH2), 6.32 (2H, s, NH2), 11.12 (2H, s, COOH), 7.52-7.95 (12H, m,

Ar-H). Anal. Calcd. for C29H18O5N3Cl2I (686.28): C, 50.75%; H, 2.64%; N, 6.12%.

Found: C, 50.68%; H, 2.56%; N, 6.05%.

Step-4: Diazotization of 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-

carboxyphenyl}-6-iodo-2-phenylquinazolin-4(3H)-one (16)


stirred suspension of 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-carboxy

phenyl}-6-iodo-2-phenylquinazolin-4(3H)-one (3.43 g, 0.005 mol) in water (25 ml)

and the mixture was heated up to 70°C and maintained at that temperature till a clear

solution obtained. After cooling the solution to 0-5°C in an ice bath, a solution of

sodium nitrite (0.35 g, 0.005 mol) in water (10 ml) was added dropwise over a period

of 10 minutes with stirring. The reaction was stirred at a temperature below 5°C for an

hour. The excess of nitrous acid (tested for using starch iodide paper) was removed by










condensation reaction with p-nitro aniline.

Step-6: Condensation with p-nitro aniline

(Synthesis of p-niro anilino cyanurated H-acid) (18)



the p-nitro aniline (1.38 g, 0.01 mol) was added dropwise at same temperature, during



a period of 30 minutes, maintaining the pH neutral by simultaneous addition of


continued for further 3 hours. The p-nitro anilino cyanurated H-acid solution thus



To an icecold and stirred solution of p-nitro anilino cyanurated H-acid (2.85 g,

0.005 mol), a freshly prepared diazo solution (16) (3.67 g, 0.005 mol) was added




temperature below 5ºC. The reaction mixture was heated up to 60oC and sodium







synthesized using p-nitro anilino cyanurated coupling components such as J-acid,






Step-1: Synthesis of 5,5'-methylene bis(2-amino-4-chlorobenzoic acid) (13)

Step-2: Synthesis of 6-Iodo-2-phenyl-4H-benzo[1,3]oxazine-4-one (14)

Step-3: Synthesis of 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-




Step-4: Diazotization of 3-{4-[2-chloro-4-amino-5-carboxybenzyl]-5-chloro-2-



Step-6: Condensation with p-nitro aniline

(Synthesis of p-niro anilino cyanurated H-acid) (18)














Step-1: Synthesis of 4,4'-methylene bis(3,5-difluoro aniline)[1,2]

(19)

3,5-Difluoro aniline (12.9 g, 0.1 mol) was dissolved in water (125 ml) and

36.5% hydrochloric acid (25 ml) at 50°C. The reaction mixture was then reacted with

3% aqueous formaldehyde (35 ml) solution at 60°C with stirring for 1 hour and

neutralized with 10% sodium hydroxide solution. The orange precipitates obtained

were filtered, washed with hot water, dried and recrystallized from acetic acid. Yield


: 3435, 3355

(N-H), 2956 (C-H), 1642 (N-H bend.), 1051 (C-F). 1H NMR (DMSO-d6) δ ppm: 2.72

(2H, s, CH2), 6.32 (4H, s, NH2), 6.22-6.28 (4H, m, Ar-H). Anal. Calcd. for

C13H10N2F4 (270.23): C, 57.78%; H, 3.73%; N, 10.37%. Found: C, 57.70%; H,

3.64%; N, 10.30%.

Step-2: Synthesis of 6-nitro-2-phenyl-4H-benzo[1,3]oxazine-4-one[3]

(20)

To a stirred solution of 5-nitro anthranilic acid (1.82 g, 0.01 mol) in pyridine




was neutralized with saturated sodium bicarbonate solution. A yellow solid which



: 3087 (C-H), 1611

(C=N), 1761 (C=O), 1060 (C-O-C), 1178 (C-O), 1532, 1343 (N=O). 1H NMR

(DMSO-d6) δ ppm: 7.50-7.98 (8H, m, Ar-H). Anal. Calcd. for C14H8O4N2 (268.22):

C, 62.69%; H, 3.01%; N, 10.44%. Found: C, 62.58%; H, 2.94%; N, 10.35%.

Step-3: Synthesis of 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluorophenyl} -6-

nitro-2-phenylquinazolin-4(3H)-one[4]

(21)

4,4'-Methylene bis(3,5-difluoro aniline) (1.35 g, 0.005 mol) and 6-nitro-2-

phenyl-4H-benzo[1,3]oxazine-4-one (1.34 g, 0.005 mol) were dissolved in pyridine

(40 ml) and heated under reflux for 6 hours under anhydrous reaction conditions and

then allowed to cool at room temperature. The reaction mixture was then treated with

ice cooled dilute hydrochloric acid and stirred. A solid separated out which was

filtered off and washed with water to remove any adhered pyridine. The crude



quinazolinone thus obtained was dried under vacuum and recrystallized from ethanol.

