Synthesis of α-phenylselanyl and α-phenylsulfanyl nitriles from aldehyde N,N-dialkylhydrazones

Article abstract of DOI:10.1016/S0040-4020(02)00232-6

Phenylselenenylation of azaenolates, formed by LDA treatment of dimethylhydrazones 1 (R²=H) and derived from linear aliphatic aldehydes, has led to α-phenylselanyl hydrazones 2. α-Phenylselanyl nitriles 3 were, however, isolated when an excess of base and of PhSeX (X=Cl, Br) were used. Hydrazones 1 bearing an α-alkyl substituent (R²≠H) gave also nitriles 3. SAMP-hydrazones 4 showed the same reactivity and the corresponding nitriles 3 were obtained in a racemic form. The use of PhSCl, in the place of PhSeBr, has led to α-phenylsulfanyl nitriles 6 from hydrazones 1 derived from α-branched aldehydes (R²≠H).

Full text of DOI:10.1016/S0040-4020(02)00232-6

TETRAHEDRON
Pergamon
Tetrahedron 58 02002) 3275±3279
Synthesis of a-phenylselanyl and a-phenylsulfanyl nitriles
from aldehyde N,N-dialkylhydrazones
p
Michael Ternon, Xavier Pannecoucke, Francis Outurquin and Claude Paulmier
È
Á Â Â Â
Laboratoire de Synthese Thio-et-Seleno-organique, IRCOF-UFR Sciences, Univertsite de Rouen, F-76821,
Mont Saint Aignan Cedex, France
In memoriam Professor Claude Paulmier who deceased on 28 November 2001
Received 15 November 2001; revised 13 February 2002; accepted 26 February 2002
AbstractÐPhenylselenenylation of azaenolates, formed by LDA treatment of dimethylhydrazones 1 0R2ˆH) and derived from linear
aliphatic aldehydes, has led to a-phenylselanyl hydrazones 2. a-Phenylselanyl nitriles 3 were, however, isolated when an excess of base
and of PhSeX 0XˆCl, Br) were used. Hydrazones 1 bearing an a-alkyl substituent 0R2±H) gave also nitriles 3. SAMP-hydrazones 4 showed
the same reactivity and the corresponding nitriles 3 were obtained in a racemic form. The use of PhSCl, in the place of PhSeBr, has led to
a-phenylsulfanyl nitriles 6 from hydrazones 1 derived from a-branched aldehydes 0R2±H). q 2002 Elsevier Science Ltd. All rights
reserved.
Some years ago, we prepared, with modest enantiomeric
excesses, 0R)-2-arylselanyl-2-phenylpropanals by a-selene-
nylation of 2-phenylpropanal using chiral selenenamides,
especially those derived from 0S)-proline methyl ester.1 In
the search of a general method for the synthesis of enantio-
merically enriched a-phenylselanyl carbonyl compounds,2±4
we were interested in the metalation±alkylation method of
SAMP and RAMP-hydrazones developed by Enders and
Eichenauer.6 After regeneration of the carbonyl group,
a-alkyl carbonyl compounds were prepared with excellent
ee. Optically active a-phenylsulfanyl aldehydes were
prepared either by alkylation of the azaenolate formed
from phenylsulfanylethanal SAMP-hydrazone5,7 or by
sulfenylation of azaenolates derived from aldehyde or
ketone SAMP-hydrazones.8
Dimethylhydrazones 1d±f, formed from a-branched alde-
hydes, were also treated with excesses of LDA and PhSeBr.
The corresponding a-phenylselanyl nitriles 3d±f were
obtained in good yields 0entries 5, 7 and 9). With
1.2 equiv. of base and 1.2 equiv. of PhSeBr, the nitrile 3
could also be obtained, but with lower yields 0entries 6
and 8).
