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Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci. International Science Congress Association 54 Chlorination of Aromatic Compounds in Aqueous Media using N- Chlorosuccinimide Sushil Kumar Sharma* Department of Chemistry, JJTU Rajasthan, INDIA Available online at: www.isca.in, www.isca.me Received 30 th July 2015, revised 12 th October 2015, accepted 18 th November 2015 Abstract A proficient/effective method for the synthesis of chlorinated arenes is revealed. The system involves the use of N- Chlorosuccinimide (NCS) as chlorinating and oxidizing agent in aqueous medium under mild conditions to chlorinate the aromatic compounds in virtuous to excellent yields (75-96 percent). The reagent system is efficient, organic solvent-free and easy to handle. N-Chlorosuccinimide is an advantageous reagent for aromatic halogenation, while at the same time, circumventing electrophilic addition of chlorine to a pi bond. Keywords: Chlorination, arenes, N-Chlorosuccinimide (NCS), aqueous medium, aromatic compounds. Introduction Chlorination of arenes is a protruding organic reaction with widespread laboratory use and industrial uses. The introduction of chlorine onto aromatic ring is a significant synthetic transformation because chlorinated compounds are acknowledged as versatile initial materials and added ingredient in the manufacture of high eminence insecticides, selective weedicides, bulk drugs, fungicides, industrial chemicals, pharmaceutical etc 1-4 . Hence, there are several known traditional approaches in the literature that have been established for the chlorination of aromatic compounds. The industrial/large scale chlorination of higher paraffin’s is usually carried out in the liquid phase at above 110° without any catalyst or light initiation 5-6 . Theoretically all the possible isomeric mono substituted products are formed under these conditions in definite ratios. The dihalogens elementally are very toxic, corrosive, and can be hazardous to handle, it is an irritant to the respiratory tract and eyes because it attacks their mucous membranes, process those involve their transport and handling are very difficult and risky 7-11 . Levels of 10-20 ppm of chlorine gas in air cause immediate irritation and brief exposure of 800 ppm of Cl 2 can be fatal. Generally, the chlorination of arenes can be accomplished by using chlorinating agents such as t- butyl hypochlorite in attendance of zeolites, metal chloride-H 2 O 2 in acid aqueous medium, m-chloroperbenzoic acid/HCl/DMF,. Sulfuryl chloride, acetyl chloride in presence of ceric ammonium nitrate, SnCl 4 /Pb(OAC) 4 , HCl-H 2 O 2 under microwave surroundings, N- chlorosuccinimide, etc 12 . Chlorination is a vital reaction of organic chemistry because of extensive variety of uses of chloro-substituted organic compounds in fine chemicals and pharmaceutical intermediates. Consequently, large number of methods are accessible in the prior art for chlorination of organic compounds 13-15 . However, most of the traditional and existing bromination approaches intricate the use of toxic and hazards organic solvents which have serious ecological effects and also having disadvantages of long reaction period, high temperature and use of catalyst, so there is need for the expansion of a method which is efficient, free from organic solvent, cost effective and easy to handle 16-17 . Also, one of the key principles of sustainable chemistry is the reducing derivatives (solvents) in chemical processes or the replacement of toxic/hazards solvent with planet-friendly solvents to help us make substantial developments in the direction of a more sustainable future. Water is the most capable solvent because it is readily available, hydrophobic effect, high cohesive energy density, non- flammable, high surface tension, non-toxic, low viscosity and easy separation of wide range of reagents from several organic products is possible by water 18-24 . Therefore, in our present study, a method has been established for the chlorination of aromatic compounds using N- chlirosuccinimide/Hydrochloric acid (NCS/HCl) in aqueous medium 25-31 . The present system uses the water as reaction media and also provides the chlorinated aromatic products in noble yields (75- 96 percent) under the mild reaction conditions. Also, this system is cost effective, efficient and easy to handle at both the scales 29-32 (Commercial and Laboratory).
Transcript
Page 1: Chlorination of Aromatic Compounds in Aqueous Media … · Chlorination of Aromatic Compounds in Aqueous Media ... aromatic compounds in ... literature that have been established

Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X

Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci.

