Synthesis of lithium ω-(m- and p-lithiophenoxy)alkoxides modified with magnesium 2-ethoxyethoxide. Crystal structures of bis[4-(2-hydroxyethoxy)phenyl]mercury and bis[4-(3-hydroxypropoxy)phenyl]mercury

Article abstract of DOI:10.1016/S0022-328X(99)00425-8

m- and p-Chlorinated ω-phenoxyalcohols 1, were transformed into the corresponding lithium ω-(m- and p-lithiophenoxy)alkoxides 4, respectively, by successive deprotonation with n-butyllithium and subsequent chlorine-lithium exchange by lithium naphthalene radical anion in THF-methylcyclohexane. Lithium 2-(4-lithiophenoxy)ethoxide (4a′) was also prepared by bromine-lithium exchange of 2-(4-bromophenoxy)ethanol (2a′) with two equivalents of n-butyllithium. The organolithiums were modified with magnesium 2-ethoxyethoxide in order to avoid ortho-metallation of the above-mentioned substituted arenes. Subsequent reaction of these intermediates with the electrophiles carbon dioxide, benzophenone, benzonitrile and 0.5 equivalents of mercuric chloride yielded the expected m- and p-substituted (ω-hydroxyalkoxy)benzenes in yields ranging from 50 to 75%. The crystal structures of the organomercurials 8a′ and 8b′ have been determined and revealed the Hg atom to occupy a crystallographic center of symmetry in a linear C-Hg-C arrangement.

Full text of DOI:10.1016/S0022-328X(99)00425-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 590 (1999) 63–70
Synthesis of lithium v-(m- and p-lithiophenoxy)alkoxides modified
with magnesium 2-ethoxyethoxide. Crystal structures of
bis[4-(2-hydroxyethoxy)phenyl]mercury and
bis[4-(3-hydroxypropoxy)phenyl]mercury
Constantinos S. Salteris a, Ioannis D. Kostas a, Maria Micha-Screttas a,
Barry R. Steele a, George A. Heropoulos a, Constantinos G. Screttas a,*, Aris Terzis b
a National Hellenic Research Foundation, Institute of Organic and Pharmaceutical Chemistry, Vas. Constantinou 48, 116 35 Athens, Greece
b Institute of Materials Science, NCSR Democritos, 153 10 Aghia Paraske6i Attikis, Greece
Received 15 June 1999; received in revised form 8 July 1999
Abstract
m- and p-Chlorinated v-phenoxyalcohols 1, were transformed into the corresponding lithium v-(m- and p-lithiophe-
noxy)alkoxides 4, respectively, by successive deprotonation with n-butyllithium and subsequent chlorine–lithium exchange by
lithium naphthalene radical anion in THF–methylcyclohexane. Lithium 2-(4-lithiophenoxy)ethoxide (4a%) was also prepared by
bromine–lithium exchange of 2-(4-bromophenoxy)ethanol (2a%) with two equivalents of n-butyllithium. The organolithiums were
modified with magnesium 2-ethoxyethoxide in order to avoid ortho-metallation of the above-mentioned substituted arenes.
Subsequent reaction of these intermediates with the electrophiles carbon dioxide, benzophenone, benzonitrile and 0.5 equivalents
of mercuric chloride yielded the expected m- and p-substituted (v-hydroxyalkoxy)benzenes in yields ranging from 50 to 75%. The
crystal structures of the organomercurials 8a% and 8b% have been determined and revealed the Hg atom to occupy a crystallo-
graphic center of symmetry in a linear CꢀHgꢀC arrangement. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Phenoxyalcohols; Lithium naphthalene; Lithium; Magnesium; Mercury; Crystal structure
which the additional functional group should there-
fore be compatible. Reagents derived from directed
metallation are usually aryllithiums possessing special
functionalities which are responsible for directing the
site of metallation of the aromatic rings [1b]. Recently,
we reported the ortho-directed lithiation of v-phe-
noxyalcohols and v-phenoxyalkanethiols [2]. The
present report provides information on the lithiation
of the analogous m- and p-halogenated v-phenoxyal-
cohols 1, 2 by halogen–lithium exchange using n-
butyllithium or by reductive lithiation with lithium
naphthalene radical anion. The applications and ad-
vantages of lithium arene radical anions and arene-cat-
alyzed lithiation reactions have been previously
reported [1c,3].