The metalation±sulfenylation reaction 0LDA, 2.5 equiv.
and PhSCl, 2.5 equiv.) was also carried out on dimethyl-
hydrazones 1a and 1b. According to the work of Enders
et al.,8 the a-phenylsulfanyl hydrazones 5a and 5b were
isolated in correct yields but the a-phenylsulfanyl nitrile
6a 0R1ˆnBu, R2ˆH) appeared also as a by-product 0entries
10 and 11). Under the same experimental conditions, the
a-alkyl hydrazones 1d±f have led to the corresponding
a-phenylsulfanyl nitriles 6d±6f albeit in poorer yields
than those observed for the selenium analogues 0entries
12±14).
Using this method, good diastereoisomeric excesses were
observed for the metalation±alkylation of phenylselanyl-
ethanal SAMP-hydrazone.9 In the course of the selenenyl-
ation of azaenolates, formed from dimethylhydrazones
1 0R2ˆH) 0LDA, 1.2 equiv., THF, 08C then PhSeBr,
1.2 equiv.), the corresponding a-phenylselanyl hydrazones
2 were isolated with modest yields. 0Scheme 1; Table 1,
entries 1 and 2). To improve the yields, greater amounts
of base and of PhSeBr 02.5 equiv.) were used. Surprisingly,
the formation of the corresponding nitriles 3 0R2ˆH) was
observed 0Table 1, entries 3 and 4). Similar results were
obtained at 2788C and when PhSeCl or PhSeSePh were
used as selenium reagent.
The metalation±selenenylation reaction of a 1/1 diastereo-
isomeric mixture of SAMP-hydrazone 4e 0R1ˆnPr,
R2ˆMe), using an excess of reagents, afforded the 2-meth-
yl-2-phenylselanyl pentanenitrile 3e in a racemic form
0entry 15). 2S-enriched samples of SAMP-hydrazones 4e
and 4g were also subjected to the reaction. The a-phenyl-
selanyl nitriles 3e and 3g, respectively, were also obtained
without optical activity 0entries 16 and 17).
The synthesis of nitriles from aldehyde dialkylhydrazones is
well documented. Nitriles could be synthesized by oxidation
of the dialkylamino group followed by syn-elimination of
dialkylhydroxylamine. H2O2 oxidation,10,11 oxone treatment
Keywords: hydrazone; SAMP; deprotonation; nitrile.
Corresponding author. Fax: 133-2-35-52-29-59;
e-mail: francis.outurquin@univ-rouen.fr
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020002)00232-6

3276
M. Ternon et al. / Tetrahedron 58 -2002) 3275±3279
Scheme 1.
Table 1. a-Phenylselanyl hydrazones 2, nitriles 3 and sulfur analogues 5 and 6
Entry
Hydrazone no.
R1
R2
PhYX
LDA and PhYX 0n equiv.)
Yields 0%)
Hydrazone
Nitrile
1
2
3
4
5
6
7
8
1a
1b
1a
1c
1d
1e
1e
1f
nBu
Bn
nBu
iPr
Me
nPr
nPr
Et
H
H
H
H
Me
Me
Me
Et
Et
H
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSeBr
PhSCl
PhSCl
PhSCl
PhSCl
PhSCl
PhSeBr
PhSeBr
PhSeBr
1.2
1.2
2.5
2.5
2.5
1.2
2.5
1.2
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2a 042)
2b 045)
±
±
±
±
±
±
±
5a 050)
5b 057)
±
±
±
±
±
±
±
±
3a 043)
3c 052)
3d 078)
3e 048)
3e 075)
3f 035)
3f 070)
6a 010)
±
6d 048)
6e 051)
6f 062)
3e 060)
3e 072)b
3g 067)b
9
1f
Et
10
11
12
13
14
15
16
17
1a
1b
1d
1e
1f
4e
4ea
4ga
nBu
Bn
Me
nPr
Et
nPr
nPr
Et
H
Me
Me
Et
Me
Me
Me
a
2R-SAMP-hydrazone.
Racemic nitrile.
b
under microwave irradiation12 have also been proposed.
