Nickel catalysed electrosynthesis of ketones from organic halides and iron pentacarbonyl. Part 2: Unsymmetrical ketones

Article abstract of DOI:10.1016/S0040-4020(00)01017-6

Unsymmetrical aryl-benzyl or aryl-alkyl ketones are obtained by electrolysing in an undivided cell a DMF solution containing two organic halides, iron pentacarbonyl and a catalytic amount of a nickel-2,2′-bipyridine complex.

Full text of DOI:10.1016/S0040-4020(00)01017-6

TETRAHEDRON
Pergamon
Tetrahedron 57 (2001) 525±529
Nickel catalysed electrosynthesis of ketones from organic halides
and iron pentacarbonyl. Part 2: Unsymmetrical ketones
*
Â
Eric Dolhem, Rachid Barhdadi, Jean Claude Folest, Jean Yves Nedelec and Michel Troupel
Á Â
Laboratoire d'Electrochimie, Catalyse et Synthese Organique, CNRS-Universite Paris 12 Val-de-Marne,
2 rue H. Dunant, 94320 Thiais, France
Received 19 June 2000; revised 11 October 2000; accepted 27 October 2000
AbstractÐUnsymmetrical aryl±benzyl or aryl±alkyl ketones are obtained by electrolysing in an undivided cell a DMF solution containing
two organic halides, iron pentacarbonyl and a catalytic amount of a nickel-2,20-bipyridine complex. q 2001 Elsevier Science Ltd. All rights
reserved.
1. Introduction
nyl leads to aldehydes4 or symmetrical ketones4b,5 with
moderate yields.
The carbonylation of organic halides (RX) into ketones can
be achieved by coupling between RX and CO itself or, often
more ef®ciently from transition metal carbonyl complexes.1
Some years ago, we have envisaged a new approach by
the conjoined use of electrochemistry and homogeneous
catalysis based on nickel±2,20-bipyridine complexes.
Thus, we have shown that the electroreduction of Nibpy21
allows the formation of a symmetrical ketone from DMF
solutions of an organic halide maintained under a carbon
monoxide atmosphere.6 Electroanalytical investigations led
us to propose that the catalytic cycle is induced by the
electrogeneration of an unsaturated transient zerovalent
complex NibpyCO which reacts with the organic halide.7
The balance of the reaction involves necessarily a two-
electron reduction as expressed by Eq. (1).
R1X 1 R2X 1 `CO' 1 2e ! R1±CO±R2 1 2X2
ꢀ1†
Several ways can be considered to achieve this reduction.
One method consists in a preliminary conversion of one
of the organic halides into an organometallic compound
(organolithium, Grignard reagent,¼). Conversely a tran-
sition metal carbonyl complex can be initially reduced
into a nucleophilic compound. This second way has been
widely explored since Collman, two decades ago, showed
the versatility of the reagent Fe(CO)242.2 This super nucleo-
phile reacts with various organic halides to give alkyl metal
carbonyl complexes that evolve into acyl metal carbonyl
complexes in a key-step for the obtaining of carbonylated
products.1 A third way which has not been much explored
consists in performing the reduction step by an electro-
chemical method. Some work has been devoted to the elec-
trochemistry of metal carbonyl complexes and especially
iron pentacarbonyl which undergoes a cathodic reduction
at 22 V vs. SCE3. It has been reported that electrolysis of
mixtures of an alkyl- or benzyl-halide and iron pentacarbo-
This method, using CO gas in mild conditions, provides
good yields of symmetrical ketones derived from benzylic
or aliphatic halides. However, aromatic halides were much
less reactive. In addition, attempts to obtain unsymmetrical
ketones from solutions containing two halides were not
successful since the selectivity was low. Another limitation
was the necessity to adjust accurately the experimental
conditions in order to avoid a lack or an excess of carbon
monoxide. Indeed, a lack of CO results in a competition
between the obtaining of the ketone and the Ni(0)bpy cata-
lysed formation of the dimer R±R whereas an excess of CO
leads to the stable saturated complex Nibpy(CO)2 inactive
towards RX.