1. Introduction
An additional functionality on lithium reagents con-
siderably increases the synthetic utility of the organo-
lithium compounds and a number of such reagents
have already been reported [1]. The latter reagents
may be classified into two broad categories. The first
category includes those lithium reagents that derive
from displacement of a heteroatom or a heteroatom-
bearing group by lithium, while the second includes
organometallic reagents derived from ‘directed metal-
lation’. Both categories suffer from certain limitations.
The synthesis of organolithiums belonging to the first
category usually requires reductive conditions with
One of the possible competing reactions to the halo-
gen–lithium exchange of m- or p-halogenated v-phe-
noxyalcohols is the ortho-lithiation of the aromatic
* Corresponding author. Tel.: +30-1-727-3876; fax: +30-1-727-
3878.
E-mail address: kskretas@eie.gr (C.G. Screttas)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00425-8

64
C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
ring. Organoalkali reagents form complexes with mag-
nesium 2-ethoxyethoxide that exhibit normal
organometallic behavior but diminished reactivity com-
pared with the uncomplexed compounds [4], and so, in
order to suppress the undesired reactions, we decided to
carry out the halogen–lithium displacements in the
above-mentioned systems in the presence of magnesium
2-ethoxyethoxide. This reagent has previously been suc-
cessfully used in other similar cases [5].
The synthetic utility of these new reagents for car-
bon–carbon or carbonꢀmetal bond formation has been
demonstrated by their reaction with various elec-
trophiles. In addition, the crystal structures of two
organomercurials, prepared via the above-mentioned
intermediates, are reported.
originally formed organolithium 4 could also metallate
the meta-chloro derivative at the highly activated site
between the two ortho-directing groups with the forma-
tion of a benzyne precursor 9 (Scheme 2). Thus, appli-
cation of conventional reductive lithiation for the
displacement of the chlorine atom in 3 should lead to
more than one lithiated product.
The same could be said for the reaction involving
bromine–lithium exchange in cases such as 4% (Scheme
3).
Indeed, 3% presents more than one site for attack by
the lithiating agent and the situation is complicated
further by the instability of para compared with ortho
lithiated products. We reasoned that in order to sup-
press or even eliminate the undesired reactions, both in
the reductive lithiation or in the halogen–metal inter-
change reactions, we should suppress the metallating
abilities of 4, 4% and of butyllithium. This can be
achieved by carrying out these reactions in the presence
of magnesium 2-ethoxyethoxide [5]. Evidently in this
case, the BuLi–Mg(OCH2CH2OEt)2 complex exhibits a
reactivity profile analogous to that of the organomag-
nesium reagent, although it retains the ability to un-
dergo halogen–metal interchange that is characteristic
of organolithium compounds.
2. Results and discussion
2.1. General considerations
The general synthetic strategy employed in the
present work is outlined in Scheme 1.
Displacement of a chlorine atom in a meta position
can be considered as something of a challenge since the
Scheme 1.
Scheme 2.
Scheme 3.

C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
65
Scheme 4.
Table 1
Reductive cleavage of v-(m- and p-chlorophenoxy)alcohols 1, 1% and bromine–lithium exchange of 2-(4-bromophenoxy)ethanol (2a%). Reactions
of organolithiums 4, 4% with electrophiles
Haloalcohol
Organolithium
Electrophile
Product
Yield (%)
M.p. (°C) (recr. solv.)