Enders et al. have used magnesium monoperoxyphthalate
hexahydrate 0MMPP) in the case of dimethylhydrazones13
and SAMP-hydrazones allowing the synthesis of nitriles
with an a-asymmetric centre.14 The activation of the dialkyl-
amino group can be also achieved by methylation15,16 or
alkyl chloroformate addition.17 A subsequent basic treat-
ment allows the formation of the nitrile group.
deprotonation±alkylation of phenylselanyl acetonitrile,19
Bu3P±PhSeCNtreatment of aliphatic aldehydes, phenyl-
20
selenolate substitution of a a-mesyl nitrile,21 SnCl4-acti-
22
vated reaction of Me3SiCNwith selenoacetals and
conjugate addition of an enamine with a-phenylselanyl
acrylonitrile.23 a-Phenylsulfanyl nitriles have been prepared
24
by reaction of Me3SiCNwith thioacetals
sulfanyl) alkylbenzotriazoles.25
or a-0phenyl-
Some a-phenylselanyl nitriles have been prepared by dif-
Concerning the mechanistic aspect of this two-step reaction,
we ®rst observe that, when R2ˆH, the introduction of one
ferent ways: Deprotonation±selenenylation of nitriles,18
Scheme 2.

M. Ternon et al. / Tetrahedron 58 -2002) 3275±3279
3277
Scheme 3.
molar equivalent of base must lead to the lithium azaenolate
A, stabilized by the chelating effect of the dialkylamino
group. The reaction with the selenium electrophile affords
the a-phenylselanyl hydrazones 2 0Scheme 2). The forma-
tion of the chelated intermediate A has been proposed to
explain the excellent asymmetric induction observed when
SAMP-hydrazones were used as substrates.26
The formation of the nitrile function must be accompanied
by the regeneration of LDA. In a subsequent reaction, the
a-metalation±chalcogenation of the nitrile 0Scheme 3, route
B) occurred as proposed in the literature.18 Starting from
2R-SAMP hydrazones, the isolation of racemic nitriles 3
is more easily explained by route B. The formation of the
nitrile functional group must occur before a-chalcogenation
as proposed by Normant et al.27 Work is in progress to
obtain more information regarding the regiocontrol of the
deprotonation. Other bases and experimental conditions are
being used.
When R2ˆH, in the presence of LDA and PhSeBr in
excesses, the carbanionic species B must be formed and
leads to the nitrile 3 0R2ˆH) after loss of lithium dialkyl-
amide 0Table 1, entries 3 and 4, Scheme 3). The sulfur
analogue is less prone to the elimination of LiNRR0 and
6a was only isolated as a by-product 0Table 1, entries 10
and 11). Using stoichiometric amounts of reagents, Enders
et al.8 have only observed the formation of a-phenylsulfanyl
hydrazones 5. In conclusion, when R2ˆH, the a-chalco-
genated nitriles 3a,c were obtained probably through path-
way A. This is in accordance with the fact that when
1.2 equiv. of LDA and PhSeBr were used, hydrazones 2
could be isolated in modest yields. But surprisingly, even
varying the amount of base, with or without PhSeBr, we
were not able to generate a-selenylated nitriles 3a,b from
hydrazones 2a,b. Experiments are still under investigations
to try to explain this result.
We have described the synthesis of a-selanyl and a-sulfanyl
nitriles, in a one-pot metalation±chalcogenation reaction,
starting from aliphatic aldehyde dialkylhydrazones.
a-Alkyl hydrazones were ef®ciently transformed into
nitriles but those derived from linear aldehydes, needed
excesses of LDA. a-Chalcogenated hydrazones could only
be obtained from linear aldehyde hydrazones using 1 equiv.
of LDA.