This dif®culty was overcome by the use of a metal carbonyl
complex like Fe(CO)5, Fe3(CO)12, W(CO)6, Cr(CO)6,
Mo(CO)5 or Co2(CO)8 instead of gaseous CO8 that offers
the advantage of having in the solution an adjustable source
of CO. In these new conditions the electrosynthesis of
symmetrical benzyl or alkyl ketones is easily achieved
with moderate to excellent yields.
Keywords: metal carbonyl; ketone electrosynthesis; nickel catalysis;
organic halides electroreduction.
* Corresponding author. Tel.: 133-1497-811-31; fax: 133-1497-811-48;
e-mail: troupel@glvt-cnrs.fr
In this paper we wish to present our results related to
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)01017-6

526
E. Dolhem et al. / Tetrahedron 57 (2001) 525±529
Table 1. Ni-bpy catalysed electrosyntheses of aryl±alkyl ketones from organic halides and iron pentacarbonyl (general conditions: DMF (50 mL), Bu4NBF4
0
Ê
1.5 mmol, RX 10 mmol, ArX 20 mmol, Fe(CO)5 3 mmol, NiBr2bpy 3 mmol, stainless steel anode (Fe64/Ni36), nickel grid cathode, Iˆ0.3±0.5 A)
Entry
RX
ArX0
Ar±CO±R
Isolated yield (%)
1
2
3
4
5
6
7
8
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
Ph±CH2Cl
2-Cl±C6H4±CH2Cl
PhI
PhBr
PhCl
2-MeO±C6H4I
3-MeO±C6H4I
4-MeO±C6H4I
4-MeO±C6H4Br
2-HO±C6H4I
Ph±CO±CH2±Ph
Ph±CO±CH2±Ph
Ph±CO±CH2±Ph
1
82
42
Traces
54
70
88
49
80
57
84
76
43
63
Traces
60
Traces
39
32
2-MeO±C6H4±CO±CH2±Ph
3-MeO±C6H4±CO±CH2±Ph
4-MeO±C6H4±CO±CH2±Ph
4-MeO±C6H4±CO±CH2±Ph
2-HO±C6H4±CO±CH2±Ph
3-HO±C6H4±CO±CH2±Ph
4-HO±C6H4±CO±CH2±Ph
2-H2N±C6H4±CO±CH2±Ph
3-H2N±C6H4±CO±CH2±Ph
4-H2N±C6H4±CO±CH2±Ph
4-H2N±C6H4±CO±CH2±Ph
4-Me2N±C6H4±CO±CH2±Ph
4-CN±C6H4±CO±CH2±Ph
3-Et±CO±C6H4±CO±CH2±Ph
4-Et±CO±C6H4±CO±CH2±Ph
4-MeO±C6H4±CO±CH2-(2-
Cl±C6H4)
2
3
4
5
6
7
8
9
10
9
3-HO±C6H4I
4-HO±C6H4I
10
11
12
13
14
15
16
17
18
19
2-H2N±C6H4I
3-H2N±C6H4I
4-H2N±C6H4I
4-H2N±C6H4Br
4-Me2N±C6H4Br
4-CN-C6H4Br
3-Et±CO±C6H4Br
4-Et±CO±C6H4Br
4-MeO±C6H4I
11
12
13
14
15
71
20
21
3-Cl±C6H4±CH2Cl
4-Cl±C6H4±CH2Cl
4-MeO±C6H4I
4-MeO±C6H4I
4-MeO±C6H4±CO±CH2-(3-
Cl±C6H4)
4-MeO±C6H4±CO±CH2-(4-
Cl±C6H4)
Ph±CO±C8H17
16
17
72
73
22
23
24
n-C8H17I
n-C8H17I
Ph±CH2Cl
PhI
4-MeO±C6H4I
Ph±CHvCHBr (E)
18
19
20
42
35
52
4-MeO±C6H4±CO±C8H17
Ph±CHvCH±CO±CH2±Ph
the Ni-bpy catalysed one-step electrosynthesis of unsym-
metrical ketones from the mixture of two organic halides
and a metal carbonyl complex, especially iron penta-
carbonyl, as the source of CO.