1a: m, n=2
1b: m, n=3
1a%: p, n=2
2a%
1b%: p, n=3
1a: m, n=2
1a%: p, n=2
2a%
1b%: p, n=3
1a%: p, n=2
2a%
1b%: p, n=3
1a%: p, n=2
2a%
4a
4b
CO2
CO2
CO2
CO2
5a
5b
50
63
72
66
73
57
74
72
68
60
55
58
75
75
67
106–108 (toluene) a
105–108 (toluene)
4a%
4a%
4b%
4a
4a%
4a%
4b%
4a%
4a%
4b%
4a%
4a%
4b%
5a%
5a%
5b%
6a
6a%
6a%
6b%
7a%
7a%
7b%
8a%
8a%
8b%
173–175 (toluene) b
173–175 (toluene) b
136–138 (CH2Cl2–hexane)
123–125 (toluene–hexane)
104–105 (toluene)
CO2
Ph2CO
Ph2CO
Ph2CO
Ph2CO
PhCN
PhCN
PhCN
HgCl2
HgCl2
HgCl2
104–105 (toluene)
68–70 (toluene–hexane)
80–82 (toluene–hexane) c
80–82 (toluene–hexane)
73–75 (ether)
168–170 (acetone)
168–170 (acetone)
1b%: p, n=3
150–152 (isopropanol)
a Lit. [9], m.p. 111°C.
b Lit. [9], m.p. 177°C.
c Lit. [11], m.p. 84–85°C.
2.2. Chlorine–lithium exchange of m- and
p-chlorinated ꢀ-phenoxyalcohols 1, 1% by lithium
naphthalene radical anion
nated v-phenoxyalcohols 1, 1% proceeded in good yields
using two equivalents of lithium naphthalene radical
anion, after initially treating the starting materials with
n-butyllithium in order to form the corresponding phe-
noxyalkoxides (Scheme 4). Chlorine–lithium exchange
is very fast and is complete after 10–30 min at temper-
atures between −70 and −20°C. The completion of
the reaction was clearly indicated by the disappearance
of the dark green colour of the radical anion solution.
The yields of lithiated products 4, 4% were determined
by carboxylation and subsequent acidic hydrolysis
forming 3- and 4-(v-hydroxyalkoxy)benzoic acids 5, 5%,
respectively, in yields ranging between 50 and 73%
(Table 1). The derivatisation of 4, 4% with benzophe-
none yielded the primary–tertiary diols 6, 6%, respec-
tively. Reaction of 4% with benzonitrile following by
acidic hydrolysis yielded the v-(4-benzoylphe-
Attempted conversion of lithium m- and p-chlori-
nated v-phenoxyalcoholates 3, 3% to the corresponding
lithium derivatives with lithium metal, under various
reaction conditions, or by conventional reductive lithia-
tion with lithium naphthalene radical anion, led to very
low yields of the corresponding organolithiums, due to
reasons discussed in the previous section. However,
when reductive lithiation was carried out in the pres-
ence of one equivalent of magnesium 2-ethoxyethoxide
and the organolithium was subsequently carboxylated,
yields of the expected substituted benzoic acids 5, 5%
ranging between 50 and 73% were realized. On the
other hand, chlorine–lithium exchange of the chlori-

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C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
Scheme 5.
noxy)alcohols 7%. In addition to CꢀC bond formation,
dilithiated species 4% were also applied to Cꢀmetal bond
formation by their reaction with 0.5 equivalent of mer-
cury chloride, yielding hydroxy-substituted organomer-
curials 8%.
3. Experimental
3.1. General
The chlorinated v-phenoxyalcohols 1, 1% were pre-
pared by the reaction of chlorinated sodium phenoxide,
prepared from m- or p-chlorophenol and aqueous
NaOH, with the appropriate v-haloalcohol according
to a known procedure [6]. 2-(4-Bromophenoxy)ethanol
(2a%) was synthesized by acidic hydrolysis of 2-(4-bro-
mophenoxy)ethyl acetate, which in turn was prepared
by para-bromination of 2-phenoxyethanol in the pres-
ence of glacial acetic acid, following a known procedure
[7]. The halogenated phenoxyalcohols 1a, 1b, 1a%, 1b%
and 2a% are known compounds [8]. The lithium naph-
thalene radical anion used for lithiation reactions was
freshly prepared in THF in a concentration of 1.0 M,
according to a known procedure [3d]. n-BuLi was
2.3. Bromine–lithium exchange of
2-(4-bromophenoxy)ethanol (2a%) by n-butyllithium
Lithium 2-(4-lithiophenoxy)ethoxide (4a%) was also
prepared by bromine–lithium exchange of 2-(4-bro-
mophenoxy)ethanol (2a%) with two equivalents of n-
butyllithium in THF–methylcyclohexane, in the
presence of magnesium 2-ethoxyethoxide (Scheme 5). It
should be stressed that, in the absence of magnesium
alkoxide, the analogous bromine–lithium exchange of
p-bromoanisole in THF, using n-butyllithium, yielded
virtually no para-substituted aryllithium [5a].