International Science Congress Association 54

Chlorination of Aromatic Compounds in Aqueous Media using N-

Chlorosuccinimide

Sushil Kumar Sharma* Department of Chemistry, JJTU Rajasthan, INDIA

Available online at: www.isca.in, www.isca.me Received 30th July 2015, revised 12th October 2015, accepted 18th November 2015

Abstract

A proficient/effective method for the synthesis of chlorinated arenes is revealed. The system involves the use of N-

Chlorosuccinimide (NCS) as chlorinating and oxidizing agent in aqueous medium under mild conditions to chlorinate the

aromatic compounds in virtuous to excellent yields (75-96 percent). The reagent system is efficient, organic solvent-free and

easy to handle. N-Chlorosuccinimide is an advantageous reagent for aromatic halogenation, while at the same time,

circumventing electrophilic addition of chlorine to a pi bond.

Keywords: Chlorination, arenes, N-Chlorosuccinimide (NCS), aqueous medium, aromatic compounds.

Introduction

Chlorination of arenes is a protruding organic reaction with widespread laboratory use and industrial uses. The introduction of chlorine onto aromatic ring is a significant synthetic transformation because chlorinated compounds are acknowledged as versatile initial materials and added ingredient in the manufacture of high eminence insecticides, selective weedicides, bulk drugs, fungicides, industrial chemicals, pharmaceutical etc1-4. Hence, there are several known traditional approaches in the literature that have been established for the chlorination of aromatic compounds. The industrial/large scale chlorination of higher paraffin’s is usually carried out in the liquid phase at above 110° without any catalyst or light initiation5-6. Theoretically all the possible isomeric mono substituted products are formed under these conditions in definite ratios. The dihalogens elementally are very toxic, corrosive, and can be hazardous to handle, it is an irritant to the respiratory tract and eyes because it attacks their mucous membranes, process those involve their transport and handling are very difficult and risky7-11. Levels of 10-20 ppm of chlorine gas in air cause immediate irritation and brief exposure of 800 ppm of Cl2 can be fatal. Generally, the chlorination of arenes can be accomplished by using chlorinating agents such as t- butyl hypochlorite in attendance of zeolites, metal chloride-H2O2 in acid aqueous medium, m-chloroperbenzoic acid/HCl/DMF,. Sulfuryl chloride, acetyl chloride in presence of ceric ammonium nitrate, SnCl4/Pb(OAC)4, HCl-H2O2 under microwave surroundings, N-chlorosuccinimide, etc12. Chlorination is a vital reaction of organic chemistry because of

extensive variety of uses of chloro-substituted organic compounds in fine chemicals and pharmaceutical intermediates. Consequently, large number of methods are accessible in the prior art for chlorination of organic compounds13-15. However, most of the traditional and existing bromination approaches intricate the use of toxic and hazards organic solvents which have serious ecological effects and also having disadvantages of long reaction period, high temperature and use of catalyst, so there is need for the expansion of a method which is efficient, free from organic solvent, cost effective and easy to handle16-17. Also, one of the key principles of sustainable chemistry is the reducing derivatives (solvents) in chemical processes or the replacement of toxic/hazards solvent with planet-friendly solvents to help us make substantial developments in the direction of a more sustainable future. Water is the most capable solvent because it is readily available, hydrophobic effect, high cohesive energy density, non- flammable, high surface tension, non-toxic, low viscosity and easy separation of wide range of reagents from several organic products is possible by water18-24. Therefore, in our present study, a method has been established for the chlorination of aromatic compounds using N-chlirosuccinimide/Hydrochloric acid (NCS/HCl) in aqueous medium25-31. The present system uses the water as reaction media and also provides the chlorinated aromatic products in noble yields (75-96 percent) under the mild reaction conditions. Also, this system is cost effective, efficient and easy to handle at both the scales29-32 (Commercial and Laboratory).