1.Experimental
Dimethylhydrazones26 and SAMP-hydrazones6 were
prepared as described. THF was distilled over sodium-
benzophenone and diisopropylamine over NaOH. The
chromatographic separations were achieved on silica gel
00.060±0.200 nm, pore diameter ca. 4 nm) available from
Starting from a-branched aldehyde hydrazones 1 or 4
0R2±H), a-chalcogenated nitriles 3d±g 0YˆSe) and 6d±f
0YˆS) were only isolated, even when 1.2 equiv. of LDA and
1.2 equiv. PhSeBr were used 0Table 1). When 2R-SAMP
hydrazones 4e and 4g were used, we could only isolate
the racemic nitriles 3e and 3g, respectively 0Table 1, entries
16 and 17). These two facts cannot be explained by the
two-step pathway A.
1
ACROS. H and 13C NMR spectrum were recorded on
Brucker AC 200 and DPX 300 instruments and carried out
in CDCl3.
1.1. Preparation of a-phenylselanyl dimethylhydrazones 2
In addition, Normant et al.27 have observed the formation
of a-alkyl hydrazones after metalation±alkylation of
dimethylhydrazones, derived from linear aldehydes, in the
presence of HMPA. Starting from a-branched aldehyde
dimethylhydrazones, a-alkyl nitriles were only obtained.
They suggested that the chelating effect of the cosolvent
has favoured the displacement of the deprotonation site to
the iminyl carbon.
The hydrazone 1 01 mmol) in THF 010 ml) was added to a
freshly prepared solution of LDA 01.2 mmol) at 08C under
argon. After 6 h at 08C, a solution of PhSeBr 0283 mg,
1.2 mmol) in THF 01 ml) was introduced. The mixture
was stirred overnight at room temperature and then treated
with a sat. aq. NaCl solution 010 ml). The organic layer was
dried and the solvent eliminated. The hydrazones 2 were

3278
M. Ternon et al. / Tetrahedron 58 -2002) 3275±3279
1
puri®ed by silica gel chromatography 0eluent: cyclohexane±
CH2Cl2, 8:2).
yieldˆ70%. H NMR, d: 7.7 0m, 2H, Ph), 7.2 0m, 3H,
Ph), 1.72 0q, 4H, H3, Jˆ7.3 Hz), 1.04 0t, 6H, H4, Jˆ
7.3 Hz). 13C N MR,d: 137.8, 129.9, 129.2, 125.7, 121.8
0Ph, C1), 43.5 0C2), 29.8 0C3), 9.8 0C4). MS 0EI, 70 eV):
253 0M1, 70), 158 0100). Anal. calcd for C12H15NSe: C,
57.15; H, 5.99; N, 5.55; found: C, 57.56; H, 6.19; N, 5.87%.
1.1.1. 2-Phenylselanylhexanal dimethylhydrazone 2a.
1
Oil, yieldˆ42%. H NMR, d: 7.5 0m, 2H, Ph), 7.2 0m,
3H, Ph), 6.42 0d, 1H, H1, Jˆ8.1 Hz), 3.98 0q, 1H, H2, Jˆ
8.1 Hz), 2.57 0s, 6H, N0CH3)2), 1.75 0q, 2H, CH2, Jˆ
8.1 Hz), 1.39 0m, 4H, CH2), 0.86 0t, 3H, CH3, Jˆ7.5 Hz).
13C NMR, d: 137.5, 135.1, 128.6, 128.4, 127.3 0Ph, C1),
46.3 0C2), 42.8 0N0CH3)2), 32.9 0C5), 30.1 0C4), 22.1 0C3),
13.7 0C6). Anal. calcd for C14H22N2Se: C, 56.56; H, 7.46; N,
9.42; found: C, 56.30; H, 7.73; N, 9.24%.
