PAPER
Direct Chlorovinylation and Ethynylation of Some C-H Acids
95
acetylene which ethynylate C-H acids under PTC 2-Chlorovinylphenyl Ketone
Aminonitrile 3f (1.3 g, 5 mmol), CuSO .5H O (1.5 g, 6 mmol), and
6
,7
conditions cannot be excluded, taking into account
4
2
−
−
EtOH (15 mL) were refluxed for 20 min. The mixture was cooled,
diluted with H O (approx. 20 mL), and extracted with benzene (2 ×
0 mL). The organic extracts were washed with H O, dried
MgSO ), the solvent was evaporated, and the residue was purified
by column chromatography to give the title product (0.5 g, 61%) as
a colorless liquid, lit. bp: 125−127 °C/18 torr.
higher basicity of 3 than 1 (pK values of heptamethyl-
indene and 2-phenylpropionitrile are 27.4 and 23.0,
respectively ). Undoubtedly, elucidation of these mecha-
nistic problems requires further investigations.
a
2
1
(
1
2
2
4
1
8
In summary, to previously elaborated PTC ethynylation of
nitriles, dichlorovinylation of nitriles, ketones and al- 1H NMR (400 MHz): δ = 6.69 (d, 1H. J = 13.6, = CH), 6.98 (d, 1H,
6
,7
4
5
J = 13.6, = CH), 7.41−7.43 (m, 5H, ArH).
dehydes, we add now chlorovinylation of nitriles, and
ethynylation of indenes. These processes are simple, and
are applicable on available substrates leading to the prod-
ucts 3 and 5 in satisfactory yields.
Ethynylation of Indenes 4
The reactions were carried out as described above for preparation of
3
6
c, starting from indenes 4 (7 mmol) (5 h in the case of 4a, and
.5 h for 4b).
Mps (determined in capillary tube apparatus) and bps are uncorrect-
5a:
1
Yield: 1.0 g (72%); mp: 107−108 °C (hexane).
ed. H NMR spectra were measured in CDCl on a Varian Gemini
3
2
00 or Varian Gemini 400 (at 200 MHz or 400 MHz, respectively),
C NMR spectra on a Varian Gemini 200 or Varian Gemini 400 (at
0 MHz or 100 MHz, respectively). Chemical shifts (δ) are given in
1
H NMR (200 MHz): δ = 1.57 (s, 3H, CH ), 1.70 (s, 1H, CH), 2.06
3
1
3
(
d, 3H, J = 1.4, CH ), 5.98 (d, 1H, J = 1.4, = CH), 7.12−7.41 (m,
3
5
4
H, ArH).
13C NMR (50 MHz): δ = 12.69, 23.75, 79.95, 81.06, 119.26,
21.20, 126.31, 128.28, 137.64, 138.86, 142.94, 149.99.
IR (KBr): ν = 3328, 2972, 2920, 2856, 2246, 1628, 1388, 1084, 756
ppm relative to TMS and coupling constants (J) are given in Hz.
Gas chromatography (GC) analyses were performed with a
Hewlett−Packard 5890 Ser. II chromatograph, equipped with
HP50+capillary column (30 m). IR spectra were recorded on
Perkin−Elmer 577 spectrometer; liquids as films, and solids as
potassium bromide pellets. Elemental analyses were performed
1
−
1
cm .
Anal. Calcd for C H (168.2): C, 92.81; H, 7.19. Found: C, 92.68;
H 7.15.
1
3
12
with
Column chromatography was carried out on Merck Kieselgel
0 (230−400 mesh) with hexane/EtOAc as eluent. The nitriles 1a,
a Perkin−Elmer CHNO/S Ser. II 2400 microanalyzer.
5
b:
6
1
3
14
15
16
Yield: 1.2 g (62%); isolated by column chromatography (Merck sil-
ica gel 60, hexane/EtOAc, 9:1).
b, 1c−e, 1f, and indene 4a were prepared according to litera-
ture procedures. 1,3-Di-(n-butyl)indene (4b) was prepared by
alkylation of indene with excess of n-butyl bromide under PTC con-
ditions.17 The distilled mixture which consisted of 1,1- and 1,3-di-
1
H NMR (400 MHz): δ = 0.92 (t, 3H, J = 7.2, CH ), 1.01 (t, 3H,
3
J = 7.2, CH ), 1.29−2.56 (m, 12H, 6 × CH ), 2.15 (s, 1H, ≡CH), 6.14
3
2
(
(
n-butyl)indene (11% and 87%, GC) was used for chlorovinylation.