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Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606X

Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci.

International Science Congress Association 55

Material and Methods

Materials and instrumentation: All reagents and initial materials for reaction process were purchased from commercial traders and used without any additional purification. Granulated and flaking substrates were crumpled to fine powder using mortar and pestle. HPLC analyses were determined using Waters 2695 device with PDA detector, column C18 (250 mm x 4.6 mm x 5 µ), solvent system 70 per cent methanol (CH3OH) + 30 per cent water (H2O), flow rate 1.1 Ml/minute HPLC pureness is described by area percent NMR spectra were found in DMSO and CDCl3 on a Bruker Avance III 400 MHZ NMR spectrometer; the chemical shifts were described in parts per million (ppm), 1HNMR (relative to TMS referenced as 0.00 ppm) and13 C NMR (comparative to DMSO referenced as 39.50 ppm)40-51. Gas Chromatograph-Mass Spectroscopy (GCMS) analysis were carried out by Agilent GC (Model 7890) with Chemstation software; capillary column HP-5ms, 30 m x 0.25 mm x 0.25 µ; flow- 2 ml/min; detector- mass range-15 amu to 640 amu; injector temp- 280˚C; detector temp-300˚C; injection volume-1 µL of 5 per cent solution in CH3OH. Mass spectral studies done by Micromass quattro Micro API ion source. Quattro Micro API triple quadrupole mass spectra equipped with a standard Atmospheric-pressure chemical ionization source52-58. Common chlorination procedures for aromatic compounds:

Monochlorination: An aqueous solution of NCS (0.005 mol) in H2O (10-15 Ml) was added to a fine powder of aromatic substrate (0.01 mol) booked in a 100 ml EasyMax-102 Mettler Toledo’s fully equipped workstation with a magnetic stirring bar at room temperature (25°C). After that HCl (2 ml) was added drop wise slowly-slowly for 15 minutes59-63. The reaction finishing point was observed with TLC and recorded. After finishing point of the reaction, 5 ml of H2O was added to distinct the product; product was filtered, and dehydrated in vacuum oven. The identifications of end products were confirmed by 1 H NMR, mass spectra and were equated with authentic samples64. Dichlorination: Progression for the synthesis of dichlorinated product was quite similar to synthesis model given in monochlorination method, excepting 0.01 mol of N-chlorosuccinimide (NCS) and 4 ml of HCl was used wrt 0.01 mol of substrate65-71.

Results and Discussion

In present study, the chlorination was first tried on 4-chloroacetanilide by using N-chlorosuccinimide (0.01 mol), Sodium chloride (0.03 mol) and H 2 S04 (1 mL) in H2O (entry- 1, table-1). The chlorinating reagent is thus produced in-situ in the reaction mixture by oxidizing NaCI using N-Chlorosuccinimide as an oxidizing agent in acidic medium.

In a while, HCl was tried instead of NaCl and H2SO4, which performances as a chlorine source as well makes the reaction mixture acidic (table-1, entry-2). Results of table-1 display that the chlorinated product obtained in healthier yield when HCl was used in place of NaCl and H2SO4. Chlorination was also strained in water by using numerous oxidants such as sodium periodate. H2O2 (30 per cent) and sodium perborate (table-1). The results suggest that very little amount of product is formed in case of NaIO4 (13 percent) and H2O2 (21 percent) and no product was formed with sodium perborate. Therefore, it is found experimentally that sodium chlorate and HCl contributed the best results in aqueous medium72-81. Effect of surfactant: Ionic and non-ionic surfactants were used to study the consequence of surfactant on the yield and reaction time. It was observed that surfactant progresses the dispersion of aromatic substrates in water and also improves the texture of product but there was no effect on yield and reaction time82-89.

