Synthesis of a new series of 2-(2-hydroxynaphthylazo)aryltellurium compounds

Article abstract of DOI:10.1080/10426507.2010.485154

A new series of 2-(2-hydroxynaphthylazo)arylmercury chlorides (Ia-Ib) were prepared by azo coupling of diazonium salts of 2-aminophenyl-, 2-amino-5-bromophenyl-, 2-amino-5-methylphenyl-, and 2-amino-5- nitrophenylmercury chlorides with 2-naphthol. Reactio

Full text of DOI:10.1080/10426507.2010.485154

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Phosphorus, Sulfur, and Silicon and the
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Synthesis of a New Series of 2-(2-
Hydroxynaphthylazo)aryltellurium
Compounds
Ali Z. Al-Rubaie a , Adil A. Al-Fregi a & Shaker A. S. Al-Jadaan b
a Department of Chemistry, College of Science , University of
Basrah , Basrah, Iraq
b Department of Chemistry, College of Pharmacy , University of
Basrah , Basrah, Iraq
Published online: 13 Jan 2011.
To cite this article: Ali Z. Al-Rubaie , Adil A. Al-Fregi & Shaker A. S. Al-Jadaan (2010) Synthesis of a
New Series of 2-(2-Hydroxynaphthylazo)aryltellurium Compounds, Phosphorus, Sulfur, and Silicon and
the Related Elements, 186:1, 115-124, DOI: 10.1080/10426507.2010.485154
To link to this article: http://dx.doi.org/10.1080/10426507.2010.485154
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Phosphorus, Sulfur, and Silicon, 186:115–124, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.485154
SYNTHESIS OF A NEW SERIES
OF 2-(2-HYDROXYNAPHTHYLAZO)ARYLTELLURIUM
COMPOUNDS
Ali Z. Al-Rubaie,1 Adil A. Al-Fregi,1
and Shaker A. S. Al-Jadaan2
1Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq
2Department of Chemistry, College of Pharmacy, University of Basrah,
Basrah, Iraq
GRAPHICAL ABSTRACT
R
R
R
TeBr 2
Cl
TeBr4
Hg
Te Br 3
N
N
N
2
N
N
N
Ar
Ia-Id
Ar
IIIa- IIId
IIa - IId
Ar
R
R
Te
N
Te
N
N
Ar
Vc- Vd
N
2
Ar
IVa - IVc
OH
R: a= H ; b= Br; c= CH3; d= NO2; Ar =
Abstract A new series of 2-(2-hydroxynaphthylazo)arylmercury chlorides (Ia–Ib) were pre-
pared by azo coupling of diazonium salts of 2-aminophenyl-, 2-amino-5-bromophenyl-, 2-
amino-5-methylphenyl-, and 2-amino-5-nitrophenylmercury chlorides with 2-naphthol. Re-
actions of compounds Ia–Ib with tellurium tetrabromide in 1:1 and 2:1 molar ratios in
dry dioxane gave 2-(2-hydroxynaphthylazo)aryltellurium tribromides (IIa–IId) and bis(2-(2-
hydroxynaphthylazo)aryl)tellurium dibromides (IIIa–IIId), respectively, in good yields. Re-
duction of compounds IIa–IIc and IIIc–IIId by ethanolic hydrazine hydrate gave the cor-
responding ditellurides (IVa–IVc) and tellurides (Vc–Vd), respectively, in moderate to good
yields. Treatment of compounds IIIb and IIId with [Pd(PPh3)4] in acetonitrile gave new
Received 3 February 2010; accepted 7 April 2010.
The authors thank the Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq,
for providing facilities and the Petroleum Research Center, Tripoli, Libya, for providing some of the NMR
spectroscopic data.
Address correspondence to Ali Z. Al-Rubaie, Department of Chemistry, College of Science, University of
Basrah, Basrah, Iraq. E-mail: alrubaie49@yahoo.com
115