Organolithium 4a% prepared from 2a% using this
method was quenched with the electrophiles carbon
dioxide, benzophenone, benzonitrile and 0.5 equivalents
of mercury chloride, yielding the compounds 5a%, 6a%,
7a% and 8a%, respectively (Table 1). The yields range
between 55 and 75%, and they are close to the corre-
sponding yields of compounds 5a%–8a%, prepared using
the lithium naphthalene radical anion.
2.4. Crystal structures of the organomercurials 8a% and
8b%
Suitable crystals of 8a% and 8b% for X-ray crystal
structure determination were obtained by recrystalliza-
tion from acetone and isopropanol, respectively. The
structures of molecules 8a% and 8b% (Fig. 1) are as shown
with coplanar phenyl rings and the Hg atom to occupy
a crystallographic center of symmetry, similarly to the
structures
of
the
analogues
bis[o-(v-hydrox-
yalkoxy)phenyl]mercury compounds [2a]. The C(1)ꢀHg
distances in molecules 8a% and 8b% of 2.067 and 2.072 A,
,
respectively, are normal for these types of molecules.
Selected bond distances, angles and torsion angles for
8a% and 8b% are presented in Table 2.
Fig. 1. ORTEP drawings of 8a% and 8b% at the 50% probability level.
The hydrogen atoms are omitted for clarity.

C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
67
Table 2
naphthalene solution turned to red–brown. The mix-
ture was then warmed slowly to r.t. and the organo-
lithium 4a quenched with a given electrophile (vide
infra).
,
Selected bond distances (A), bond angles (°) and torsion angles (°) for
8a% and 8b%
8a%
8b%
Bond distances
HGꢀC(1)
C(4)ꢀO(1)
O(1)ꢀC(7)
C(8)ꢀO(2)
C(9)ꢀO(2A)
C(9)ꢀO(2B)
3.3. Bromine–lithium exchange of 2a% by n-butyllithium
2.067(6)
1.376(7)
1.411(1)
1.430(9)
2.072(7)
1.360(8)
1.420(1)
3.3.1. Lithium 2-(4-lithiophenoxy)ethoxide (4a%)
To a suspension of magnesium 2-ethoxyethoxide (2 g,
9.9 mmol) in THF (5 ml) under argon was added
n-BuLi (10.9 ml of 1.86 M solution in methylcyclohex-
ane, 20.3 mmol) at −78°C, and the mixture stirred for
15 min at this temperature and for 2 h at r.t. A solution
of 2-(4-bromophenoxy)ethanol (2a%) (2.2 g, 10 mmol) in
THF (10 ml) was then added at −78°C and the
mixture stirred for 30 min at this temperature and for 1
h with ice–water bath cooling. The organolithium 4a%
was then quenched with a given electrophile (vide
infra).
1.310(1)
1.310(1)
Bond angles
HGꢀC(1)ꢀC(2)
C(3)ꢀC(4)ꢀO(1)
C(7)ꢀC(8)ꢀO(2)
C(8)ꢀC(9)ꢀO(2A)
C(8)ꢀC(9)ꢀO(2B)
123.5(5)
124.6(6)
109.6(6)
120.6(5)
114.9(6)
133.0(1)
109.0(1)
Torsion angles
C(3)ꢀC(4)ꢀO(1)ꢀC(7)
C(4)ꢀO(1)ꢀC(7)ꢀC(8)
O(1)ꢀC(7)ꢀC(8)ꢀO(2)
O(1)ꢀC(7)ꢀC(8)ꢀC(9)
C(7)ꢀC(8)ꢀC(9)ꢀO(2)
7
171
75
−179
179
−62
171(−75)
3.4. Carboxylation of dilithiated species 4, 4%. Synthesis
of m- and p-(ꢀ-hydroxyalkoxy)benzoic acids 5, 5%
a In the case of disorder of the hydroxyl group the second value is
given in parentheses.