1.2.6. 2-Methyl-2-phenylselanylbutanenitrile 3g. Oil,
1
yieldˆ67%. H NMR, 7.72±7.77 0m, 2H, Ph), 7.36±7.42
0m, 3H, Ph), 1.75±1.91 0m, 2H, CH2), 1.59 0s, 3H, H5), 1.13
0t, 3H, H4, Jˆ7.4 Hz). 13C NMR, d: 137.7, 131.4, 129.9,
126.7, 122.5 0Ph, C1), 36.5 0C2), 33.2 0C3), 25.2 0C5), 10.2
0C4). MS 0CI, 200 eV): 240 0MH1, 100), 213 060). Anal.
calcd for C11H13NSe: C, 55.47; H, 5.50; N, 5.88; found: C,
55.81; H, 5.51; N, 5.81%.
1.1.2. 3-Phenyl-2-phenylselanylpropanal dimethylhydra-
zone 2b. Oil, yieldˆ45%. 1H N MR,d: 7.5 0m, 2H, Ph), 7.2
0m, 8H, Ph), 6.47 0d, 1H, H1, Jˆ7 Hz), 4.26 0q, 1H, H2,
Jˆ7.0 Hz), 3.15 0m, 2H, CH2), 2.57 0s, 6H, N0CH3)2). 13C
NMR, d: 139.6, 136.5, 135.9, 129.8, 129.5, 129.3, 129.1,
128.1, 126.7 0C1, Ph), 46.8 0C2), 42.6 0N0CH3)2), 39.4 0C3).
Anal. calcd for C17H20N2Se: C, 61.63; H, 6.08; N, 8.46;
found: C, 61.71; H, 6.16; N, 8.55%.
1.3. Preparation of a-phenylsulfanyl dimethyl-hydra-
zones 5
The reaction was carried out as for the selenylated hydra-
zones 2 using hydrazones 1 01 mmol), LDA 02.5 mmol),
PhSCl 0360 mg, 2.5 mmol). The hydrazones 5 were puri®ed
by silica gel chromatography 0eluent: cyclohexane±CH2Cl2,
8:2).
1.2. Preparation of a-phenylselanylnitriles 3
The reaction was carried out as above using hydrazones 1 or
4 01 mmol), LDA 02.5 mmol), PhSeBr 0590 mg, 2.5 mmol).
The nitriles 3 were puri®ed by silica gel chromatography
0eluent: cyclohexane±CH2Cl2, 8:2).
1.3.1. 2-Phenylsulfanylhexanal dimethylhydrazone 5a.
1
Oil, yieldˆ50%. H NMR, d: 7.7 0m, 2H, Ph), 7.2 0m,
3H, Ph), 6.27 0d, 1H, H1, Jˆ7.3 Hz), 3.77 0q, 1H, H2,
Jˆ7.3 Hz), 2.55 0s, 6H, N0CH3)2), 1.65 0q, 2H, H3, Jˆ
7.3 Hz), 1.2±1.4 0m, 4H, H4, H5), 0.82 0t, 3H, H6, Jˆ
7.3 Hz). 13C N MR,d: 137.2, 132.0, 129.1, 128.2, 126.4
0Ph, C1), 50.4 0C2), 42.9 0N0CH3)2), 32.8 0C3), 28.2 0C4),
22.3 0C5), 13.8 0C6). MS 0CI, 200 eV): 251 0MH1, 20),
141 0100). Anal. calcd for C14H22N2S: C, 67.15; H, 8.86;
N, 11.19; found: C, 67.26; H, 9.12; N, 11.41%.
1.2.1. 2-Phenylselanylhexanenitrile 3a. Oil, yieldˆ43%.
1H N MR,d: 7.7 0m, 2H, Ph), 7.2 0m, 3H, Ph), 3.53 0t, 1H,
H2, Jˆ7.3 Hz), 1.77 0q, 2H, H3, Jˆ7.3 Hz), 1.6 0m, 2H, H4),
1.25 0m, 2H, H5), 0.80 0t, 3H, H6, Jˆ7.3 Hz). 13C N MR,d:
136.9, 130.5, 129.1, 125.6, 119.7, 0Ph, C1), 32.0 0C3), 29.5
0C4), 25.6 0C2), 21.4 0C5), 13.3 0C6). MS 0EI, 70 eV): 253
0M1z, 90), 158 0100). Anal. calcd for C12H15NSe: C, 57.15;
H, 5.99; N, 5.55; found: C, 57.48; H, 6.12; N, 5.65%.
