system action of copper diacetate and triphenylbismuth...

AASCIT Journal of Chemistry 2018; 4(2): 18-26

http://www.aascit.org/journal/chemistry

System Action of Copper Diacetate and Triphenylbismuth Diacetate on the Arylation of a Variety of Heteroarylamine

Abdellah Miloudi1, 2, *

, Mohamed El Hadi Benhalouche2

1Department of Physics / Chemistry, National Polytechnic School of Oran, El Mnaouer, Oran, Algeria 2Laboratory of Fine Chemistry, Department of Chemistry, Faculty of Exact and Applied Sciences, University of Oran-1 Ahmed Ben-Bella, El

Mnaouer, Oran, Algeria

Email address

*Corresponding author

Citation Abdellah Miloudi, Mohamed El Hadi Benhalouche. System Action of Copper Diacetate and Triphenylbismuth Diacetate on the Arylation of

a Variety of Heteroarylamine. AASCIT Journal of Chemistry. Vol. 4, No. 2, 2018, pp. 18-26.

Received: March 22, 2018; Accepted: April 2, 2018; Published: June 1, 2018

Abstract: The triphenylbismuth diacetate reacted selectively with different various groups of primary heteroarylamines in

presence of copper diacetate to engender a new compounds of N-phenyl secondary heteroarylamines in good yields. Moreover,

a similar reaction with 2,5 diaminobenzothiazoles and 2,6- diaminobenzothiazoles gave mixtures of di- and tri phenylated

products of 2,5- and 2,6-aminoobenzothiazoliques.

Keywords: Copper Diacetate, Triphenylbismuth Diacetate, Primary Heteroarylamines, Secondary Heteroarylamines

1. Introduction

The heterocycles belong to the family of compounds

having particular importance in biology and medicine like

agronomy, [1] cosmetic [2] and various pharmaceutical

activities (anti-parasitic, [3, 4] anti-fungal, [5] anti-

inflammatory, [6] and psychotropic [7]).

We present in this paper the arylation reactions that are very

important in organic synthesis. A variety of methods have been

developed reaction of arylation over a 20th century. [8]

The first arylation to obtain the product of biaryls was that

developed by Ullmann in 1901. This reaction consists in

condensing aromatic halides (Scheme 1) in the presence of

copper powder and in the absence of the base. The reaction

requires a high temperature. [9]

Figure 1. First Ullmann condensation with aromatic halides.

The Ullmann reaction was extended to a wide variety of

heterocyclic substrates such as furan, thiophene, pyridine,

pyrimidine, aniline, etc...

In 1903, Ullmann found that the reaction of the acid ortho-

chloro benzoic acid, the aniline and the metallic copper at

reflux led to the N-phenyl-anthranilic acid (Scheme 2). [10]

Tuong & Hida studied later the role of copper in a

condensation reaction of anthracene derivatives. [11]

Figure 2. Synthesis of N-phenyl-anthranilic acid by Ullmann reaction.

The N-phenylation of aniline and amino-cyclohexane with

trivalent triphenylbismuth assisted by the copper diacetate

amount leads to N-monophenyle product with respectively in

48% and 76% of yield under room temperature (Scheme 3

and 4). [12]

Figure 3. Phenylation of aniline under action of triphenylbismuth and

copper diacetate.

AASCIT Journal of Chemistry 2018; 4(2): 18-26 19

Figure 4. Phenylation of aminocyclohexane under action of

triphenylbismuth and copper diacetate.

N-phenylation of aromatic amine such as aniline with

triphenyl bismuth diacetate in the presence of copper at

ambient temperature leads to diphenylamine with a yield

quantitative (Scheme 5). [13]

Figure 5. Synthesis of diphenylamine with triphenylbismuth diacetate.

Similarly, the monophenyl compound 2-methyl-6-

phenylaminobenzothiazole is obtained with 70% yield when

2-methyl-6-amino-benzothiazole was treated with 1.1 molar

equivalents of triphenylbismuth diacetate and 0.1 equivalent

of copper diacetate in dichloromethane at room temperature

(Scheme 6). [14]

Figure 6. Phenylation of 2- methyl-6-phenylaminobenzothiazole.

The derivatives of 1-Me and 2-Me indazole were reacted with 1.1 equivalent of triphenylbismuth diacetate in the presence of

a catalytic quantity of copper diacetate (0.1 equiv) in methylene chloride at room temperature product only N-

monophenylation with 74% and 66% respectively (Scheme 7). [15]

Figure 7. Arylation of indazole derivatives.