3.4.1. Typical procedure
3.4.1.1. 3-(2-Hydroxyethoxy)benzoic acid (5a). The mix-
ture of 4a in THF, prepared from 1a (20 mmol) as
described above, was poured rapidly into a beaker
containing a slurry of crushed dry ice and anhydrous
ether. When the carboxylation mixture had reached r.t.,
water was added and the volume was reduced by
evaporation. After filtration, the aqueous phase was
washed with toluene and hexane and acidified with 20%
H2SO4. The product was extracted with ether (4×50
ml) and dried. After removing the drying agent, the
extract was evaporated yielding 5a (1.82 g, 50%) as a
white solid which was recrystallized from toluene, m.p.
prepared from lithium metal and n-BuCl in methylcy-
clohexane. Lithiation reactions were performed in stan-
dard glassware with ground joints under argon. THF
was distilled from LiAlH4. The organic extracts of all
compounds prepared in this paper were dried over
1
Mg2SO4. NMR: Bruker AC 300 or Varian FT 80; H-
and 13C-NMR shifts were referenced to the solvents.
DEI MS: Finnigan MAT 95Q. Melting points were
measured on a Bu¨chi melting point apparatus and were
not corrected.
3.2. Reducti6e lithiations of 1, 1% by lithium
naphthalene radical anion
1
106–108°C (lit. [9] m.p. 111°C). H-NMR (CD3OD): l
7.77–6.80 (m, 4H, Ar), 4.85 (s, 2H, OH and COOH),
4.20–3.87 (m, 4H, (CH2)2). 13C{1H}-NMR (CD3OD): l
167.76 (CꢁO), 158.38, 131.19, 128.55, 121.23, 118.69
and 114.32 (Ar), 68.77 and 59.64 (OCH2 and CH2OH).
3.2.1. Typical procedure
3.2.1.1. Lithium 2-(3-lithiophenoxy)ethoxide (4a). To a
suspension of magnesium 2-ethoxyethoxide (4 g, 19.8
mmol) in THF (10 ml) under argon was added n-BuLi
(10.9 ml of 1.86 M solution in methylcyclohexane, 20.3
mmol) at −78°C, and the mixture stirred for 15 min at
this temperature and then for 2 h at room temperature
(r.t.). A solution of 2-(3-chlorophenoxy)ethanol (1a)
(3.45 g, 20 mmol) in THF (15 ml) was then added at
−78°C and the mixture stirred for 15 min, after which
a solution of freshly prepared lithium naphthalene rad-
ical anion (40 mmol) in THF (40 ml) was added slowly
over 20 min. The addition was carried out at such a
rate that the temperature did not rise above −50°C.
During the addition, the dark green color of lithium
3.4.1.2. 3-(3-Hydroxypropoxy)benzoic acid (5b). 1H-
NMR (CD3OD): l 7.64–6.90 (m, 4H, Ar), 4.87 (s, 2H,
3
OH and COOH), 4.10 (t, J=6.2 Hz, 2H, OCH2), 3.74
3
(t, J=6.2 Hz, 2H, CH2O), 2.12-1.83 (m, 2H, CH2).
13C{1H}-NMR (CD3OD): l 167.70 (CꢁO), 158.30,
131.09, 128.59, 121.19, 118.60 and 114.40 (Ar), 67.70
and 58.58 (OCH2 and CH2OH), 32.25 (CH2). Anal.
Calc. for C21H20O3: C, 61.22; H, 6.16. Found: C, 61.05;
H, 6.31%.
1
3.4.1.3. 4-(2-Hydroxyethoxy)benzoic acid (5a%) [9]. H-
NMR (CD3OD): l 7.98 and 7.01 (sym. dd, 4H, Ar),
4.85 (s, 2H, OH and COOH), 4.20–3.84 (m, 4H,

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C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
(CH2)2). 13C{1H}-NMR (CD3OD): l 168.05 (CꢁO),
160.10, 134.27, 125.62 and 116.74 (Ar), 71.28 and 61.98
(OCH2 and CH2OH).