Effect of concentration of HCl: The quantity of HCl from 2.5 ml to 2 ml, the resultant end product yield of 2, 4- dichloroacetanilide get reduced up to 70 percent. Also, dejection in melting point exposes that under chlorinated product was formed due to reduction in the amount of HCl. On further diminishing the amount of HCl from 1.5 ml to 1 ml, no product was achieved90-92. It was observed that the yield and melting point of 2, 4-dichloroacetanilide became immobile on increasing the amount of HCl from 2 ml to 2.4 ml. henceforth; the ideal amount of HCl is 2 ml93. Effect of concentration of NaCIO

3: Diminishing in N-Chlorosuccinimide (NCS) concentration from 0.005 mol to 0.0033 mol resulted in reduction of the yield of 2, 4-dichloroacetanilide. Melting point of product was similarly not within the preferred range due to under chlorination of 4-chloroacetanilide in the attendance of 0.0033 mol of NCS. Though increasing the concentration of NCS from 0.005 to 0.015 mol, there was no influence on these both factors. Therefore, it was concluded experimentally that 2 ml of HCl and 0.005 mol of NCS afforded the best yield of chlorinated product94-97. The dichlorination can also be performed by increasing the amount of HCl along with the amount of N-Chlorosuccinimide. To show the general application of the scheme, it was applied to a variability of aromatic compounds to give analogous chlorinated products in decent yields. The outcome of this study is summarized in table number 2. It is clear from the results that all aromatic substrates were chlorinated within 1.5-3.0 h in decent yields. 2, 4-dichloroacetanilide (table-2, entry-1) was obtained in greatest yield (95 per cent) from 4-chloroacetanilide within 2 h at room temperature and having an HPLC pureness of 96.8 per cent (table-3, e ntry-1).

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Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606X

Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci.

International Science Congress Association 56

Table-1

Screening of optimum reaction conditions for oxychlorination using dissimilar reagent systems in a aqueous media

Entry Reagent

System

Reaction

Conditions Starting Material Product

Yielda

(per

cent)

1. NaCl/NCS/H2SO4b 2 h at r.t.

87

2. HCl/NCSc 2 h at r.t.

95

3. HCl/NaIO4d

4 h at r.t.

16

4. HCl/H2O2e 4 h at r.t.

22

5. HCl/NaBO3.3H2 Ot 4 h at r.t.

---

aIsolated yields, bConditions: Substrate, 0.01 mol; NaCl, 0.03 mol; NCS, 0.005 mol; H2SO4, 1Ml;H2O, 8Ml, cConditions: Substrate, 0.01 mol; NCS, 0.005 mol; HCl, 2 Ml; H2O, 8Ml, dConditions: Substrate, 0.01 mol;NalO4, 0.005 mol; HCl, 2 Ml; H2O, 8Ml, eConditions: Substrate, 0.01 mol; HCl.2 mulch2O2, 3mL; H2O.8Ml, fConditions: Substrate, 0.01 mol; NaBO3.3H2O,0.01 mol; HCl, 2 mL; H2O, 8 mL 4-Nitroacetanilide showed no reactivity up to 4 h at room temperature (25˚C) while at marginally higher temperature (45˚C), 2-chloro-4-nitroacetanilide was obtained in good yield (75 per cent) within 3 h of chemical reaction (Table 2, Entry 3, 4). Previously Jerzy et al. has synthesized 2- chloro-4-nitroacetanilide from 4-nitroacetanilide in poor yield (32 per cent) along with formation of 2, 6-dichloro-4-nitroacetanilide (68 per cent) at 50˚C. 3, 5-dichloro-4- hydroxybenzoic acid which is used as an intermediary in organic syntheses was attained in 86 per cent yield (table-2, entry-13) with an HPLC purity of 86 per cent. 3-chloro-4-hydroxybenzonitrile (Table 4.2, Entry 14) which is used as intermediate of selective agrochemicals, pharmaceuticals and dyes was obtained in 82 per cent within 1.5 h at room temperature from 4-hydroxybenzonitrile. The same compound was also produced in past research study by H.A.Muathen using SnCl4/Pb(OAc)4 in ethyl acetate in 77 per cent yield98. In case of benzanilide, a mix of substrate and product