We limited this work on the N-arylation or phenylation

reactions that have N-H included mainly in various amino

aromatics and amino heterocyclics, in presence of

organobismuthic agents.

2. Results and Discussion

2.1. Phenylation of Aminobenzimidazolics

Derivatives

The 5- aminobenzimidazole in the presence of 1.1 eq.

triphenyl bismuth diacetate and 0.1 eq. copper diacetate in a

solution of methylene chloride at room temperature, leads

two compounds of mono and diphenylated 1 and 2 with

respectively with 34% and 37% yield. But the 2-chloro- 5-

aminobenzimidazole, with similar conditions gives only

compound 3 in 70%yield.

The 2-aminobenzimidazole leads to only 2-

phenylaminobenzimidazole 4 under normal conditions in

yield of 65%.

Furthermore 1-trimethylsilanebenzimida -zole treated

under the same operating conditions as 1-

phenylbenzimidazole 5 in excellent yield (91%).

The yields of various phenylated aminobenzimidazole 1- 5

are listed in Table -1.

Table 1. Derivatives of obtaining benzimidazole phenylated 1- 5.

Com<pound R1 R2 R3 Yield%

1 H H NHPh 34

2 NPh H NHPh 37

3 H Cl NHPh 70

4 H NHPh H 65

5 NPh H H 91

It is observed that the introduction of the trimethylsilyl

group in the 1-position nitrogen of the imidazole ring

20 Abdellah Miloudi and Mohamed El Hadi Benhalouche: System Action of Copper Diacetate and Triphenylbismuth

Diacetate on the Arylation of a Variety of Heteroarylamine

significantly increases the yield of the reaction with respect

to hydrogen.

2.2. Phenylation of Aminoindolics Derivatives

Phenylation of 5-amino indoles derivatives by

triphénylbimuth diacetate catalyzed by copper diacetate in

methylene chloride at room temperature (Scheme-8) leads to

N- monophenyle compounds 6 - 10 with good to average

yields ranging from 32 to 77%.

Figure 8. Synthesis of phenylated aminoindolics derivatives.

The yields of the products 6 - 10 are summarized in Table 2.

Table 2. Yield of deriving 5- aminophenylindole 6 – 10.

Compound R1 R2 Rdt%

6 H H 60

7 H Me 45

8 Me H 77

9 C(Me)3 H 32

10 COMe H 59

We noted that the phenylation of a methyl group bonded to

the nitrogen of the indole is obtained in good yield. Against by

the tert- butyl group strongly lowers the yield of the reaction.

2.3. Phenylation of Diaminobenzothiazolic

Derivatives

The phenylation of 6-aminobenzo thiazolic and 2-

aminothiazolics derivatives have been cited in literature since

2004.14

We want to describe following these works on the

phenylation of 2,5- and 2,6- diaminobenzothiazoles. This

phenylation was carried out in presence of the system Ph3Bi

(OAc)2 / Cu (OAc)2 (2.2 / 0.1 eq.). N- bi and tri-

phenylaminoobenzothiazolics derivatives compounds are

obtained 11, 12, 13, 14 (Scheme 9).

Figure 9. Obtention of di and tri-phenylaminibenzothiazoles.

Yields of obtaining di- and tri-phenylated compounds 11 to 14 are summarized in Table 3.

Table 3. Yield of compounds di- and tri- phenylaminoobenzothiazolic obtained 11 to 14.

Compound NH2 position yield%

11 5-NH2

55

12 35

13 6-NH2

50

14 30


2.4. Phenylation of Various Hetroaromatic

Amines

We wanted in this case to phenyl some aromatic amines of

varied structures by triphenylbismuth diacetate under copper

diacetate catalysis in solution of CH2Cl2 at room temperature.

Different phenylations were conducted on the following

compounds:

2.4.1. Phenylation of 5-Aminoisatine

The reaction took place only at the nitrogen grafted on the

benzene ring (Scheme 10). The monophenylated product was

isolated with a low yield.

Figure 10. Phenylation of 5-aminoisatine.

2.4.2. Phenylation of 4-Aminophtalimide

Also the 4-aminophthalimide underwent phenylation on the primary amino group of the aromatic ring by conducting the

monophenyl compound 16 with a yield of 25% (Scheme 11).

Figure 11. Phenylation of 4-aminophtalimide.