116
A. Z. AL-RUBAIE ET AL.
symmetrical biaryls containing azo groups. All compounds were characterized by spectroscopic
data and elemental analysis.
Keywords Azo compounds; coupling reactions; mercury(II) chloride; organotellurium com-
pounds; palladium(0)
INTRODUCTION
There are few examples of tellurated derivatives of azobenzene in the literature,
although the first example was prepared in 1979,1 by mercuration of azobenzene followed by
trans-metallation with tellurium tetrachloride. This method provided a satisfactory route to
tellurated azobenzene.1 2-Phenylazophenyl(C,Nꢁ)tellurium trichloride was also prepared by
a direct reaction of azobenzene with tellurium tetrachloride.2 Several new organotellurium
compounds derived from 4-aminoazobenzene were prepared by reaction of 3-HgCl-4-NH2-
C6H3N NC6H5 with TeBr4 or p-CH3OC6H4TeCl3.3 Organotellurium containing an azo
group, such as 2-phenylazophenyl(C,Nꢁ) tellurium(II)-halides4 and pseudohalides5,6 were
prepared by metathesis. Sodium benzene- and 4-methoxybenzenetellurolate was added to
the C C triple bond in 4-nitrophenyl- and 3-nitrophenylethyne and concomitantly catalyzed
the reduction of the nitro groups to azo groups by sodium borohydride.7 Reduction of
(3,5-dimethylphenyl)(2-nitrophenyl)tellurium(II) gave the first example of an azo group
bridging two tellurium(II) centers.8 Reaction of 4-CH3-2-TeClC6H3N NC6H4-4-CH3 with
silver perchlorate gave 4,5-benzo-1,2,3-telluradiazolium perchlorate as a first example of a
compound containing a tellurazole ring.9
It is worth noting that there is a considerable interest in preparation of organomercury
and organotellurium compounds possessing a photoactive substituent such as CH N.10
This article describes the synthesis of several new types of organotellurium compounds
containing an azo group (Figure 1) by diazo-coupling reaction of halomercury-substituted
diazobenzene derivatives and transmetallation from mercury to tellurium. Furthermore, the
use of tellurium dibromides derivatives IIIb and IIId in organic synthesis using [Pd(PPh3)4]
is also described.
RESULTS AND DISCUSSION
In the present study, 2-aminoarylmercury chlorides were satisfactorily diazotized
at 0–5◦C by sodium nitrite solution to form the corresponding diazonium salts, and by
Ar2Te 2
Ar2TeBr 2
Ar2Te
ArTeBr3
IIa-IId
IIIa-IIId
IVa-IVc
Vc-Vd
OH
2
3
3'
4'
1
2'
5'
4
6
N
N
R
Ar =
1'
5
10
6'
9
7
8
R;
a= H; b= Br; c= CH3; d= NO2
Figure 1 General structure formula.