(under chlorinated product) was formed at room temperature within 3 h (table-2, entry-7) but at marginally higher temperature (40'C), para-substituted product was obtained within 1.5 h (table-1.2, e ntry 8) with an HPLC purity of 95.23 per cent which is an industrially important compound. 3-chloro-4-hydroxybenzoic acid (table-2, entry-10) was obtained in 82 per cent yield and pureness of 98.01per cent. Mukhopadhyay et al. prepared this compound with lowly conversion (53 per cent) at 45°C in 4 h using H202 and aqueous HCL an important pharmaceutical intermediate 3-chloro-4-hydroxybenzonitrile (table-2, entry- 14) was prepared from 4-hydroxybenzonitrile within 1.5 h in 82 per cent yield (98.8 per cent purity by HPLC). 3, 5-dichloro 4-hydroxybenzonitrile was synthesized from the dichlorination of 4-hydroxybenzonitrile in 85 per cent yield at room temperature within 2 h, which is extensively used as a pesticide. Extremely activated aromatic compounds like aniline and phenol undergo oxidation sooner than chlorination by this method. Though, the substituted anilines and phenols were chlorinated in upright yields at room temperature99.

NHCOCH3Cl NHCOCH 3Cl

Cl

NHCOCH3Cl NHCOCH 3Cl

Cl

NHCOCH3Cl NHCOCH 3Cl

Cl

NHCOCH3Cl NHCOCH 3Cl

C l

NHCOCH3Cl NHCOCH 3Cl

C l

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Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606X

Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci.

International Science Congress Association 57

Table-2

Oxidative chlorination of aromatic compounds in aqueous medium

R2

R1

NCS / HCl

H2O, r.t.

R1

R2

Cl(n)

Entry Starting Material Reaction

Conditions Product

Yielda

(per cent) Mp °C (lit.)

1. NHCONH 3Cl

2 h, r.t. NHCONH3Cl

Cl

95b 145(143-146)

2. NHCONH3Br

2 h, r.t. NHCONH3

Cl

Br

93b 152(151-152)

3. OH CHO

4 h, r.t. OH CHO

Cl

82b 130(128-132)

4. COOH

OH

2 h, r.t. COOH

O H

C l

C l

83c 222(221-224)

5. NH2O2N

2 h, r.t. NH2O2N

Cl

90b 107(107-110)

6. OH

NO2

2 h, r.t. O H

NO 2

C l

84b 83(85-87)

7. NHCOPh

3 h, 40°C. -------- Complex Mixture

---

8.. NHCOPh

1.5h, r.t. NHCOPhCl

93b 190(192-193)

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Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606X

Vol. 5(12), 54-73, December (2015) Res. J. Chem. Sci.

International Science Congress Association 58

9. CHO

OH

1.5h, r.t. CHO

O H

C l

85b 100(99-103)

10. COOHOH

1.5h, r.t. COOHOH

Cl

82b 166(168-170)

11. NHCOCH 3O2N

4 h, r.t. ---- --- ---

12. O2N NHCOCH3

3 h, 45 °C O2N NHCOCH 3

Cl 75b 138(138-139)

13. COOHOH

4 h, r.t. COOHOH

C l

C l

86c 264(264-266)

14. CNOH

1.5h, r.t. CNOH

C l

82b 149(150)

a Isolated yields, b Monochlorination: Substrate, 0.01 mol; NCS, 0.005 mol; HCl, 2mL; H 20, 8-10 mL., c Dichlorination:

Substrate, 0.01 mol; NCS, 0.01 mol; HCl, 4mL; H20, 8-10 mL.