2.4.3. Phenylation of 2-Aminoindan-1,3-dione

Of the same phenylation of 2-aminoindan-1,3-dione by the presence of system BiV / CuII leads to compound 17 with yield

30% (Scheme 12).

Figure 12. Phenylation of 2-Aminoindan-1,3-dione.

2.4.4. 2-Amino-4-methylpyrimidine

The mixture consisting of 2-Amino-4-methylpyrimidine, triphenylbismuth diacetate and copper diacetate in solution in

dichloromethane gives the 2-(phenylamino)-1H-indene-1,3(2H)-dione 18 with a yield of 60% (Scheme 13).

Figure 13. Phenylation of 2-amino-4-methylpyrimidine.

2.4.5. 2-aminonicotinic Acid

The same procedure is performed on the substrate 2-aminonicotinic acid. The compound obtained 19 is also obtained in the



order of low to medium yield 26% (Scheme 14).

Figure 14. Phenylation of 2-aminonicotinic acid.

2.4.6. (1S,2R)-1-amino 2, 3-dihydro-1H-indenol

When the system of bismuth pentavalent and copper diacetate is in the mixture with the substrate Cis-1-amino-2-indanol, the

compound-monophyle (1S,2R)-1-(phenylamino)-2,3-dihydro-1H-inden-ol 20 is only produced with a yield of 70%, but the

compounds from the O- phenylation 20a or the O- and N- diphenylation 20b are not formed (Scheme-15).

Figure 15. Phenylation of (1S,2R)-1-amino 2,3-dihydro-1H-indenol.

2.4.7. 4-Amino-2-methylquinoline

The same phenylation reaction of 4-Amino-2-methylquinoline is carried in the same procedure as previously, in leading to

desired product 21 in excellent yield (90%) (Scheme 16).

Figure 16. Phenylation of 4-amino-2-methylquinoline.

In any cases, we find that, the attack is done only at the

level of the exocyclic nitrogen atom. This atom seems to be

the most responsive to have labile proton N-H

We note also a good returns for compound 20 (70%) and

21 (90%), by cons for the other compounds yields are poor.

These low yields can probably be explained by the presence

of conjugaison and carbonyl groups.


3. Experimental Section

3.1. General Procedures

Melting points were determined by the Büchi Melting

Point apparatus and are not corrected. The 1H and

13C NMR

spectra were measured on a Bruker Avance 300 spectrometer

operating at 500 MHz for 1H NMR and 125MHz for

13C

NMR.

Chemical shifts were recorded as units relative to DMSO-

d6 or CDCl3 as the solvent unless otherwise stated, and J

values in Hertz. Combustion analyses were performed in the

("Laboratoire de Microanalyse du centre National de la

Recherche Scientifique", Vernaison (France)). Separations by

chromatography were performed with "silica gel" Merck.

3.2. General Procedure of Preparation of N-

phenylaminoheteroaromatics

Derivatives

Into a two-necked flask under a nitrogen atmosphere, 1 eq.

of aminoaromatic derivative, 1.1 eq. triphenyl bismuth

diacetate, 0.1 eq. copper diacetate in solution in a variable

volume (x mL) of CH2Cl2 according to the substrate. The

mixture was stirred at room temperature for 5 hours. The

solution is filtered, evaporated. Then, the residue is purified

by chromatography on a silica column; eluent: diethyl ether /

pentane (1/1) for N-phenylaminobenzimidazolic, N-

phenylaminoindole and N-phenylaminobenzothiazolic

derivatives and with the ethyl acetate / pentane (1/1) for

others products of N-phenylaminoheteroaromatics

derivatives.

I- N-Phenylation of Benzimidazole Derivatives

* Reaction with 5- aminobenzimidazole

0.5 g (3.07 mmol) of 5-aminobenzimidazole

1.88 g (3.37 mmol) of triphenylbismuth diacetate

0.056 g (0.31 mmol) of Cu(OAc)2

15 mL of CH2Cl2.

Products obtained:

(Benzimidazol-5-yl) phenylamine 1, M= 209.5g/mol, m =

217 mg, (1.04 mmol), mp: 345°C, Yield: 34%. 1H NMR (δ ppm, DMSO-d6): 8.66 (s, 1H), 8.20 (s, 1H),

7.59 (m, 5H), 7.48 (d, 1H, J = 8.7 Hz), 6.72, (dd, 1H, J =1.5

Hz and 8.5 Hz), 6.45 (d, 1H, J = 1.5 Hz); 13

C NMR (δ ppm,

DMSO-d6): 146.36, 140.52, 136.80, 135.96, 134.72, 130.24,

127.55, 123.69, 120.34, 112.35, 93.94.