2-(2-HYDROXYNAPHTHYLAZO)ARYLTELLURIUM COMPOUNDS
117
subsequent coupling with 2-naphthol, the required 2-(2-hydroxy-naphthylazo)arylmercury
chlorides [i.e., 2-HOC10H6N NC6H4-1-HgCl-5-R; where 2-HOC10H6 = 2-hydroxy-
naphthyl, R H (Ia), Br(Ib), CH3(Ic), NO2(Id)] were obtained in good yields
(Scheme 1). Reaction of tellurium tetrabromide with the corresponding 2-(2-hydroxy
naphthylazo)arylmercury chloride in 1:1 and 1:2 molar ratio gave the tribromides (IIa–IId)
and the dibromides (IIIa–IIId) derivatives, respectively, as dark brown solids in good
yields (Scheme 1). Reduction of compounds IIa–IIc and IIIc–IIId using ethanolic
hydrazine hydrate gave the ditellurides IVa–IVc and the tellurides Vc–Vd, respectively in
moderate to good yields (Scheme 1).
In general all the prepared compounds are reddish brown to dark brown solids
with high melting points, and they are soluble in common organic solvents. The carbon,
hydrogen, and nitrogen analyses for these compounds agreed well with the calculated
values and are presented in Table 1.
The FT-IR spectra of all mercurated and tellurated azo derivatives show the disappear-
ance of the asymmetric and symmetric stretching bands near 3450–3300 and 1450 cm−1
due to the N H bonds of NH2. This supports the conversion of primary amino groups to
azo groups. The stretching of N N bonds could not be observed, as they are proba-
bly masked by the aromatic vibrations. In general, the IR spectra of compounds IIa–IId,
IIIa–IIId, IVa–IVc, and Vc–Vd are quite similar to those of azo organomercury chloride
derivatives (i.e., compounds Ia–Id), which confirms that telluration has occurred at the
position initially occupied by HgCl. For compounds Id, IId, IIId, and Vd, the bands at
1363–1330 cm−1 and 1573–1531 cm−1 are assigned to the symmetrical and asymmetrical
stretching vibration of the NO2 group, respectively.11,12
The UV-Vis spectra of all compounds were recorded in absolute ethanol solution
at 10−4 M. Generally, the UV-Vis spectra for all compounds showed three absorption
regions. The first region appeared around 208nm (ε = 9150–11510 M−1 cm−1), which
may be attributed to π → π∗ transition of the benzene ring.10–12 The second band was
observed around 228 nm (ε = 9510–11990 M−1 cm−1), which is due to π → π∗ transition
of the naphthyl rings.11–13 The third band was observed as a broad shoulder between
473–480 nm (ε = 2384–4000 M−1 cm−1), which is attributed to π → π∗ transition of the azo
groups.11–13
The 1H NMR spectra of the synthesized compounds show that the resonance of the
aromatic rings were observed in the range 6.94–8.58 ppm. The signal characteristic of the
proton of the hydroxyl group was observed in region 8.00–11.23 ppm. The 1H NMR spectra
of all compounds show that in each case a distinct doublet appears between 6.94–7.12 ppm
due to H3 of the naphthyl group (Table 1). The 1H NMR data for the studied compounds
are presented in Table 1. The 13C NMR spectra for compounds IIb and Vc agree well with
their structures (Table 1).
When tellurium dibromides IIIb and IIId were reacted with Ph(PPh3)4 in
acetonitrile,1415 the corresponding biaryls (i.e., 2,2ꢁ-bis(2-hydroxynaphthylazo)5,5ꢁ-
dibromobiphenyl (VIb) and 2,2ꢁ-bis(2-hydroxynaphthylazo)5,5ꢁ-dinitrobiphenyl (VId)
were obtained in 75% and 84% yields, respectively, as the only products (Scheme 2).
Both compounds gave satisfactory elemental analysis, and their IR and UV-Vis spectra are
similar to the spectra of tellurated azo compounds.
In conclusion, we have introduced a new and efficient synthetic route for preparation
of a new range of organotellurium compounds containing azo groups. These compounds
could be useful for synthesis of organic compounds and as organic dyes.