1.3.2. 3-Phenyl-2-phenylsulfanylpropanal dimethylhydra-
zone 5b. Oil, yieldˆ57%. 1H NMR, d: 7.10±7.40 0m, 10H,
Ph), 6.32 0d, 1H, H1, Jˆ7.2 Hz), 4.07 0q, 1H, H2, Jˆ7.2 Hz),
2.92±3.10 0m, 2H, CH2), 2.53 0s, 6H, N0CH3)2). 13C N MR,
d: 137.2, 134.5, 133.5, 131.3, 128.3, 128.0, 127.4, 125.9,
125.4, 51.4 0C2), 42.6 0N0CH3)2), 39.4 0C3). MS 0CI,
200 eV): 285 0MH1, 20), 141 0175). Anal. calcd for
C17H20N2S: C, 71.79; H, 7.09; N, 9.85; found: C, 71.52;
H, 7.02; N, 9.99%.
1.2.2. 3-Methyl-2-phenylselanylbutanenitrile 3c. Oil,
1
yieldˆ52%. H N MR,d: 7.7 0m, 2H, Ph), 7.2 0m, 3H,
Ph), 3.45 0d, 1H, H2, Jˆ6.0 Hz), 2.01 0oct, 1H, H3, Jˆ
6.0 Hz), 1.09 0d, 6H, H4, Jˆ6.0 Hz). 13C NMR, d: 136.0,
131.3, 129.5, 121.7, 120.0 0Ph, C1), 35.3 0C2), 31.3 0C3),
21.1, 19.8 0C4). MS 0EI, 70 eV): 239 0M1z, 70), 170 040),
157 0100), 82 030), 77 0100). Anal. calcd for C11H13NSe: C,
55.47; H, 5.50; N, 5.88; found: C, 55.65; H, 5.86; N, 5.96%.
1.2.3. 2-Methyl-2-phenylselanylpropanenitrile 3d.28 Oil,
1.4. Preparation of a-phenylsulfanylnitriles 6
1
yieldˆ78%. H N MR,d: 7.7 0m, 2H, Ph), 7.43±7.30 0m,
3H, Ph), 1.63 0s, 6H, CH3). 13C NMR, d: 137.4, 129.9,
129.2, 126.9 0Ph), 123.0 0C1), 30.0 0C2), 27.9 0C3). MS
0EI, 70 eV): 225 0M1z, 40), 77 090).
The reaction was carried out as above using hydrazones 1
01 mmol), LDA 02.5 mmol), PhSCl 0360 mg, 2.5 mmol).
The nitriles 6 were puri®ed by silica gel chromatography
0eluent: cyclohexane±CH2Cl2, 8:2).
1.2.4. 2-Methyl-2-phenylselanylpentanenitrile 3e. Oil,
1.4.1. 2-Phenylsulfanylhexanenitrile 6a.29 Oil, yieldˆ
1
yieldˆ75%. H N MR,d: 7.7 0m, 2H, Ph), 7.2 0m, 3H,
1
57%. H N MR,d: 7.7 0m, 2H, Ph), 7.2 0m, 3H, Ph), 3.60
Ph), 1.70 0m, 2H, H3), 1.50 0m, 2H, H4), 1.53 0s, 3H, H6),
0.88 0t, 3H, H5, Jˆ7.3 Hz). 13C NMR, d: 137.5, 129.7,
128.9, 125.8, 122.4 0Ph, C1), 41.8 0C3), 35.4 0C2), 25.7
0C6), 19.1 0C4), 13.8 0C5). MS 0EI, 70 eV): 253 0M1z, 60),
158 0100), 78 050). Anal. calcd for C12H15NSe: C, 57.15; H,
5.99; N, 5.55; found: C, 57.56; H, 6.19; N, 5.87%.