(1-Phényl-benzimidazol-5yl) phénylamine 2, M= 285.34

g/mol, m = 327 mg, (1.15 mmol), mp: 370°C, Yield: 37%. 1H NMR (δ ppm, CDCl3): 7.74 (d, 1H, J = 8.5 Hz), 7.51 (t,

2H, J = 7.1 Hz), 7.45 (sbr, 2H), 7.26 (sbr, 2H), 7.22 (d, 2H, J

= 7.4 Hz), 7.21 (sbr, 1H), 7.20 (s, 1H), 7.08 (dd, 1H, J = 2.1

Hz et 8.5 Hz), 6.87 (t, 1H, J = 7.4 Hz), 6.72 (dd, 1H, J=1.20

Hz and 7.50 Hz); 13

C NMR (δ ppm, CDCl3): 156.43, 144.10,

139.65, 136.40, 130.05, 129.40, 127.94, 126.96, 123.94,

122.82, 121.14, 120.52, 116.78, 116.55, 100.07.

* Reaction with 5- amino-2- chlorobenzimidazole

0.650 g (3.90 mmol) of 5-amino-2-chlorobenzimidazole

2.396 g (4.29 mmol) of triphénylbismuth diacetate

0.071 g (0.39 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(2-Chloro-benzimidazol-5yl) phenylamine 3, M= 243.69

g/mol, m = 665 mg, (2.73 mmol), mp: 180°C, Yield: 70%. 1H NMR (δ ppm, DMSO-d6): 7.68 (sbr, 1H), 7.54 (sbr, 1H),

7.36 (s, 1H), 7.18 (m, 2H), 7.05 (m, 2H), 6.78 (m, 1H); 13

C

NMR (δ ppm, DMSO-d6): 174.98, 151.77, 145.40, 130.99,

130.29, 129.50, 128.31, 127.63, 116.69, 112.87, 109.25.

* Reaction with 2- aminobenzimidazole

0.5 g (3.760 mmol) of 2-amino-benzimidazole


0.068 g (0.37 mmol) of Cu(OAc)2

15 mL de CH2Cl2

Product obtained:

(Benzimidazol-2-yl)-phénylamine 4, M= 209.25 g/mol, m

= 511 mg, (2.44mmol), mp: 160°C, Yield: 65%. 1H NMR (δ ppm, DMSO-d6): 8.17 (s, H), 7.60, (sbr, 4H),

7.43, (dd, 2H, J = 8.70 Hz and 4.5 Hz), 6.76, (sbr, 1H), 6.63,

(dd, 2H, J = 6.6 Hz et 1.3 Hz); 13

C NMR (δ ppm, DMSO-d6):

146.29, 140.41, 135.96, 134.66, 130.16, 127.44, 123.66,

120.27, 112.22, 93.83.

* Reaction with 1- trimethylsilane benzimidazole

0.4 g (2.10 mmol) of 1-trimethylsilanebenzimidazole


0.038 g (0.21 mmol) of Cu(OAc)2

15 mL of CH2Cl2.

Product obtained:

1-Phenyl-benzimidazole 5, M= 194.23 g/mol, m = 371 mg,

(1.91 mmol), mp: 250°C, Yield: 91%. 1H NMR (δ ppm, DMSO-d6): 8.56 (s, 1H), 7.80 (td, 1H, J

=7.4 Hz et 2.70 Hz), 7.60 (t, 2H, J = 7.2 Hz), (d, 2H, J = 8.3

Hz), 7.43 (td, 1H, J =7.0 Hz et 1.5 Hz), 7.29 (q, 2H, J=8.9

Hz, 4.9 Hz and 2.0 Hz), 7.14 (t, 1H, J = 4.8 Hz); 13

C NMR (δ

ppm, DMSO-d6): 137.80, 136.23, 132.33, 130.27, 128.35,

127.93, 123.85, 123.76, 122.77, 120.26, 110.89

II- N-PHENYLATION Of AMINOINDOLES

DERIVATIVES

* 5-AMINOINDOLE

0.224 g (1.71 mmol) of 5-aminoindole


0.031 g (0.171 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(Indol-5-yl) phenylamine 6, M= 208.26 g/mol, m = 214

mg, (1.03 mmol), mp: 131°C, Yield: 60%. 1H NMR (δ ppm, DMSO-d6): 10.93, (s, 1H), 7.72, (s, 1H),

