J. CHEM. RESEARCH (S), 1999 331
r.t.
2
+
R'Li or R'MgBr
RCHR'
NH2
4a–m
S
R =
,
,
,
,
,
O2N
MeO
Cl
R' = Me, Ph, n-Bu, PhCH2, CN, CH2CN, CH2SiMe3, PhC≡C, Me3SiC≡C
Scheme 2
were taken on a Matt Son 1000 Unicam FTIR, 1H and 13C NMR
spectra on Bruker AC 80 spectrometer. All reactions were
performed under argon. Chemicals were purchased from Fluka and
used as received.
Caution: Although we did not have any accidents using LiClO4, it
is advised to dry lithium perchlorate in a hood using a suitable
lab-shield. The ether solution should be freshly prepared and not
stored.
We acknowledge Volkswagen-Stiftung, Federal Republic of
Germany for ¢nancial support to purchase laboratory
chemicals. We also thank the Research Council of the Sharif
University of Technology for its partial ¢nancial support
of this work.
a
Received, 30th October 1998; Accepted, 2nd February 1999
Paper E/8/08424F
Procedure for the Preparation of Primary Amines (Entries 1^13 in
Ta bl e 1).öHexamethyldisilazane, HMDS (3.3 mmol, 0.54 g), was
placed in a two-necked £ask ¢tted with a condenser and a stirring
bar, under argon, 3.5 mmol of sodium hydride (60^65%, after
washing with light petroleum) or 3.3 mmol of methyllithium in diethyl
ether were added, and the mixture was stirred for about 5 min. Then
3 mL solution of 5 M LPDE and 2 mmol of aldehyde were added
via a syringe. After stirring for 30 min, organometallic reagent or
other nucleophile (4 mmol) was added via syringe, and the mixture
stirred for 30 min. Water (10 mL) was added and the product
extracted with ether ꢀ2 Â 10 mL). The organic layer was separated
and extracted with cold 0.5 MHCl solution. Neutralization with a
2.0 M solution of KOH gave the desired product. Further puri¢cation
was by preparative gas chromatography if needed. The structures of
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4
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12
and compared with those reported.10
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All new products showed
7
Selected Spectroscopic Data.ö4b: 1H NMR (CDCl3) d 7.00^7.41
(m, 5 H), 5.35 (s, 1H), 1.12 (s, 2 H); IR (neat) n 3392, 3320, 2238 cm
1
.
4g: 1H NMR (CDCl3) d 6.61^7.80 (m, 9 H), 5.38 (s, 1H), 3.62 (s, 3 H),
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(C), 104.48 (C), 126.78 (CH), 128.02 (CH), 128.54 (CH), 129.41 (CH),
131.92 (CH), 136.15 (C); IR (neat) n 3434, 2173, 843 cm 1. 4m:
1H NMR (CDCl3) d 0.00 (s, 9 H), 1.30 (d, J 7:4, 2 H), 3.26 (br
s, 2 H), 5.06 (t, J 7:4 1H), 6.80^7.47 (m, 3 H); 13C NMR (CDCl3)
8
9
C. Sahlberg, S. B. Ross, I. Fagerwall, A. L. Ask and A. J.
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d
1:13 (CH3), 28.88 (CH2), 67.67 (CH), 123.26 (CH), 124.19 (CH),
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1
126.27 (CH), 151.20 (C); IR (neat) n 3394, 1251, 852 cm
.