Fe(CO)5, we have shown, as for the synthesis of symmetri-
cal ketones,8 that, when Fe(CO)5 is in default, more than
4 mol of CO per mole of Fe(CO)5 are available for the
formation of ketones. Presumably, Fe(CO)5 loose one CO
group and forms dimers and trimers (e.g. Fe2(CO)9 and
Fe3(CO)12) which subsequently function as CO source. A
moderate excess of Fe(CO)5 (3 mmol of Fe(CO)5 vs.
10 mmol of RX) is then suf®cient to prevent the formation
of uncarbonylated side-products like R±R, Ar±Ar or Ar±R.
This avoids also, at the end of the electrolysis, the presence
in the solution of large amounts of hazardous metal carbonyl
species that would complicate the further workup.
We were particularly interested in the preparation of aryl±
alkyl-ketones, which are important synthetic intermediates.
The overall reaction accords with Eq. (2):
FeꢀCO†
NiBr2bpy; e
5
RX 1 ArX0
!
Ar±CO±R
ꢀ2†
Results given in Table 1 show that an aryl iodide is effective
as a partner of benzylic chlorides. Yields become moderate
to poor for aryl bromides (Table 1, entries 2, 7, 14, 16±18)
and still lower from chlorobenzene (Table 1, entry 3), the
formation of dibenzylketone being then largely competitive.
2. Results and discussion
The experimental conditions were similar to those
employed for the synthesis of symmetrical ketones.8 To
DMF was added a supporting electrolyte (Bu4NBF4), iron
pentacarbonyl, the catalytic precursor NiBr2bpy and the two
organic halides. The undivided cell was ®tted with a sacri-
®cial stainless steel rod as the anode surrounded by a cylind-
rical nickel grid as the cathode (40 cm2). A calomel
reference electrode was set near the nickel grid allowing
us to measure the potential of the cathode during the elec-
trolysis which were carried out at room temperature and at
constant current intensity until the full consumption of the
Various substituted aryl iodides are compatible but yields
depend on the position of the substitutent. When the
aromatic halide is iodophenol (Table 1, entries 8±10) or
iodoaniline (Table 1, entries 11±13) yields decrease in the
order ortho<para.meta while the ortho position of the
OMe group is the less favourable for iodoanisoles (Table
1, entries 4±6). The presence of an electron-withdrawing
group on the aryl halide (Table 1, entries 16±18) give yields
lower than in the presence of an electron-donating group.
No clear interpretation of the effect of the substitutent was
possible. Substitution on the aromatic group of benzyl
chloride has no effect on the reaction (Table 1, entries
19±21).
È
benzyl (or alkyl) halide. The faradaõc yields stand in the
range of 50±70%.
Our ®rst experiments were conducted with PhCH2Cl and
PhI as model reagents. Starting from equal amounts of
both halides, only 50±60% of the unsymmetrical ketone
was obtained, the formation of dibenzyl ketone being a
non negligible side reaction. Then we used a two-fold
excess of the aromatic halide. Concerning the amount of
The merits of this electrochemical method lie in the access
to unsymmetrical ketones which would not be accessible by

E. Dolhem et al. / Tetrahedron 57 (2001) 525±529
527
of CO,7 we suppose that the reduction of Nibpy21 is
followed by a fast capture of CO to yield a mixed zerovalent
complex Ni0bpyCO or Ni0bpy(CO)2. However, we think
that the role of Fe(CO)5 does not consist only in being a
donor of CO and several arguments can be put forward.
First, cyclic voltammograms of solutions containing
Nibpy21 and Fe(CO)5 (see Fig. 1) show that the reduction
step of Nibpy21 is followed by another signal at 21.3 V vs.