7.33, (d, 1H, J = 8.7 Hz), 7.28, (sbr, 2H), 7.13, (t, 2H, J =

7.1Hz), 6.92, (d, 3H, J = 8.5Hz), 6.65 (t, 1H, J = 7.2Hz),

6.33, (se, 1H); 13

C NMR (δ ppm, DMSO-d6): 146.76, 134.81,

132.37, 129.15, 128.38, 125.75, 117.59, 116.70, 114.39,

111.97, 110.91, 108.84

* 5-AMINO-2-METHYLINDOLE

0.20 g (1.379 mmol) of 5-amino-2-methyl-indole


0.05 g (0.275 mmole) of Cu(OAc)2

20 mL of CH2Cl2



Product obtained:

(2-Methyl-indol-5yl)phenylamine 7, M= 222.29 g/mol, m

= 138 mg, (0.62 mmol), mp: 151°C, Yield: 45%. 1H NMR (δ ppm, DMSO-d6): 7.66 (s, 1H), 7,20 (d, 1H, J

=.5 Hz), 7.12 (t, 2H, J = 7.1 Hz), 6.90 (d, 1H, J = 8.3 Hz),

6.82 (d, 2H, J = 8.5 Hz), 6.64 (t, 1H, J = 7.2 Hz), 6.03 (s,

1H), 2.36,(s, 3H); 13

C NMR (δ ppm, DMSO-d6): 146.85,

136.14, 134.55, 132.60, 129.42, 129.13, 118.54, 117.42,

114.22, 111.00, 110.48, 99.04, 13.69).

* 5-AMINO-1-N-METHYL-INDOLE

0.176 g (1.630 mmol) du 5-amino-1-methylindole

1 g (1.792 mmol) of triphenylbismuth diacetate

0.03 g (0.163 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(1-Methyl-indol-5yl) phenylamine 8, M= 222.29 g/mol, m

= 279 mg, (1.26 mmol), mp: 95°C, Yield: 77%. 1H NMR (δ ppm, DMSO-d6): 7.76 (s, 1H), 7.34 (d, 1H, J =

8.5 Hz), 7.28 (sbr, 1H), 7.24 (d, 1H, J = 3.1 Hz), 7.13 (t, 2H,

J = 8.3 Hz), 6.98 (d, 1H, J = 6.1 Hz), 6.94 (d, 2H, J = 11.0

Hz), 6.66 (t, 1H, J = 7.4 Hz), 6.30 (d, 1H, J = 2.8 Hz), 3.75

(s, 3H). 13

C NMR (δ ppm, DMSO-d6): 146.48, 135.06,

132.95, 130.02, 129.15, 128.75, 117.71, 116.53, 114.43,

110.96, 110.26, 99.91, 32.68.

* 1-TERTIOBUTYL-5-AMINOINDOLE

0.26 g (1.383 mmol) of 1-tert-butyl-5-aminoindole


0.026 g (0.138 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(1-Tert-butyl-indol-5yl)phenylamine 9, M = 264.36 g/mol,

m = 117 mg, (0.44mmol), mp: 75°C, Yield: 32%. 1H NMR (δ ppm, DMSO-d6): 8.13 (s, 1H), 7.32 (d, 1H, J =

8.5 Hz), 7.30 (d, 2H, J = 8.2 Hz), 7.11 (m, 3H), 6.90 (d, 1H, J

= 8.5 Hz), 6.24 (d, 1H, J = 8.2 Hz), 5.90 (d, 1H, J = 8.2 Hz),

1.68 (s, 9H); 13

C NMR (δ ppm, DMSO-d6): 145.15, 142.86,

135.18, 134.17, 133.65, 121.29, 119.83, 115.33, 114.15,

107.57, 103.91, 89.79, 23.94, 18.93.