3.6. Reaction of 4% with benzonitrile. Synthesis of
ꢀ-(4-benzoylphenoxy)alcohols (7%)
3.6.1. Typical procedure
3.4.1.4. 4-(3-Hydroxypropoxy)benzoic acid (5b%) [10].
1H-NMR (CD3OD): l 7.91 and 6.98 (sym. dd, 4H,
3.6.1.1. 2-(4-Benzoylphenoxy)ethanol (7a%). To a mix-
ture of 4a% in THF, prepared from 1a% (10 mmol)
as described above, was added a solution of benzoni-
trile (1 g, 9.7 mmol) in THF (10 ml), with ice–water
bath cooling, after which the reaction mixture was
stirred at r.t. overnight. Water was then added and,
after filtration, the product was extracted with toluene.
The organic phase was treated with 3.6 N aqueous
solution HCl (15 ml), the aqueous phase was separ-
ated and refluxed for 2 h. The product was extracted
with toluene, washed with water and dried. After filtra-
tion, the solvent was removed by evaporation. The
remaining viscous oil was treated with hexane, yiel-
ding 7a% (1.4 g, 60%) as a white solid, which was
recrystallized from toluene–hexane, m.p. 80–82°C (lit.
[11] m.p. 84–85°C). The 1H- and 13C-NMR spectra
were in accordance with those previously reported
[11].
3
Ar), 4.74 (s, 2H, OH and COOH), 4.15 (t, J=6.2 Hz,
2H, OCH2), 3.74 (t, 3J=6.2 Hz, 2H, CH2O), 2.15–
1.84 (m, 2H, CH2). 13C{1H}-NMR (CDCl3): l 167.91
(CꢁO), 162.41, 130.84, 121.91 and 113.21 (Ar), 64.08
and 57.49 (OCH2 and CH2OH), 31.14 (CH2).
3.5. Reaction of 4, 4% with benzophenone. Synthesis of
carbinols 6, 6%
3.5.1. Typical procedure
3.5.1.1. Diphenyl-[m-(2-hydroxyethoxy)phenyl]methanol
(6a). To a mixture of 4a in THF, prepared from 1a (20
mmol) as described above, was added a solution of
benzophenone (3 g, 16.5 mmol) in THF (10 ml), with
ice–water bath cooling, after which the reaction mix-
ture was stirred at r.t. for 1 h. Water was then added
and after filtration to remove Mg(OH)2, the product
was extracted with toluene and dried. After filtration,
the solvent was removed by evaporation and the
residue was heated under vacuum to remove naph-
thalene and the liberated 2-ethoxyethanol. The remain-
ing viscous oil was treated with hexane yielding 6a (3
g, 57%) as a white solid, which was recrystallized from
3.6.1.2. 3-(4-Benzoylphenoxy)propanol (7b%). 1H-NMR
(CDCl3): l 7.90–6.88 (m, 9H, Ar), 4.17 (t, J=6.1 Hz,
3
2H, OCH2), 3.91 (t, 3J=6.2 Hz, 2H, CH2O), 2.20–
1.94 (m, 2H, CH2), 2.55 (brs, 1H, OH). 13C{1H}-NMR
(CDCl3): l 195.76 (CꢁO), 162.80, 138.29, 132.56,
131.96, 130.04, 129.67, 128.23 and 114.16 (Ar), 65.47
and 59.29 (OCH2 and CH2OH), 32.06 (CH2). Anal.
Calc. for C16H16O3: C, 74.98; H, 6.29. Found: C, 74.69;
H, 6.34%.
1
toluene–hexane, m.p. 123–125°C. H-NMR (CD3OD):
l 7.38–6.79 (m, 14H, Ar), 4.07–3.80 (m, 4H, (CH2)2),
2.06 and 1.67 (brs, 2H, 2×OH). 13C{1H}-NMR
(CD3OD): l 157.94, 148.46, 146.69, 127.57, 127.24,
126.60, 125.97, 120.07, 114.15 and 112.04 (Ar), 80.90
(CHOH), 68.53 and 59.70 (OCH2 and CH2OH). Anal.