SCE which was not observed for the electroreduction of
Nibpy21 in the presence of CO.7 We then suppose that
this new unidenti®ed signal might be related to a transient
iron carbonyl species resulting from the rapid loss of CO
from Fe(CO)5 to Ni0bpy. Besides, the presence of Fe(CO)5
allows the ef®cient formation of unsymmetrical ketones,
while the yields are poor when CO gas itself is the source
of CO.6 Moreover we have found, on the model reaction
involving PhCH2Cl and PhI, that the yield in PhCH2COPh is
very dependent on the nature of the metal carbonyl
complex. The use of W(CO)6 or Mo(CO)6 leads only to
35 and 45% (GC yields), respectively, of the mixed ketone
instead of 90% from Fe(CO)5, while no difference between
the three metal carbonyls was observed for the synthesis of
symmetrical ketones.8 Obviously, further experiments are
necessary for a better understanding of the very role of
Fe(CO)5.
Figure 1. Cylic voltametry in DMF1Bu4NBF4 0.1 mol L21 at a gold disk
electrode (1 mm diameter); scan rate of 0.1 Vs21 at room temperature.
Curve a: Nibpy21 0.02 mol L21, curve b: after addition of Fe(CO)5
0.02 mol L21
.
3. Conclusions
a Friedel±Crafts coupling between an arene and an aryl-
acetyl chloride. Indeed, no Friedel±Crafts coupling product
at the meta position will be obtained between phenol,
aniline or anisole and phenylacetyl chloride. Furthermore,
from phenol or aniline, O- or N-acylation will compete with
C-acylation.
We have shown that the Nibpy21 electroreduction into a
zerovalent nickel complex provides a good catalytic
system to achieve the synthesis of unsymmetrical ketones
especially from benzylic chlorides and aromatic iodides
using iron pentacarbonyl as the source of CO. This method,
as well as the electrochemical device, are very simple and
the experimental conditions are mild.
The carbonylating coupling between an aliphatic iodide and
an aromatic iodide is also possible but yields are moderate
(Table 1, entries 22, 23). Some other experiments involving
a heteroaromatic halide instead of the aromatic halide have
not been very successful since benzyl chloride and 2-bromo-
pyridine or 3-bromothiophene leads only to 10±20% (GC
yields) of the corresponding unsymmetrical ketone. On the
other hand, moderate yields are obtained when starting from
benzyl chloride and b-bromostyrene (Table 1, entry 24).
4. Experimental
CAUTION: Fe(CO)5 is toxic and easily ¯ammable. It must
be handled with care.
Electrolysis was conducted according to the conditions
described above. The progress of the reaction was moni-
tored by GC analysis of samples. The electrolytic solution
were poured in HCl 6 mol L21 (1/1 v/v) during at least 2 h in
order to destroy residual metal complexes. The resulting
mixtures were extracted with a suitable organic solvent
(generally diethyl ether) and evaporated. The ketones
were recovered by chromatography on a silica gel column
(elution by a mixture pentane±diethyl ether) and character-
ized by GC±MS by EI (Finnigan Ion Trap Detector 800), 1H
NMR (CDCl3/TMS, 200 MHz), 13C NMR (CDCl3/TMS,
50 MHz), and IR plus elementary analysis for unregistered
products. The analytical data given below are satisfactory.