118

2-(2-HYDROXYNAPHTHYLAZO)ARYLTELLURIUM COMPOUNDS
119
Table 1 CHN analysis and 1H NMR data for the new mercurated and tellurated azo compounds based on
2-(2-hydroxynaphthylazo)aryl
Elemental analysis% Found (calcd.)
Compounds
C
H
N
1H NMR(DMSO-d6) TMS = 0 ppm
Ia
39.55(39.76) 2.33(2.29) 5.78(5.80) 6.95(d, 1H, Ar H); 7.48–7.65(m, 5H, Ar H);
7.78–7.98(m,4H, Ar H+OH); 8.58(d, 1H, J =
8.1Hz, Ar H).
Ic
40.91(41.05) 2.46(2.63) 5.88(5.63) 2.26(s, 3H, CH3); 6.94(d, 1H, J = 8.3Hz, Ar H);
7.27–7.36(m, 4H. Ar H); 7.63–7.69(m, 4H. Ar H);
7.75(d, 1H, Ar H); 7.87(d, 1H, Ar H); 10.23(s, 1H,
OH).
IIa
IIb
IIc
31.10(31.27) 1.72(1.80) 4.34(4.56) 7.02(d, 1H, J = 7.4Hz), Ar H); 7.25–7.48(m, 5H,
Ar H); 7.63–7.79(m, 3H, Ar H); 7.89–8.01(m, 2H,
Ar H); 9.95(s, 1H, OH).
27.58(27.71) 1.39(1.45) 4.23(4.04) 7.00(d, 1H, J = 7.2Hz, Ar H); 7.30–7.35(m, 2H,
Ar H); 7.59–7.75(m, 5H, Ar H); 7.87(d, 1H, J =
7.6Hz, Ar H); 10.7(s, 1H, OH).
32.32(32.48) 1.98(2.08) 4.28(4.46) 2.28(s, 3H, CH3); 6.94(d, 1H, J = 7.55Hz, Ar H);
7.58–7.73(m, 2H, Ar H); 7.80(d, 1H, J = 7.63Hz,
Ar H); 7.91(s, 1H, Ar H); 8.84(s, 1H, OH).
IId∗
IIIa
29.08(29.14) 1.67(1.53) 6.31(6.37) 6.85(d, 1H, Ar H); 6.92–7.74(m, 5H, Ar H);
7.82–8.45(m, 3H, Ar H); 9.50(s, 1H, OH).
48.98(49.15) 2.80(2.84) 7.19(7.17) 6.94(d, 2H, J = 9.3Hz); 7.26–7.70(m, 10H, Ar H));
7.30–8.15(m, 6H, Ar H); 8.21–8.45(m, 2H,Ar H);
8.92(s, 2H, OH).
IIIb
IIIc
40.79(40.90) 2.37(2.15) 5.90(5.96) 6.98(d, 2H, J = 7.2Hz, Ar H); 7.24–7.34(m, 4H,
Ar H); 7.61–7.72(m, 10H, Ar H); 8.02(d, 2H, J =
6.92, Ar H); 11.23(s, 2H, OH).
50.52(50.42) 3.18(3.24) 6.90(6.92) 2.31(s, 6H, CH3); 6.94(d, 2H, J = 7.52Hz, Ar H);
7.21–7.38(m, 8H, Ar H); 7,58–7.74(m, 4H, Ar H);
7.80(d, 2H, J = 8.40Hz); 7.91(s, 2H, Ar H); 9.24(s,
2H, OH).
IIId
Iva
43.81(44.08) 2.09(2.31) 9.57(9.64) 7.01(d, 2H, J = 7.2Hz, Ar H); 7.30–7.79(m,14H,
Ar H); 8.13(d, 2H, J = 7.2); 9.98(s, 2H, OH).
51.63(51.26) 2.90(2.96) 7.28(7.47) 6.92 (d, 2H, J = 7.1Hz, Ar H). 7.18–8.30 (m, 16H,
Ar H); 9.95 (s, 2H, 2OH);
IVc
52.48(52.50) 3.16(3.37) 7.06(7.20) 2.23(s, 6H, CH3); 6.96(d, 2H, J = 7.0Hz); 7.28–7.35(m,
8H, Ar H); 7.62–7.99(m, 8H, Ar H); 11.53(s, 2H,
OH).
IVd
45.52(45.77) 2.38(2.40) 9.85(10.01) 7.01(d, 2H, J = 7.70Hz, Ar H); 7.31–7.48(m, 4H,
Ar H); 7.79(s, 2H, Ar H); 8.01–8.23(m, 6H,
Ar H); 10.83(s, 2H, OH).
Vc∗
Vd
62.56(62.81) 3.92(4.03) 8.86(8.62) 2.30 (s, 6H, 2CH3); 6.90 (d, 2H, J = 6.95Hz, Ar H);
7.32–8.12(m, 16H, Ar H); 9.35(s, 2H, OH).
53.92(53.97) 2.79(2.83) 11.55(11.80) 6.94(d, 2H, J = 6.96Hz, Ar H); 7.22–7.42(m, 4H,
Ar H); 7.62–7.80(m, 6H, Ar H); 8.01–8.25(m, 2H,
OH).
VIb
VId
58.60(58.92) 2.92(3.09) 8.50(8.59)
66.01(65.75) 3.52(3.45) 14.12(14.38)
13C NMR(DMSO-d6) δ: Carbon numbers as shown in Fig. 1.∗
IId: 153.2 (C2ꢁ), 152.9 (C2), 152.1 (C5ꢁ), 144.0 (C4), 135.0 (C5), 134.1 (C5), 130.8 (C10), 129.3 (C6), 128.5
(C9), 128.13(C8), 126.75(C6ꢁ)), 126.01(C4ꢁ), 125.19(C3ꢁ), 124.90(C7), 118.84(C3), 110.06(C1ꢁ).
Vc: 151.98(C2), 149.44(C2ꢁ), 146.95(C1), 136.77(5ꢁ), 136.34(C4), 129.83(C6ꢁ), 128.94(C4ꢁ),127.75(C5),
126.51(C10),126.34(C6), 125.32(C9), 124.14(C8), 123.60(C7), 117.71(C3), 117.15(C3ꢁ), 109.47(C1ꢁ),
22.68(CH3).