* 1-ACETYL-5-AMINOINDOLINE

0.135 g (0.844 mmol) of 1-acetyl-5-aminoindoline

0.517 g (0.928 mmol) of Ph3Bi(OAc)2

0.0153 g (0.084 mmol) of Cu(OAc)2

20 mL of CH2Cl2

Product obtained:

(1-Acetyl-indolin-5-yl) phenylamine 10, M = 252.31

g/mol, m = 126 mg, (0.5mmol), mp: 168°C, Yield: 59%. 1H NMR (δ ppm, DMSO-d6): 8.13 (s, 1H), 7.96 (s, 1H),

7.20 (t, 2H, J = 6.6 Hz), 7.05 (sbr, 3H), 6.89 (d, 1H, J = 6.8

Hz), 6.73 (d, 1H, J = 8.1 Hz), 4.04 (t, 2H, J = 7.1 Hz), 3.02

(t, 1H, J = 7.6 Hz), 2.13 (s, 3H); 13

C NMR (δ ppm, DMSO-

d6): 168.63, 146.48, 135.06, 132.95, 130.00, 129.15, 128.75,

117.71, 116.53, 114.43, 110.96, 110.26, 99.91, 32.68

III- Phenylation of diaminobenzothiazolics derivatives

* 2, 5-Diamino-1,3-benzothiazole

0.135 g (0.844 mmol) of 1-acetyl-5-aminoindoline

0.517 g (0.928 mmol) of Ph3Bi(OAc)2

0.0153 g (0.084 mmol) of Cu(OAc)2

20 mL of CH2Cl2

Products obtained:

a) (Benzothiazol-2,5-yl) diphenylamine 11, M = 393.50

g/mol, m = 183 mg, (0.46 mmol), mp: 96°C, Yield: 55%. 1H NMR (δ ppm, CDCl3): 7.51 (s, 1H), 7.48 (s, 1H), 7.45

(m, 2H), 7.43 (m, 2H), 7.32 (sbr, 1H), 7.30 (m, 1H), 7.28 (sbr,

2 H), 7.23 (s, 1H), 7.11 (m, 1H), 7.04 (d, 2H, J = 7.5 Hz),

6.99 (t, 1H, J = 7.2 Hz); 13

C NMR (δ ppm, CDCl3): 166.33,

142.27, 141.21, 139.01, 138.62, 133.71, 130.03, 129.61,

127.09, 121.14, 121.56, 119.01, 118.55, 116.16, 109.23

Elemental analysis (found C=72.15%, H=5.16%,

N=13.53%, calc C=71.90%, H=4.76%, N=13.24%).

b) (3-Phenyl-2-phenylimino-benzothiazol-5-yl)

phenylamine 12, M = 393.50 g/mol, m = 116 mg,

(0.29mmol), mp: 96 °C, Rdt: 35%. 1H NMR (δ ppm, DMSO-d6): 8.08 (s, 1H), 7.61 (d, 2H, J =

7.3 Hz), 7.57 (t, 2H, J = 8.5 Hz), 7.49 (t, 1H, J = 7.2 Hz),

7.31 (t, 2H, J = 7.4 Hz), 7.30 (sbr, 1H), 7.17 (t, 2 H, J= 7.5

Hz), 7.04 (t, 1H, J = 7.4 Hz), 6.94 (d, 2H, J = 7.3 Hz), 6.98

(d, 2H, J = 7.6 Hz), 6.92 (d, 1H, J = 8.3 Hz), 6.74 (t,1 H, J =

7.3 Hz), 6.54 (d, 1H, J = 8.7 Hz); 13


d6): 156.02, 151.13, 144.32, 138.62, 136.85, 134.54, 129.90,

129.51, 129.20, 128.60, 128.47, 123.36, 122.20, 121.12,

119.10, 117.29, 115.68, 112.48, 110.73. Elemental analysis

(found C=76.66%, H=4.99%, N=10.78%, calc C=76.31%,

H=4.87%, N=10.68%).

* 2,6-DIAMINO -1,3-BENZO THIAZOLE

0,680 g (4.12 mmol) 2,6-diamine -1,3-benzothiazole

2,53 g (4.532 mmol) of triphenylbismuth diacetate

0,153 g (0. 824 mmol) of copper (II) diacetate

50 mL of CH2Cl2

Products obtained:

a) (Benzothiazol-2,6-yl) diphenylamine 13, M = 317.41

g/mol, m = 653 mg, (2.06 mmol), mp: 120 °C, yield: 50%. 1H NMR (δ ppm, DMSO-d6): 10.35, (s, 1H), 8.12, (s, 1H),