With regard to the mechanism of the reaction, our electro-
analytical work is not suf®cient to propose a well argued
pathway and we can only give partial data. During the elec-
trolysis achieved under controlled-current conditions, we
monitored the potential of the cathode which was about
21.1±21.3 V vs SCE. This indicates that direct electro-
reductions of benzyl chlorides10 or Fe(CO)5 are not
3
involved since they both require a potential lower than
22 V.
As shown on Fig. 1, the cathodic potential agrees with the
electrochemical reduction at 21.2 V vs. SCE of the cata-
lytic precursor Nibpy21.9 In the presence of Fe(CO)5 (or
other metal carbonyl complexes), cyclic voltammetry at
potential scan rates of 0.1±5 Vs21 indicates the total lack
of reversibility of the bielectronic Nibpy21/Ni0bpy tran-
sition. As previously reported when CO itself was the source
4.1. 1,2-Diphenylethanone RN [451-40-1]
IR nCO: 1685 cm21; Mass., m/z (rel. intensity): 197(6),
105(100), 89(10), 77(57), 65(29), 51(46); 1H NMR (d

528
E. Dolhem et al. / Tetrahedron 57 (2001) 525±529
ppm) 7.97±7.2 (10H, m), 4.2 (2H, s); 13C NMR (d ppm):
197.4 (1C, CvO), 136.4±126.9 (12C, Ar), 45.3 (1C, CH2).
ppm): 7.76±6.53 (9H, m), 6.22 (2H, s, NH2), 4.19 (2H, s,
CH2). 13C NMR (d ppm): 199.7 (1C, CvO), 150.7 (1C,
C±N), 135.2±115.5 (11C, Ar), 45.9 (1C, CH2).
4.2. 1-(2-Methoxyphenyl)-2-phenylethanone RN [33470-
10-9]
4.9. 1-(3-Aminophenyl)-2-phenylethanone RN [55221-
36-0]
IR: nCO: 1680 cm21; Mass., m/z (rel. intensity): 227(4),
1
135(100), 91(8), 77(8), 63(7), 51(4); H NMR (d ppm):
IR nCO 1680 cm21; Mass., m/z (rel. intensity): 212(24),
211(48), 121(56), 120(100), 92(57), 65(58); H NMR (d
7.57±6.80 (9H, m), 4.2 (2H, s), 3.8 (3H, s); 13C NMR (d
ppm): 200.0 (1C, CvO), 158.4 (1C, C±O), 135.3±120.6
(11C, Ar), 55.4 (1C, O±CH3), 50.1 (1C, CH2).
1
ppm): 7.34±7.11 (8H, m), 6.80±6.74 (1H, m), 4.16 (2H, s,
CH2), 3.71 (2H, s, NH2); 13C NMR (d ppm): 197.7 (1C,
CvO), 146.7 (1C, C±N), 137.5±114.1 (11C, Ar), 45.3
(1C, CH2).
4.3. 1-(3-Methoxyphenyl)-2-phenylethanone RN [62381-
24-2]
4.10. 1-(4-Aminophenyl)-2-phenylethanone RN [72433-
45-5]
IR: nCO 1680 cm21; Mass., m/z (rel. intensity): 227(5),
135(100), 91(30), 77(20), 63(20), 51(7); 1H NMR (d
ppm): 7.56±7.0 (9H, m), 4.2 (2H, s), 3.8 (3H, s); 13C
NMR (d ppm): 197. 2 (1C, CvO), 159. 6 (1C, C±O),
137.7±112.6 (11C, Ar), 55.1 (1C, O±CH3), 45.3 (1C, CH2).
IR nCO 1680 cm21; Mass., m/z (rel. intensity) 212(6),
121(100), 120(85), 92(27), 77(1), 65(42); 1H NMR (d
ppm): 7.70 (2H, d, Jˆ8.6 Hz), 7.16±7.02 (5H, m), 6.55
(2H,d, Jˆ8.6 Hz), 5.4 (2H, s, NH2), 4.0 (2H, s, CH2); 13C
NMR (d ppm): 195.6 (1C, CvO), 150.9 (1C, C±N), 135.2±
126.3 (11C, Ar), 44.7 (1C, CH2).
4.4. 1-(4-Methoxyphenyl)-2-phenylethanone RN [1023-
17-2]
IR: nCO 1680 cm21; Mass., m/z (rel. intensity): 227(3),
135(100), 91(9), 77(8), 63(10); H NMR (d ppm): 7.93
4.11. 1-[4-(Dimethylamino)phenyl]-2-phenylethanone
RN [97606-39-8]
1
(2H, d, Jˆ6.9 Hz), 7.29±7.13 (5H, m), 6.86 (2H, d,
Jˆ6.9 Hz), 4.2 (2H, s), 3.8 (3H, s); 13C NMR (d ppm):
196.5 (1C, CvO), 163.5 (1C, O±C), 135.0±113.8 (11C,
Ar), 55.4 (O±CH3), 45.2 (1C, CH2).