E)-Dichloroethylene (Fluka, ≥ 95%), other reagents and all sol-
(
s, 1H, = CH), 7.31−7.48 (m, 4H, ArH).
13C NMR (100 MHz): δ = 13.90, 13.96, 22.63, 22.95, 27.08, 27.96,
vents were commercial.
2
1
9.79, 39.01, 49.38, 68.12, 85.33, 119.45, 122.40, 125.84, 127.20,
33.75, 143.48, 143.60, 149.09.
Chlorovinylation of Nitriles 1; General Procedure
Into a round-bottomed flask equipped with a sealed mechanical stir-
IR (KBr): ν = 3304, 3068, 2956, 2864, 2824, 2772, 2244, 1616,
−
1
1
460, 1036, 700 cm .
rer, a thermometer, a cold-trap with acetone/solid CO , a septum,
2
and an inlet for Ar were introduced nitrile 1 (10 mmol), (E)-dichlo-
roethylene (2, 2.9 g, 2.3 mL, 30 mmol), TBAHS (0.34 g, 1 mmol),
Anal. Calcd for C H (252.4): C, 90.41; H, 9.58. Found: C, 90.38;
H, 9.58.
1
9
24
and a mixture of Et O (8 mL) and cyclohexane (8 mL). The contents
2
of the flask were stirred, flushed with Ar, and 50% NaOH (9.6 g,
6
.4 mL, 120 mmol) was added with syringe (small exothermal ef- Acknowledgement
fect is observed, and the mixture darkened). Then the mixture was
heated at 48−55 °C for the time indicated in Table 1, cooled, diluted
with H O (25 mL), and extracted with CH Cl (3 × 15 mL). The or-
Support of this work by the State Committee for Scientific Research
Grant No. 3 TO9A 013 15) is gratefully acknowledged.
(
2
2
2
ganic extracts were washed with H O, dried (MgSO ), the solvent
2
4
was evaporated, and the residue was purified as reported in Table 1
to give chlorovinylated nitriles 3a, b, d−f.
References
(
1) Pielichowski, J.; Popielarz, R. Synthesis 1984, 433.
Nitrile 3c
(2) KuliÒski, T.; JoÒczyk, A. Synthesis 1992, 757.
(3) Dehmlow, E. V.; Dehmlow, S. S Phase Transfer Catalysis,
3rd ed.; Verlag Chemie: Weinheim, 1993.
The reaction was carried out according to general procedure using
1
c (1.6 g, 10 mmol), TBAHS (0.34 g, 1 mmol), Et O (8 mL), cyclo-
2
hexane (8 mL) and powdered KOH (6.7 g, 120 mmol). To this
mixture, during stirring, the solution of (E)-dichloroethylene (2.9 g,
Starks, C. M.; Liotta, C. L.; Halpern, M. Phase-transfer
Catalysis; Chapman & Hall: New York, London, 1994.
Mπkosza, M.; FedoryÒski, M. Pol. J. Chem. 1996, 70, 1093.
Mπkosza, M.; FedoryÒski, M. In Handbook of Phase Transfer
Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic
& Professional: London, 1997; p 135.
2
.3 mL, 30 mmol) in Et O (3 mL) was added with syringe and the
2
reaction was carried out at 48–55 °C and for the time indicated in
Table 1. The crude reaction mixture which contained 74% of 1c and
9
1
5% of 3c (GC) was treated with iso-propyl β-chloropropionate
(
2.2 g) and finally the product 3c was purified by means of column
(4) JoÒczyk, A.; Gierczak, A. H. Synthesis 1998, 962.
(5) JoÒczyk, A.; Gierczak, A. H. Tetrahedron, 2000, 56, 6083.
chromatography (Table 1).
(
6) JoÒczyk, A.; KuliÒski, T.; Czupryniak, M.; Balcerzak, P.
Synlett 1991, 639.
(
7) KuliÒski, T.; JoÒczyk, A. Pol. J. Chem. 1994, 68, 2455.
Synthesis 2001, No. 1, 93–96 ISSN 0039-7881 © Thieme Stuttgart · New York