Encouraged by the results of activated arenes, same system, i.e., NCS/HCl using water as reaction media was also tried for the chlorination of deactivated arenes such as benzoic acid and nitrobenzene. Nevertheless, the present system failed to chlorinate the deactivated aromatic compounds at 60˚C and 80˚C even after 20 h. Therefore, this system can be used to chlorinate activated arenes in good yield under mild conditions. It is obvious from literature that in case of oxychlorination the oxidation of chloride is possible under acidic conditions to get hypochlorous acid and/or Cl2; these oxidized classes then react in-situ with substrates such as arenes to yield chlorinated product. Consequently, under certain conditions whichever Cl2 or HOCl can be main chlorinating agents or together can act simultaneously to yield chlorinated product100-102. However, it has been described recently that at very low pH (Ph < 3) Cl2 functions as an active chlorinating agent though at higher pH (3-6.5) HOCl is the activechlorinating classes. Mechanism: It is obvious from literature that in case of oxychlorination the oxidation of chloride is possible under acidic conditions to get hypochlorous acid and/or Cl2; these oxidized classes then react in-situ with substrates such as arenes to yield chlorinated product. Consequently, under certain conditions whichever Cl2 or HOCl can be main chlorinating agents or together can act simultaneously to yield chlorinated

product. However, it has been described recently that at very low pH (Ph < 3) Cl2 functions as an active chlorinating agent though at higher pH (3-6.5) HOCl is the activechlorinating classes

Figure-1

Active Chlorination

The pH of our reaction medium is very low (pH < 1) so the active chlorinating classes may be Cl2 slightly than HOCl. Also, from rate data and comparative reactivities studies it has been acknowledged that Cl2 is much more reactive chlorinating agent than HOCl and addition of large amount of acid or sinking the pH of the reaction will overwhelm the hydrolysis of Cl2 to HOCl (equation-1). Consequently, it can be determined that N-chlorosuccinimide will oxidize the chloride to form chlorine and due to higher reactivity of Cl2 it will help as an active chlorinating species which provides the Cl+ ion to achieve a rapid chlorination of substrates (scheme-2). Academically, one equivalent of chlorate produces three equivalents of chlorinating agent; though, this was not accorded exactly by investigational results103-107.

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Spectroscopic Data of Few Chlorinated Aromatic

Compounds: 2,4-Dichloroacetanilide (I): White needles; 1H NMR (400 MHz,CDCl3) δ 2.35 (s, CH3, 3H), δ 6.96 ( d, j = 2.33 Hz, Ar, 1H), δ 7.18 (dd, j = 8.77, 2.41 Hz, Ar, 1H), δ 7.82 (brs, NH, 1H), δ 8.42 (d, j = 8.91 Hz, Ar, 1H) ppm; 13C NMR (100 MHz, DMSO): 168.75, 133.76, 129.07, 128.49, 126.89, 126.20, 125.80, 23.39 ppm; Mass Spectral data: calculated for C8H7Cl2NO [M]+ 204.26, found 204.1 [M-1]+. 4-Bromo-2-chloroacetanilide (2): White needles; 1H NMR (400 MHz, Deuterated Chloroform) δ 2.25 (s, 3H, CH3), δ 7.49 ( d, j = 2.25 Hz, Ar, 1H), δ 7.38 (dd, j = 8.78, 2.34 Hz, 1H, Ar), δ 7.48 (brs, NH, 1H), δ 8.31 (d, j = 8.77 Hz, Ar, 1H) parts per million; Mass Spectral data: calculated for C8H7BrCINO [M]+ 239, found 248 [M+1]+. 2-Chloro-4-nitroacetanilide (4): Yellow powder; 1H NMR (400 MHz, Deuterated Chloroform) δ 2.26 (s, CH3, 3H), δ 8.68 ( d, j = 9.18 Hz, Ar, 1H), δ 8.34 (d, j = 2.62 Hz, Ar, 1H), δ 8.22 (dd, j = 9.32, 2.48 Hz, Ar, 1H), δ 7.88 (brs, NH, 1H) parts per million; Mass Spectral data: calculated for C8H7CIN2O3 [M]+ 214.61, found 216.8 [M+2]+. 3-Chloro-4-hydroxybenzaldehyde, ClC6H3(OH)CHO, (5):