IR nCO 1680 cm21; Mass., m/z (rel. intensity): 239(8),
148(100), 120(6), 104(7), 91(17), 77(12), 65(8), 51(6); H
NMR (d ppm): 7.86 (2H, d, Jˆ7.2 Hz), 7.23±7.13 (5H, m),
6.56 (2H,d, Jˆ7.2 Hz), 4.1 (2H, s), 3.0 (6H, s); 13C NMR (d
ppm): 195.5 (1C, CvO), 153.2 (1C, C±N), 135.6±126.3
(11C, Ar), 44.7 (1C, CH2), 39.7 (2C, CH3).
1
4.5. 1-(2-Hydroxyphenyl)-2-phenylethanone RN [2491-
31-8]
IR: nCO 1680 cm21; Mass., m/z (rel. intensity): 212(6),
122(7), 121(100), 93(12), 91(12), 65(40), 63(10); 1H
NMR (d ppm): 12.1 (1H, s), 7.73±6.7 (9H, m), 4.2 (2H,
s); 13C NMR (d ppm): 203.7 (1C, CvO), 162.7 (1C, C±O),
136.3±118.4 (11C, Ar), 44.9 (1C, CH2).
4.12. 1-[3-(1-Oxo-propyl)-phenyl]-2-phenylethanone
Calcd for C17H16O2: C, 80.7; H, 6.4. Found: C, 80.4; H, 6.6;
IR: nCO 1685 and 1681 cm21; Mass., m/z (rel. intensity):
253(19), 162(100),133(6), 105(25), 91(21), 77(15), 65(14),
1
51(10); H NMR (d ppm): 8.5 (1H, s), 8.14±8.05 (2H, m),
4.6. 1-(3-Hydroxyphenyl)-2-phenylethanone
7.53±7.15 (6H, m), 4.3 (2H, s), 2.96 (2H, q, Jˆ7.3 Hz), 1.17
(3H, t, Jˆ7.3 Hz); 13C NMR (d ppm): 199.8 (1C, CvO),
196.7 (1C, CvO), 137.1±127.0 (12C, Ar), 45.6 (1C, CH2±
Ph), 31.9 (1C, CH2±CH3), 8.0 (1C, CH2±CH3).
Calcd for C14H12O2: C, 79.2; H, 5.7. Found: C, 78.6; H, 5.8;
IR nCO 1680 cm21; Mass., m/z (rel. intensity): 213(3),
122(7), 121(100), 93(25), 65(44), 51(6); 1H NMR (d
ppm): 9.77 (1H, s), 7.47±6.91 (9H, m), 4.14 (2H, s); 13C
NMR (d ppm): 199.5 (1C, CvO), 156.6 (1C, C±O), 137.7±
115.3 (11C, Ar), 45.6 (1C, CH2).
4.13. 1-[4-(1-Oxo-propyl)-phenyl]-2-phenylethanone
Calcd for C17H16O2: C, 80.7; H, 6.4. Found: C, 80.4; H, 6.6;
IR: nCO 1684 and 1680 cm21; Mass., m/z (rel. intensity):
253(23), 162(100), 133(25), 104(37), 91(29), 76(14),
4.7. 1-(4-Hydroxyphenyl)-2-phenylethanone RN [2491-
32-9]
1
65(18), 51(10); H NMR (d ppm): 8.02±7.91 (4H, m),
7.30±7.14 (5H, m), 4.2 (2H, s), 2.94 (2H, q, Jˆ7.3 Hz),
1.16 (3H, t, Jˆ7.3 Hz); 13C NMR (d ppm): 200.1 (1C,
CvO), 197.1 (1C, CvO), 140.1 -127.1 (12C, Ar), 45.8
(1C, CH2±Ph), 32.2 ((1C, CH2±CH3), 8.1 (1C, CH2±CH3).