Yield 70%, m.p. 112-115°C. Rf = 0.58 (PhMe:EtOAc, 3:1 v/v). IR (KBr) cm-1

: 3434,

3365 (N-H) 3095 (C-H), 1618 (C=N), 1687 (C=O), 1495 (C-N), 1585 (asym.), 1343

(sym.) (N=O), 1052 (C-F). 1H NMR (DMSO-d6) δ ppm: 2.78 (2H, s, CH2), 6.28 (2H,

s, NH2), 7.40-7.96 (12H, m, Ar-H). Anal. Calcd. for C27H16O3N4F4 (520.43): C,

62.31%; H, 3.10%; N, 10.77%. Found: C, 62.24%; H, 3.02%; N, 10.70%.

Step-4: Diazotization of 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluorophenyl}-6-

nitro-2-phenylquinazolin-4(3H)-one (22)


stirred suspension of 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluorophenyl}-6-nitro-

2-phenylquinazolin-4(3H)-one (2.60 g, 0.005 mol) in water (25 ml) and the mixture

was heated up to 70°C and maintained at that temperature till a clear solution

obtained. After cooling the solution to 0-5°C in an ice bath, a solution of sodium

nitrite (0.35 g, 0.005 mol) in water (10 ml) was added dropwise over a period of 10

minutes with stirring. The reaction was stirred at a temperature below 5°C for an hour.

The excess of nitrous acid (tested for using starch iodide paper) was removed by










condensation reaction with o-chloro-p-nitro aniline.

Step-6: Condensation with o-chloro-p-nitro aniline

(Synthesis of o-chloro-p-niro anilino cyanurated H-acid) (24)



the o-chloro-p-nitro aniline (1.73 g, 0.01 mol) was added dropwise at same



temperature, during a period of 30 minutes, maintaining the pH neutral by

simultaneous addition of sodium bicarbonate (1% w/v). After the addition was

completed, stirring was continued for further 3 hours. The o-chloro-p-nitro anilino

cyanurated H-acid solution thus obtained was subsequently used for further coupling

reaction.


To an icecold and stirred solution of o-chloro-p-nitro anilino cyanurated

H-acid (3.02 g, 0.005 mol), a freshly prepared diazo solution (22) (2.84 g, 0.005 mol)

was added dropwise over a period of 10-15 minutes. The pH was maintained at 7.5 to

8.5 by simultaneous addition of sodium carbonate solution (10% w/v). During

coupling the purple solution was formed. The stirring was continued for 3-4 hours to

maintain the temperature below 5°C. The reaction mixture was heated up to 60oC and

sodium chloride (12 g) added until the coloring material was precipitated. Further

stirred for an hour, filtered and washed with a small amount of sodium chloride

solution (5% w/v). The solid was dried at 80-90oC and extracted with DMF. The dye

was precipitated by diluting the DMF-extract with excess of chloroform. A violet dye

was then filtered, washed with chloroform and dried at 60oC.


synthesized using o-chloro-p-nitro anilino cyanurated coupling components such as

J-acid, N-methyl-J-acid, N-phenyl-J-acid, Bronner acid, Gamma acid, Tobias acid,

Sulpho Tobias acid, Peri acid and Koch acid.




Step-1: Synthesis of 4,4'-methylene bis(3,5-difluoro aniline) (19)

Step-2: Synthesis of 6-nitro-2-phenyl-4H-benzo[1,3]oxazine-4-one (20)

Step-3: Synthesis of 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluorophenyl} -6-

nitro-2-phenylquinazolin-4(3H)-one (21)



Step-4: Diazotization of 3-{4-[4-amino-2,6-difluorobenzyl]-3,5-difluoro phenyl}-

6-nitro-2-phenylquinazolin-4(3H)-one (22)


Step-6: Condensation with o-chloro-p-nitro aniline

(Synthesis of o-chloro-p-niro anilino cyanurated H-acid) (24)













References

1. D. R. Patel, J. A. Patel, K. C. Patel, Proc. Nat. Acad. Sci. India Sect. A, 80-II

(2010) 109.

2. D. R. Patel, A. L. Patel, K. C. Patel, L. A. Patel, Colorage, 57(4) (2010) 72.

3. X. Gao, X. Cai, K. Yan, B. Song, L. Gao, Z. Chen, Molecules, 12 (2007)

2621.

4. V. K. Pandey, J. Kumar, S. K. Saxena, Mukesh, M. N. Joshi, S. K. Bajpai, J.

Indian Chem. Soc., 84 (2007) 593.

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