120
A. Z. AL-RUBAIE ET AL.
R
N
R
N
Pd(PPh3)4
TeBr 2
N
CH3CN
N
OH
OH
2
2
VIb
VId
; R= Br ;
: R= NO2
IIIb
; R= Br ;
IIId
: R= NO2
Scheme 2
EXPERIMENTAL
Synthesis
2-Aminophenylmercury chloride,16 2-amino-5-bromophenylmercury chloride,17 2-
amino-5-methylphenylmercury chloride,17 and 2-amino-5-nitrophenylmercury chloride17
were prepared by methods in the literature.
2-(2-Hydroxynaphthylazo)phenylmercury Chloride (Ia)
A solution of sodium nitrite (0.55 g, 8 mmol) in distilled water (25 mL) was added
slowly to a cold solution of 2-aminophenylmercury chloride (2.62 g, 8 mmol) in 1.0 M
hydrochloric acid (25 mL). To this clear solution, a cold solution of 2-naphthol (1.15 g,
8 mmol) in 10% NaOH was added portionwise with stirring over a period of 30 min.
The reaction mixture was stirred for 2 h at 0–5◦C. The reaction mixture was neutralized
with 10% HCl. A yellowish brown solid was formed, collected, washed several times with
distilled water, and dried over P2O5. Yield: 71%, mp 188–190◦C. IR (KBr) cm−1: 3420s,br,
3056w, 1610s, 1488s, 1262s, 1144s, 856s, 837s, 752s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 208(10950), 228(11200) and 478(3350).
The following compounds were prepared by the same above method using the ap-
propriate 2-aminoarylmercury chloride.
2-(2-Hydroxynaphthylazo)-5-bromophenylmercury Chloride (Ib)
A dark brown solid was obtained in 75% yield, mp 230–232◦C. IR (KBr) cm−1
:
3430br, 3057w, 1612s, 1465s, 1271s, 1141s, 851s, 830s, 750s. UV-Vis (λmax, nm (ꢀ
M
−1.cm−1), EtOH): 280(10000), 227(10505) and 473(3110).
2-(2-Hydroxynaphthylazo)-5-methylphenylmercury Chloride (Ic)
A dark brown solid, 80% yield, mp 198–200◦C. IR (KBr) cm−1: 3449s,br, 3070w,
1626s, 1521s, 1401s, 1336s, 1212s, 855s, 845s, 757s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 209 (10850), 228(11330) and 480(3500).

2-(2-HYDROXYNAPHTHYLAZO)ARYLTELLURIUM COMPOUNDS
121
2-(2-Hydroxynaphthylazo)-5-nitrophenylmercury Chloride (Id)
A dark brown solid was obtained in 73% yield, mp 241–243◦C. IR (KBr) cm−1
:
3420s,br, 3056w, 2865w, 2917w,1610s, 1488s, 1350 m, 1262s, 1144s, 856s, 837s, 752s.
UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH): 208(10990), 227(11750) and 476(3560).
2-(2-Hydroxynaphthylazo)phenyltellurium Tribromide (IIa)
2-(2-hydroxynaphthylazo)phenylmercury chloride (1.44 g; 3 mmol) and tellurium
tetrabromide (1.34 g, 3 mmol) were mixed in dry dioxane (60 mL). The mixture was stirred
under reflux for 6 h. Cooling the mixture gave crystals of a mercury(II) halide.2dioxane
complex, which was removed by filtration. The filtrate was poured into ice-water, and
a brown precipitate was formed. The product was recrystallized from a methanol and
dichloromethane (4:1) to give a brown solid of mp 209–211◦C in 79% yield. IR (KBr)
cm−1: 3441br, 3059w, 1602s, 1446s, 1272s, 1138s, 868s, 838s, 749s. UV-Vis (λmax, nm
(ꢀ M−1.cm−1), EtOH): 208 (11259), 226(11400) and 478(3750).
The following compounds were prepared by the same above method using the ap-
propriate azo mercurated compound.
2-(2-Hydroxynaphthylazo)-5-bromophenyltellurium Tribromide (IIb)
A brown solid was obtained in 68%, mp 197–199◦C. IR (KBr) cm−1: 3425br, 3061w,
1611s, 1464s, 1275s, 1147s,1147m, 871s, 811s, 745s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 207 (9153), 228(9880) and 475(2384).
2-(2-Hydroxynaphthylazo)-5-methylphenyltellurium Tribromide (IIc)
A brown solid was obtained in 61%, mp 220–222◦C. IR (KBr) cm−1: 3428br, 3065w,
2923w, 2858w,1599s, 1480s, 1350m, 1270s, 1139s, 861s, 839s, 749s. UV-Vis (λmax, nm
(ꢀ M−1.cm−1), EtOH): 208 (9250), 228(9510) and 478(3840).
2-(2-Hydroxynaphthylazo)-5-nitrophenyltellurium Tribromide (IId)
A brown solid was obtained in 75%, mp 233–235◦C. IR (KBr) cm−1: 3425br, 3061w,
1601s, 1525s, 1484s, 1339s, 851s, 843s, 749s. UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH):
208 (10000), 227(10200) and 477(3700).
Bis(2-(2-hydroxynaphthylazo)phenyl)tellurium Dibromide (IIIa)
2-(2-Hydroxynaphthylazo)phenylmercury chloride (3.86 g, 8 mmol) and tellurium
tetrabromide (1.78 g, 4 mmol) were refluxed in dry dioxane (60 mL) for 6h. The reaction
mixture was treated as described for the preparation of compound IIa to give a brown solid
in 72% yield, mp 171–172◦C. IR (KBr) cm−1: 3480br, 3058w, 1612s, 1449s, 1264s, 1140s,
850w, 837w, 751w. UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH): 206 (10700), 228(11100)
and 478(3550).
The following compounds were prepared by the same above method using the ap-
propriate 2-(2-Hydroxynaphthylazo)arylmercury chloride.