IR nCO 1680 cm21; Mass., m/z (rel. intensity): 213(1),
121(100), 93(13), 91(11), 77(1), 65(30); 1H NMR (d
ppm): 9.2 (1H, s), 7.97 (2H, d, Jˆ8.5 Hz), 7.3±7.2 (5H,
m), 6.93 (2H, d, Jˆ8.5 Hz), 4.3 (2H, s); 13C NMR (d
ppm): 196.1 (1C, CvO), 162.6 (1C, C±O), 131.9±116.0
(11C, Ar), 45.3 (1C, CH2).
4.14. 2-(2-Chlorophenyl)-1-(4-methoxyphenyl)ethanone
RN [41840-95-3]
4.8. 1-(2-Aminophenyl)-2-phenylethanone RN [835-38-1]
IR: nCO 1680 cm21; Mass., m/z (rel. intensity): 261(1),
152(1), 135(100), 125(6), 107(9), 92(14), 77(26), 63(16);
1H NMR (d ppm): 7.94 (2H, d, Jˆ 6.9 Hz), 7.34±7.28
(1H, m), 7.17±7.10 (3H, m), 6.86 (2H, d, Jˆ6.9 Hz), 4.3
IR nCO 1676 cm21; Mass., m/z (rel. intensity): 333(100),
212(29), 121(28), 120(77), 92(18), 65(30); H NMR (d
1

E. Dolhem et al. / Tetrahedron 57 (2001) 525±529
529
(2H, s), 3.8 (3H, s); 13C NMR (d ppm): 194.7 (1C, CvO),
4.19. 1,4-Diphenylbut-3-en-2-one (E) RN [5409-59-6]
163.5 (1C, O±C), 134.2±113.7 (11C, Ar), 55.3 (1C, O±
CH3), 42.7 (1C, CH2).
IR nCO 1690 cm21; Mass., m/z (rel. intensity): 223(14),
131(100), 103(45), 91(35), 77(37), 65(16), 51(23); 1H
NMR (d ppm): 7.54 (1H, d, Jˆ16 Hz), 7.48±7.07 (10H,
m), 6.70 (1H, d, Jˆ16 Hz), 3.9 (2H, s); 13C NMR (d
ppm): 197.4 (1C, CvO), 143.4±125.5 (14C, Ar1CvC),
48.4 (1C, CH2).
4.15. 2-(3-Chlorophenyl)-1-(4-methoxyphenyl)ethanone
RN [68968-13-8]
IR: nCO 1683 cm21; Mass., m/z (rel. intensity): 261(3),
152(1), 136(100), 125(5), 107(6), 92(13), 77(15), 64(8);
1H NMR (d ppm):7.91 (2H, d, Jˆ6.9 Hz), 7.19±7.03 (4H,
m), 6.86 (2H, d, Jˆ6.9 Hz), 4.1 (2H, s), 3.8 (3H, s); 13C
NMR (d ppm): 195.1 (1C, CvO), 163.5 (1C, O±C),
136.6±113.7 (11C, Ar), 55.2 (1C, O±CH3), 44.3 (1C, CH2).
References
1. Colquhoun, H. M.; Thomson, D. J.; Twigg, M. V. Carbonyl-
ation: Direct Synthesis of Carbonyl Compounds; Plenum:
New York, 1991.
4.16. 2-(4-Chlorophenyl)-1-(4-methoxyphenyl)ethanone
RN [52578-11-7]
2. (a) Collman, J. P. Acc. Chem. Res. 1975, 8, 342±347.
(b) Collman, J. P.; Finke, R. G.; Cawse, J. N.; Brauman, J. I.