0t, 1H, H2, Jˆ7.4 Hz), 1.77 0q, 2H, H3, Jˆ7.4 Hz), 1.6 0m,
2H, H4), 1.25 0m, 2H, H5), 0.82 0t, 3H, H6, Jˆ7.4 Hz). 13C
NMR, d: 135.2, 130.8, 129.2, 125.6, 119.1, 0Ph, C1), 36.8
0C2), 32.0 0C3), 28.8 0C4), 21.7 0C5), 13.5 0C6).
1.4.2. 2-Methyl-2-phenylsulfanylpropanenitrile 6d.25 Oil,
yieldˆ48%. 1H NMR, d: 7.7 0m, 2H, Ph), 7.2 0m, 3H, Ph),
1.2.5. 2-Ethyl-2-phenylselanylbutanenitrile 3f. Oil,

M. Ternon et al. / Tetrahedron 58 -2002) 3275±3279
3279
1.53 0s, 6H, H3). 13C NMR, d: 136.6, 130.1, 128.6, 124.1,
122.1 0Ph, C1), 39.6 0C2), 27.4 0C3).
9. Ternon, M.; Outurquin, F.; Paulmier, C. Unpublished results.
10. Smith, R. F.; Albright, J. A.; Waring, A. M. J. Org. Chem.
1966, 31, 4100.
1.4.3. 2-Methyl-2-phenylsulfanylpentanenitrile 6e. Oil,
11. Stantovic, S.; Espenson, J. H. Chem. Commun. 1998, 1579.
12. Ramalingam, T.; Subba Reddy, B. V.; Srinivas, R.; Yadav,
J. S. Synth. Commun. 2000, 30, 4507.
1
yieldˆ51%. H NMR, d: 7.7 0m, 2H, Ph), 7.2 0m, 3H,
Ph), 1.55±1.75 0m, 4H, H3, H4), 1.44 0s, 3H, H6), 0.90 0t,
3H, H5, Jˆ7.2 Hz). 13C N MR,d: 136.8, 130.0, 129.1, 129.0,
121.7 0Ph, C1), 44.3 0C2), 41.55 0C3), 25.2 0C6), 18.4 0C4),
13.7 0C5). MS 0EI, 70 eV): 205 0M1, 70), 110 0100). Anal.
calcd for C12H15NS: C, 70.20; H, 7.36; N, 6.82; found: C,
70.27; H, 7.67; N, 7.13%.
13. Enders, D.; Plant, A. Synlett 1990, 725.
14. Enders, D.; Plant, A. Synlett 1994, 1054. Enders, D.; Plant, A.;
Backhaus, D.; Reinhold, U. Tetrahedron 1995, 51, 10699.
15. Moore, J. S.; Stupp, S. I. J. Org. Chem. 1990, 55, 3374.
16. Kamal, A.; Arifuddin, M.; Venugopal Rao, N. Synth.
Commun. 1998, 28, 4507.
1.4.4. 2-Ethyl-2-phenylsulfanylbutanenitrile 6f.24 Oil,
17. Xiao, Z.; Timberlake, J. W. Tetrahedron 1998, 54, 12715.
18. Brattesani, D. N.; Heathcock, C. H. Tetrahedron Lett. 1974,
2279.
1
yieldˆ62%. H NMR, d: 7.7 0m, 2H, Ph), 7.2 0m, 3H,
Ph), 1.72 0q, 4H, H3, Jˆ7.3 Hz), 1.05 0t, 6H, H4,
Jˆ7.3 Hz). 13C NMR, d: 136.9, 130.0, 129.2, 129.1, 121.0
0Ph, C1), 50.5 0C2), 29.1 0C3), 8.8 0C4).
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21. Misjashita, M.; Makino, N.; Singh, M.; Yoshikoshi, J. Chem.
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