122
A. Z. AL-RUBAIE ET AL.
Bis(2-(2-hydroxynaphthylazo)-5-bromophenyl)tellurium Dibromide (IIIb)
Brown solid. Yield: 70%, mp 202–204◦C. IR (KBr) cm−1: 3450br, 3042w, 1605s,
1456s, 1275s, 1174s,1145s, 1080m, 846s, 837s, 759s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 210 (11510), 227(11990) and 478(3012).
Bis(2-(2-hydroxynaphthylazo)-5-methylphenyl)tellurium Dibromide (IIIc)
Brown solid. Yield: 81%, mp 177–179◦C. IR (KBr) cm−1: 3430br, 3047w, 2920w,
2870w,1597s, 1480s, 1354m, 1275s, 1148s, 830s, 812s, 756s. UV-Vis [λmax, nm (ꢀ
M
−1.cm−1), EtOH]: 208 (10350), 228(10800) and 476(4000).
Bis(2-(2-hydroxynaphthylazo)-5-nitrophenyl)tellurium Dibromide (IIId)
Brown solid. Yield: 77%, mp 215–217◦C. IR (KBr) cm−1: 3435br, 3056w, 1595w,
1570s, 1456m, 1328s, 1258m, 1147s, 854s, 842s, 747s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 207 (10350), 228(10800) and 476(3952).
Bis(2-(2-hydroxynaphthylazo)phenyl)ditelluride (IVa)
To a suspension of compounds IIa (1.19 g, 2 mmol) in hot ethanol (25 mL), a
solution of hydrazine hydrate (0.26 g, 8 mmol) in ethanol (25 mL) was added dropwise.
The mixture was warmed gently until all the solid had dissolved, and was then poured
into water (300 mL). After extraction with ether (3 × 50 mL), the ethereal layer was
separated and dried over anhydrous calcium chloride, and the solvent was removed on a
rotary evaporator. The reddish brown solid was recrystallized from ethanol to give reddish
brown crystals in 60% yield, mp 135–137◦C.
IR (KBr) cm−1 3421br, 3049w, 1600w, 1462s, 1269s, 1141s, 8595s, 836s, 750s.
UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH): 208 (10488), 227(10550), and 476(3528).
The following compounds were prepared by the same method described for the
preparation of compound IVa and by reduction of compounds IIb and IIc with hydrazine
hydrate.
Bis(2-(2-hydroxynaphthylazo)-5-bromophenyl)ditelluride (IVb)
Reddish brown crystals in 61% yield, mp 169–171◦C. IR (KBr) cm−1: 3414br, 3028w,
11597s, 1466s, 1278s, 1130s, 1082m, 845s, 813s, 748s. UV-Vis (λmax, nm (ꢀ M−1.cm−1),
EtOH): 208 (10890), 228(11220) and 478(2900).
Bis(2-(2-hydroxynaphthylazo)-5-methylphenyl)ditelluride (IVc)
Reddish brown crystals in 58% yield, mp 141–143◦C. IR (KBr) cm−1: 3422br, 3030w,
2936w, 2886w, 1597s, 1460s, 1353m, 1265s, 1142s, 852s, 819s, 749s. UV-Vis (λmax, nm
(ꢀ M−1.cm−1), EtOH): 206 (10750), 226(11250) and 478(3760).