Calc. for C21H20O3: C, 78.73; H, 6.29. Found: C, 78.59;
H, 6.31%.
3.7. Reaction of 4% with mercury chloride. Synthesis of
bis[4-(ꢀ-hydroxyalkoxy)phenyl]mercuric compounds 8%
3.7.1. Typical procedure
3.5.1.2. Diphenyl-[4-(2-hydroxyethoxy)phenyl]methanol
(6a%). 1H-NMR (CDCl3): l 7.44–6.80 (m, 14H, Ar),
4.04–3.90 (m, 4H, (CH2)2), 3.00 and 2.22 (brs, brs, 2H,
2×OH). 13C{1H}-NMR (CDCl3): l 157.84, 147.21,
139.90, 129.39, 127.92, 127.19 and 114.01 (Ar), 81.78
(CHOH), 69.39, 61.43 (OCH2 and CH2OH). Anal.
Calc. for C21H20O3: C, 78.73; H, 6.29. Found: C, 78.55;
H, 6.36%.
3.7.1.1. Bis[4-(2-hydroxyethoxy)phenyl]mercury (8a%).
To a mixture of 4a% in THF, prepared from 1a% (20
mmol) as described above, was added dropwise a solu-
tion of mercury chloride (2.3 g, 8.5 mmol) in THF (20
ml), with ice–water bath cooling, after which the reac-
tion mixture was stirred at r.t. overnight. The work-up
procedure was as described for 6a. Purification of the
crude product was carried out by recrystallization from
acetone yielding 8a% (3.03 g, 75%) as a white solid, m.p.
168–170°C. 1H-NMR (DMSO-d6): l 7.49 and 6.99
3.5.1.3. Diphenyl-[4-(3-hydroxypropoxy)phenyl]methanol
(6b%). 1H-NMR (CDCl3): l 7.44–6.80 (m, 14H, Ar),
3
3
4.09 (t, J=5.8 Hz, 2H, OCH2), 3.80 (t, J=5.9 Hz,
2H, CH2O), 2.21–1.85 (m, 4H, CH2 and 2×OH).
13C{1H}-NMR (CDCl3): l 157.79, 147.29, 139.76,
129.30, 127.98, 127.10 and 114.10 (Ar), 81.67 (CHOH),
68.5 and 61.58 (OCH2 and CH2OH), 32.43 (CH2).
Anal. Calc. for C22H22O3: C, 79.02; H, 6.63. Found: C,
78.85; H, 6.67%.
3
(sym. dd, 4H, Ar), 4.87 (t, J=5.5 Hz, 1H, OH), 4.01
3
(t, J=5.1 Hz, 2H, OCH2), 3.79–3.74 (m, 2H, CH2O).
13C{1H}-NMR (DMSO-d6): l 162.46, 157.96, 138.75
and 114.10 (Ar), 69.04 and 59.62 (OCH2 and CH2OH).
DEI MS: m/z (relative intensity) 476 (M+;
202
18
C16H HgO4, 100), 431 (5), 388 (34), 339 (5), 293 (14),

C.S. Salteris et al. / Journal of Organometallic Chemistry 590 (1999) 63–70
69
137 (59), 93 (52), 65 (39). HRMS: Anal. Calc. for
3.8. X-ray structure determinations of 8a% and 8b%
C16H18HgO4 476.0930. Found 476.0921.
Numerical data on the structure determinations have
been collected in Table 3. Intensity data were obtained
at 297 K on a Syntex P21 automatic diffractometer by
variable-rate q−2q scans with Nb-filtered Mo–Ka ra-
3.7.1.2. Bis[4-(3-hydroxypropoxy)phenyl]mercury (8b%).
1H-NMR (DMSO-d6): l 7.48 and 6.98 (sym. dd, 4H,
Ar), 4.58 (s, 1H, OH), 4.06 (t, 3J=6.20 Hz, 2H,
OCH2), 3.64–3.38 (m, 2H, CH2O), 1.93–1.89 (m, 2H,
CH2). 13C{1H}-NMR (DMSO-d6): l 162.14, 157.70,
138.49 and 113.80 (Ar), 63.83 and 57.08 (OCH2 and
CH2OH), 31.92 (CH2). DEI MS: m/z (relative intensity)
,
diation (u=0.71069 A). Lattice parameters were ob-
tained by a least-squares analysis of 15 reflections
scattered in reciprocal space. Three reflections moni-
tored periodically showed a B3% intensity fluctuation.