J. Am. Chem. Soc. 1978, 100, 4766±4772.
IR: nCO 1682 cm21; Mass., m/z (rel. intensity): 261(2),
152(1), 135(100), 125(5), 107(8), 92(16), 77(24), 63(17);
1H NMR (d ppm): 7.91 (2H, d, Jˆ 6.9 Hz), 7.2±7.1 (4H,
m), 6.86 (2H, d, Jˆ6.9 Hz), 4.1 (2H, s), 3.8 (3H, s); 13C
NMR (d ppm): 195.7 (1C, CvO), 163.7 (1C, O±C),
133.4±113.9 (11C, Ar), 55.6 (1C, O±CH3), 44.4 (1C, CH2).
3. (a) Amatore, C.; Krusic, P. J.; Pedersen, S. U.; Verpeaux, J. N.
Organometallics 1995, 14, 640±649. (b) Pickett, C. J.;
Pletcher, D. J. Chem. Soc., Dalton Trans. 1975, 879±886.
4. (a) Vanhoye, D.; Bedioui, F.; Mortreux, A.; Petit, F.
Tetrahedron Lett. 1988, 29, (49), 6441±6442. (b) Yoshida,
K.; Kunugita, E. I.; Kobayashi, M.; Amano, S. I. Tetrahedron
Lett. 1989, 30 (46), 6371±6374. (c) Yoshida, K.; Kobayashi,
M.; Amano, S. I. J. Chem. Soc., Perkin Trans. 1 1992, 1127±
1129.
4.17. 1-Phenylnonan-1-one RN [6008-36-2]
IR nCO 1685 cm21; Mass., m/z (rel. intensity): 219(38),
120(35), 105(100), 77(58), 51(21); 1H NMR (d ppm):
7.88±7.82 (2H, m), 7.42±7.27 (3H, m), 2.8 (2H, t;
Jˆ7.4 Hz), 1.2 (12H, m), 0.8 (3H, t, Jˆ6.5 Hz); 13C NMR
(d ppm): 200.1 (1C, CvO), 136.9±128.1 (6C, Ar), 38.3
(1C, CH2), 32.0±22.5 (6C, Aliph), 13.9 (1C, CH3).
5. Yoshida, K.; Kuwata, H. J. Chem. Soc., Perkin Trans. 1 1996,
1873±1877.
Â
6. OcËafrain, M.; Devaud, M.; Troupel, M.; Perichon, J. J. Chem.
Soc., Chem. Commun. 1995, 2331±2332.
7. (a) OcËafrain, M.; Devaud, M.; Nedelec, J. Y.; Troupel, M.
J. Organometall. Chem. 1998, 560, 103±107. (b) OcËafrain,
M.; Dolhem, E.; Nedelec, J. Y.; Troupel, M. J. Organometall.
Chem. 1998, 571, 37±42.
4.18. 1-(4-Methoxyphenyl)-nonan-1-one RN [52754-68-4]
IR nCO 1683 cm21; Mass., m/z (rel. intensity): 249(42),
150(68), 135(100), 92(10), 77(11); 1H NMR (d ppm):
7.87 (2H, d, Jˆ8.5 Hz), 6.87 (2H, d, Jˆ8.5 Hz), 3.8 (3H,
s), 2.85 (2H, t, Jˆ7.5 Hz), 1.25±1.14 (12H, m), 0.84±0.78
(3H, t, Jˆ7.0 Hz); 13C NMR (d ppm): 199.6 (1C, CvO),
163.1 (1C, C±O), 130.1 (2C, Ar), 113.4 (2C, Ar), 55.2 (1C,
O±CH3), 38.1(1C, CH2), 31.6±18.3 (6C, Aliph.), 13.9 (1C,
CH2±CH3).
8. Dolhem, E.; OcËafrain, M.; Nedelec, J. Y.; Troupel, M.
Tetrahedron 1997, 53 (50), 17089±17096.
9. Durandetti, M.; Devaud, M. New J. Chem. 1996, 20, 659±667.
10. Baizer, M. M.; Chruma, J. L. J.Org. Chem. 1972, 37, 1951±
1957.