2-(2-HYDROXYNAPHTHYLAZO)ARYLTELLURIUM COMPOUNDS
123
Bis(2-(2-hydroxynaphthylazo)-5-methylphenyl)telluride (Vc)
Bis(2-(2-hydroxynaphthylazo)-5-methylphenyl)tellurium dibromide (IIIa) (4.05 g, 5
mmol) was treated with hydrazine hydrate as described for compound IVa. Recrystalliza-
tion of the brown solid with a mixture of ethanol and chloroform gave a brown solid in
62% yield, mp 122–124◦C. IR (KBr) cm−1: 3402br, 3049w, 2931w, 2884w,1600s, 1458s,
1350m, 1273s, 851s, 817s, 758s. UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH): 208 (10650),
227(10800) and 477(3500).
Compound Vd was prepared by the same above method.
Bis(2-(2-hydroxynaphthylazo)-5-nitrophenyl)telluride (Vd)
Brown solid was obtained in 66% yield, mp 167–168◦C. IR (KBr) cm−1: 3416br,
3046w, 1607s, 1523s, 1461s, 1334s, 1275s, 1148s, 854s, 819s, 751s. UV-Vis (λmax, nm (ꢀ
M
−1.cm−1), EtOH): 208 (9900), 228(10800) and 477(3310).
Coupling Reaction of IIIb and IIId with Pd(PPh3)4
2,2ꢁ-Bis(2-hydroxynaphthylazo)-5,5ꢁ-dibromobiphenyl(VIb)
and
2,2ꢁ-bis(2-
hydroxynaphthylazo)-5,5ꢁ-dinitrobiphenyl (VId) were prepared by the same general
coupling procedure and as follows:
To a solution of tetrakis(triphenylphosphane)palladium(0) (0.346 g, 0.30 mmol) in
acetonitrile (10 mL) was added a solution of compound IIIb or IIId (0.30 mmol) in
of acetonitrile (10 mL) dropwise with stirring. The mixture was stirred for 8 h at room
temperature under an argon atmosphere and filtered. The filtrate was evaporated on a rotary
evaporator to dryness. The crude solids of compounds VId and VId were recrystallized
from a mixture of ethanol and diethyl ether. The corresponding biaryls (VIb and VId) were
obtained as brown solids.
2,2ꢀ-Bis(2-hydroxynaphthylazo)5,5ꢀ-dibromobiphenyl (VIb)
Brown solid, mp 149–151◦C. Yield: 75%. IR (KBr) cm−1: 3411br, 1483s, 1433s,
1166s, 1118s, 1012m, 754s, 723s, 692s. UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH): 242
(10576), 266(8820) and 507(280).
2,2ꢀ-Bis(2-hydroxynaphthylazo) 5,5ꢀ-dinitrobiphenyl (VId)
Brown solid, mp 161–163◦C. Yield: 84%. IR (KBr) cm−1: 3410br, 1501s, 1480m,
1435s, 1330s, 1176s, 1118s, 754s, 726s, 696s. UV-Vis (λmax, nm (ꢀ M−1.cm−1), EtOH):
242 (10250), 266(9677) and 510(550).
Physical Measurements
Analysis for C, H, and N was done by the Analytical Service Unit, Al al-Bayt
University, Jordan. FT-IR spectra were recorded for KBr discs with a FT-IR-8400 Shimadzu
instrument. NMR spectra were recorded with a Bruker DPX-300 (300 MHz) and Bruker
LA-250 (250 MHz) using TMS as internal standard. Melting points were determined on a
Gallenkamp melting point apparatus and are uncorrected. The electronic absorption spectra

124
A. Z. AL-RUBAIE ET AL.
in the 800–200 nm range were recorded on a Sean-80D UV-Vis spectrophotometer, using
1 cm quartz cells.
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