7.76, (m, 1H), 7.53, (m, 1H), 7.49, (d, 1H, J = 8.8 Hz), 7.35,

(m, 3H), 7.21, (t, 2H, J =7.4 Hz), 7.05, (d, 2H, J = 8.4 Hz),

7.00, (t, 2H, J = 7.3 Hz), 6.77, (t, 1H, J = 7.5Hz); 13

C NMR

(δ ppm, DMSO-d6): 159.51, 146.25, 144.27, 140.90, 138.59,

137.33, 130.32, 129.20, 128.97, 121.63, 119.69, 119.07,

117.43, 115.85, 109.48. Elemental analysis (found

C=72.12%, H=5.09%, N=13.65%, calc C=71.90%,

H=4.76%, N=13.24%).

b) (3-Phenyl-2-phenylimin-benzothiazol-6-yl)

phenylamine 14, M= 393.50 g/mol, m = 486 mg, (1.24

mmol), mp: 110 °C, Yield: 30%. 1H NMR (δ ppm, DMSO-d6): 8.10 (s, 1 H), 7.60 (d, 2H, J

= 7.8 Hz), 7.57 (d, 2H, J = 6.4 Hz), 7.50 (d, 2 H, J = 7.4 Hz),

7.44 (m, 1H), 7.33 (t, 1 H, J = 7.0 Hz), 7.17 (t, 2H, J = 7.6

Hz), 7.04 (t, 1 H, J = 7.4 Hz), 6.99 (t, 2 H, J = 7.4 Hz), 6.95

(t, 2 H, J = 7.7 Hz), 6.92 (d, 1 H, J = 2.1), 6.75 (t, 1 H, J =

7.2 Hz), 6.55 (m, 1 H); 13

C NMR (δ ppm, DMSO-d6): 156.03,

144.24, 138.54, 137.09, 134.46, 129.86, 129.48, 129.17,

128.55, 128.43, 126.45, 123.32, 122.16, 121.10, 119.12,

117.20, 115.59, 112.39, 110.69. Elemental analysis (found

C=76.69%, H=4.96%, N=10.73%, calc C=76.31%,

H=4.87%, N=10.68%).


IV Phenylation of various aminohetroaromatics

* 5-AMINOISATINE

0.5 g (3.1 mmol) of 5-aminoisatine


0.054 g (0.31 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

5-Phenylaminoisatine 15, M= 238.24 g/mol, m = 148 mg,

(0.62 mmol), mp: 170-172 °C, Yield: 20%. 1H NMR (δ, ppm,

DMSO-d6): 8.32 (d, 1H, J =2.5 Hz), 8.19 (dd, 1H, J = 2.4 Hz

et 8.70 Hz), 7.64 (t, 2H, J = 7.6 Hz), (t, 1H, J = 7.5 Hz), 7.43

(d, 2H, J = 8.2 Hz), 6.85 (d, 1H, J = 8.7 Hz); 13

C NMR (δ,

ppm, DMSO-d6): 196.26, 188.68, 172.01, 164.18, 140.41,

130.10, 128.89, 126.83, 126.66, 119.75, 117.07, 109.12.

* 4-AMINOPHTHALIMIDE

0.237 g (1.466 mmol) of 4-aminophthalimide


0.026 g (1.15 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(Phthalimide –5-yl) phenylamine 16, M= 238.24 g/mol, m

= 87 mg, (0.37 mmol), mp: 210 °C, Yield: 25%. 1H NMR (δ, ppm, DMSO-d6): 10.95 (s, 1H), H-8 = 9.10 (s,

1H), H-7 = 7.60 (d, 1H, J = 8.7 Hz), H-11 = 7.37 (t, 2H, J =

7.2 Hz), H-10 = 7.24 (m, 2H), H-4 = 7.21 (sbr, 1H), H-6 =

7.21 (sbr, 1H), H-12 = 7.07 (t, 1H, J = 7.0 Hz); 13

C NMR (δ,

ppm, DMSO-d6): 230.01, 207.63, 169.46, 150.31, 140.80,

135.42, 129.70, 124.99, 123.08, 120.44, 118.40, 107.50.