Light brown powder; 1H NMR (400 MHz, Deuterated Chloroform) δ 9.82 (s, 1H, CHO), δ 7.78 (d, j = 1.68 Hz, Ar, 1H), δ 7.64 (dd, j = 8.56, 1.79 Hz, Ar, 1H), δ 7.12 (d, j = 8.32 Hz, Ar, 1H) parts per million; Mass Spectral data: calculated for C7H5CIO2 [M]+ 167,6, found 166 [M-1]+. 5-Chlorosalicylic acid (6): White crystalline; 1H NMR (400 MHz, Deuterated Chloroform) δ 8.98 (s, OH, 1H), δ 7.68 (d, j = 2.46 Hz, Ar, 1H), δ 7.41 (dd, j = 8.77, 2.49 Ar, Hz, 1H), δ 6.89 (d, j = 8.78 Hz, Ar, 1H) ppm; MS: calcd. For C7H5CIO3 [M]+ 172, found 171. 3,5-Dichlorosalicylic acid (7): White crystalline; 1H NMR (400 MHz, Deuterated Chloroform) δ 7.92 (d, j = 2.38 Hz, Ar, 1H), δ 7.79 (d, j = 2.52 Hz, Ar, 1H), ppm; MS: calcd. for C7H4CI2O3 [M]+ 208.10, found 207 [M-1]+. 4-Chloro-2-nitroaniline (8): Yellow Orange powder form; 1H NMR (400 MHz, Deuterated Chloroform) δ 8.05 (d, j = 2.54, Ar, 1H), δ 7.36 (dd, j = 9.20, 2.33, Ar, 1H), δ 7.12 (d, j = 9.22, Ar, 1H) δ 7.67 (bs, 1H, NH2) ppm; MS (APCI): calcd. for C6H5CIN2O2 [M]+ 172.57, found 172 [M]+. 2-Chloro-4-nitroaniline (9): Yellow fine powder; 1H NMR (400 MHz, Deuterated Chloroform) δ 7.78 (d, j = 2.62 Hz, Ar 1H), δ 7.58 (dd, j = 9.32, 2.60 Hz, Ar, 1H), δ 7.58 (d, j = 9.18 Hz, Ar, 1H) δ 3.79 (bs, 2H, NH2) ppm; MS (APCI): calcd. for C6H5CIN2O2 [M]+ 173.62, found 173 [M]+.

4-Chloro-2-nitrophenol (10): Yellow needles; 1H NMR (400 MHz, Deuterated Chloroform) δ 8.32 (d, j = 9.30, Ar, 1H), δ 7.92 (dd, j = 9.42, 2.38, Ar, 1H), δ 7.18 (d, j = 2.38, Ar, 1H) δ 10.82 (s, OH, 1H) parts per million; MS (Atmospheric Pressure Chemical Ionisation): calcd. for C6H4CINO3 [M]+ 173.88, found 173 [M]+. 4-Chlorobenzanilide (12): White powder; 1H NMR (400 MHz, Deuterated Chloroform) δ 8.10-8.36 (m, Ar, 9H), parts per million; MS (Atmospheric Pressure Chemical Ionisation): calcd. for C13H10CINO [M]+ 236, found 237 [M+1]+. 5-Chlorosalicyladehyde (13): White fine powdered form; 1H NMR (400 MHz, Deuterated Chloroform) δ 9.78 (s, CHO, 1H), δ 10.77 (s, OH, 1H), δ 6.88 (d, j = 8.77, Ar, 1H) δ 7.42 (dd, j = 8.79, 2.50, Ar, 1H) δ 7.56 (d. j = 2.38, Ar, 1H) ppm; MS (APCI): calcd. For C7H5CIO2 [M]+ 157.87, found 157 [M]+. 3,5-Dichloro-4-hydroxybenzoic acid (15): White needles; 1H NMR (400 MHz, Dimethyl Sulfoxide) δ 11.12 (s, OH, 1H), δ 8.24 (s, Ar, 2H), parts per million; MS: calculated for C7H4CI2O3 [M]+ 210.12, found 210 [M-1]+. 3-Chloro-4-hydroxybenzonitrile (16). White fine needles; 1H NMR (400 MHz, Dimethyl Sulfoxide) δ 8.18 (d, j = 8.56 Hz, Ar, 1H), δ 7.82 (dd, j = 8.54, 1.88 Hz, 1H, Ar), δ 7.86 (d, j = 1.77 Hz, Ar, 1H) ppm; 13C NMR (100 MHz, DMSO): 166.49. 156.91, 131.25, 129.29, 122.41, 119.74, 115.79 ppm; MS: calcd. For C7H4CINO [M]+ 155.66, found 155. 3, 5-Dichloro-4-hydroxybenzonitrile (17): White needles; 1H NMR (400 MHz, Dimethyl Sulfoxide) δ 8.78 (s, Ar, 2H), parts per million; MS: calculated for C7H3CI2NO [M]+ 189, found 188 [M]+.