Lp and numerical absorption corrections were applied.
The density was measured by flotation, and the position
of the Hg atom was located from a Patterson map.
Subsequent Fourier synthesis revealed the positions of
all the other non-H atoms. Refinement proceeded by
full-matrix least-squares in which ꢀwZ2 was minimized
with SHELX76 [12]. The non-H atoms were refined using
anisotropic temperature factors and the hydrogen
atoms isotropic. The hydroxyl group was disordered
over two positions with occupancy 0.5 in 8b%. Atomic
scattering factors were taken from International Tables
for X-ray Crystallography [13].
504 (M+; C18H HgO4, 100), 446 (13), 388 (36), 293
202
22
(12), 151 (32), 94 (68), 65 (32). HRMS: Anal. Calc. for
C18H22HgO4 504.1226. Found 504.1225.
Table 3
Numerical data of the structure determination for 8a% and 8b%
Compound
8a%
8b%
Formula
Formula weight
Hg(C8H9O2)2
474.9
Hg(C9H11O2)2
502.96
,
a (A)
13.645(3)
5.000(1)
11.203(2)
99.77(2)
753.3(3)
2
11.279(2)
4.9039(8)
31.551(9)
95.96(2)
1735.7(6)
4
,
b (A)
,
c (A)
i (°)
V (A )
3
,
4. Supplementary material
Z
Dcalc. (Mg m−3
)
2.093
2.00
1.924
1.91
Dmeasd. (Mg m−3
)
Crystallographic data (excluding structure factors)
for the structures in this paper have been deposited
with the Cambridge Crystallographic Data Centre,
CCDC no. 125123 for compound 8a% and CCDC no.
125124 for compound 8b%. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(Fax. +44-1223-336-033, or e-mail: deposit@ccdc.-
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Space group
P21/c
A2/n
Crystal dimensions (mm)
0.1×0.03×0.38
10.195
0.03×0.31×0.42
8.851
v (mm−1
)
Transmission factors
Scan speed (deg min−1
Scan range (°)
2u limit (°)
Data collected
Data unique
Data used
0.7366/0.3465
1.5–15.0
1.6 plus a1–a2
53.0
1449
1324
0.7403/0.1376
1.8–18.0
1.7 plus a1–a2
50.0
2296
1810
)
1324
1292
Fo\
Rint
3.0|(Fo)
0.0157
0–14
0.0116
−16–16
−5–0
0–13
Range of h
Range of k
Range of l
Weighting scheme
With g
Acknowledgements
0–5
−36–36
e
The investigation was supported by the National
Hellenic Research Foundation and a grant to A.T. by
Mr John Boutaris. We are grateful to Dr W. Spahl of
the Ludwig-Maximilians-Universita¨t Mu¨nchen for mea-
suring the mass spectra and for the HRMS measure-
ments of 8a% and 8b%.
(unit)
0.00017
968
124
F(000)
452
133
Nr a
ꢁD/|ꢁmax
0.168
0.629
−0.588
l.69
0.0294
0.0298
0.0311
0.0323
0.006
1.128
−0.994
1.58
0.0328
0.0486
0.0350
0.0371
−3
,
(Dz)max (e A
)
−3
,
(Dz)min (e A
)
b
S
R
R
c
(observed)
(all data)
c
References
d
Rw (observed)
d
Rw (all data)
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a Nr=number of refined parameters.
b S=[ꢀw(DF)2/(N−P)]1/2; P=no. of parameters; N=no. of ob-
served reflections.
c R=ꢀꢁDFꢁ/ꢀꢁFoꢁ.
2 1/2
d Rw=[ꢀw(DF)2/ꢀwꢁFoꢁ ]
.
e w=(|2(Fo)+gFo2)−1
.

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