* 2-AMINO-1,3-INDANEDIONE

0.3 g (1.875 mmol) of 2-amino-indan-1,3-dione


0.034 g (0.187 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(1, 3-Dione –indan-2-yl) phenylamine 17, M= 237.25

g/mol, m = 133 mg, (0.56 mmol), mp: 110 °C, Yield: 30%. 1H NMR (δ ppm, DMSO-d6): 7.47 (s, 1H), 7.41 (sbr 1H),

7.39 (m, 1H), 7.27 (m, 1H), 7.02 (sbr, 1H), 7.00 (m, 1H), 6.80

(m, 1H), 6.52 (m, 1H), 5.86 (s, 1H); 13

C NMR (δ ppm,

DMSO-d6): 181.63, 181.63, 156.00, 130.20, 129.59, 121.36,

120.83, 118.77, 116.80, 113.50, 123.59, 78.00

* (1S,2R)-1-amino2,3-dihydro-1H-indenol

0.25 g (1.675 mmol) of (1S,2R) – (-) cis-1-amino-2-

indanol


0.03 g (0.167 mmol) of Cu(OAc)2

15 mL of CH2Cl2

Product obtained:

(1S,2R)-1-(phenylamino)-2,3-dihydro-1H-inden-2-ol 18,

M= 225.29 g/mol, m = 264 mg, (1.2mmol), oil, Yield: 70%. 1H NMR (δ ppm, DMSO-d6): 7.26 (d.1H. J=7.3 Hz), 7.26

(d.1H. J=7.3Hz), 7.21 (t, 1H, J=6.7), 7.17 (t, 1H, 7.2Hz),

7.13 (t, 1H, 8.1Hz), 6.86 (d, 2H, J=8.1Hz), 6.60 (t, 1H, J=7.2

Hz), 5.54 (d,1H, J=9.0Hz), 4.90 (dd, 1H, J=8.6, 4.5Hz), 4.86

(d, 1H, J=4.1Hz), 4.56 (q, 1H, J=4.0Hz), 3.07 (dd, 1H, J=16,

4.60Hz), 2.85 (d, 1H, J=6.1Hz); 13


d6): 148.86, 143.61, 140.94, 129.08, 127.25, 126.29, 125.08,

124.24, 116.17, 112.4, 71.99, 60.72, 39.83.

* 2-aminonicotinic acid

0.5g (3.623 mmol) of 2-aminonicotinic acid

2.224g (3.985 mmol) of triphenylbismuth diacetate

0.066 g (0.362 mmol) of Cu(OAc)2

15 mL of CH2Cl2

2-(phenylamino) nicotinic acid 19, M= 214.22 g/mol, m =

201 mg, (0.94 mmol), mp: oil, Yield: 26%. 1H NMR (δ ppm, DMSO-d6): 8.37 (d.1H. J=6.0 Hz), 7.72

(t,1H, J=5.5Hz), 7.39 (t, 2H, J=6.0Hz), 7.57 (d, 1H, J=5.4Hz),

7.25 (dd, 2H, J=5.2,2.6Hz), 7.22 (s, 1H), 6.71 (t, 1H, J=6.0 Hz); 13

C NMR (δ ppm, DMSO-d6): 165.43, 160.07, 155.01, 150.59,

140.46, 137.38, 131.14, 130.47, 112.31.

* 4-Amino-2-methylquinoline

0.25g (1.58 mmol) of 4-Amino-2-methylquinoline

0.969g (1.74 mmol) of triphenylbismuth diacetate

0.03 g (0.167 mmol) of Cu(OAc)2

15 mL of CH2Cl2

(2-methyl-quinolin-4-yl)-phenylamine 21, M=234.30

g/mol, m = 333 mg, (1.4 mmol), mp: 305°C, Yield: 90%. 1H NMR (δ ppm, DMSO-d6): 8.32 (d.1H. J=8.3 Hz), 7.78

(d,1H, J=8.3Hz), 7.64 (t, 2H, J=6.8Hz), 7.45 (d, 2H, 7.2Hz),

7.41 (t, 1H, 8.3Hz), 7.41 (t, 1H, J=6.0Hz), 7.37 (t, 1H, J=6.8

Hz), 6.84 (s,1H), 2.44 (s, 3H); 13

C NMR (δ ppm, DMSO-d6):

158.85, 148.80, 147.96, 140.97, 127.25, 129.35, 128.60,

123.66, 122.13, 11.62, 101.63, 25.32.

4. Conclusion

The use of triphenyl bismuth diacetate by catalysis with

copper diacetate allowed us to phenyle various heterocyclic

amines pattern aminobenzimidazole, amonoindole and

aminobenzo -thiazole derivatives and others various

aminoheteroaromatic derivatives studied under mild and

neutral conditions.

The yields of the isolated arylamine vary depending on the

structure of the amine used.

The obtained compounds were characterized by physical

properties suitable namely the melting point and magnetic

resonance of proton and carbon 13.

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system action of copper diacetate and triphenylbismuth...

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