Figure-2

Credible Mechanism of Oxidative Chlorination

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Table-3

Selectivity of products in the chlorination of various aromatic substrates

Entry Substrate Product Yielda (per cent)

Product Purityb (per cent)

Main Product Others

1. NHCONH3

Cl

NHCONH 3Cl

Cl

97 96.90 3.10

2. COOHOH

COOHOH

C l

83 98.30 1.70

3. CNOH

CNOH

C l

85 98.50 1.50

4.

NHCOPh

NHCOPhCl

93 97 3.00

5. NHCOCH3

Br

NHCOCH 3B r

C l

95 96.35 3.65

6. CHOOH

CHOOH

C l

82 98.20 1.80

a Isolated yield, b Quantification and purity determined by HPLC

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Figure-3

1H spectra of 2, 4-dichloroacetanilide

Figure-4

13C-NMR spectra of 2, 4-dichloroacetanilide

Figure-5

IR spectra of 2, 4-dichloroacetanilide

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Figure-6

Mass spectra of 2, 4-dichloroacetanilide

Figure-7

HPLC chromatogram of 2, 4-dichloroacetanilide

Figure-8

1H-NMR spectra of 2-chloro-4-nitroacetanilide

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Figure-9

Mass Spectra of 2-chloro-4-nitroacetanilide

Figure-10

Mass spectra of 3-chloro-4-hydroxybenzaldehyde

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Figure-11

1H-NMR spectra of 3-chloro-4 hydroxybenzaldehyde

Figure-12

HPLC chromatogram of 3-chloro-4 hydroxybenzaldehyde

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Figure-13

1H-NMR spectra of 5-chlorosalicylic acid

Figure-14

Mass spectra of 5-chlorosalicylic acid

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Figure-15

Mass Spectra of 3-chloro-4-hydroxybenzonitrile

Figure-16

1H-NMR Spectra of 3-chloro-4-hydroxybenzonitrile

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Figure-17

HPLC chromatogram of 3-chloro-4-hydroxybenzonitrile

Figure-18

Mass spectra of 3-chloro-4-hydroxybenzonitrile

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Figure-19

13C-NMR spectra of 3-chloro-4-hydroxybenzonitrile

Figure-20

IR spectra of 3,5-dibromosalisylic acid

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Figure

21 GC-MS spectra of 3, 5-dibromosalicyladehyde

Conclusion

In conclusion, we have established a useful method using N-Chlorosuccinimide as an substitute to sodium periodate, sodium perborate and hydrogen peroxide in the oxidative chlorination of arenes by HCl in aqueous medium. The compensations of this method comprise no use of organic solvent, mild reaction surroundings and good yield of chlorinated product.

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