ACYL IODIDES IN ORGANIC SYNTHESIS.
1477
Scheme 3.
O
O
O
+
O
O
O
O
R
R
NMe2
O
R'
I
+
I–
R
N
R'
R
I
R'
NMe2
Me
Me
+
MeI
N
R'
Me
R = Me, Ph; R′ = H, Me.
EXPERIMENTAL
5 ml of methylene chloride. The mxture was heated for
3 h under reflux, and distillation gave 0.18 g of MeI,
bp 42°C, nD20 = 1.5317 [1H NMR spectrum: δ 2.12 ppm,
s (3H, CH3)] and 0.58 g (0.065 mol, 36%) of initial
DMA, bp 165°C, nD20 = 1.4380; published data [6]:
The H and 13C NMR spectra were recorded on
a Bruker DPX-400 spectrometer at 400.1 and
100.61 MHz, respectively, using chloroform-d as
solvent and cyclohexane as internal reference. Gas
chromatographic–mass spectrometric analysis was per-
formed using a Hewlett–Packard 5971A mass-selective
detector (electron impact, 70 eV) coupled with
an HP-5890 gas chromatograph (Ultra-2 column,
5% of phenylmethylsilicone; injector temperature
250°C, oven temperature programming from 70 to
280°C at a rate of 20 deg/min. Chromatographic
analysis was performed on an LKhM-8M instrument
equipped with a thermal conductivity detector, carrier
gas helium, 2000×4-mm column; linear temperature
programming at a rate of 15 deg/min.
1
bp 165°C, nD20 = 1.4380; H NMR spectrum, δ, ppm:
1
2.93 s (3H, CH3), 2.1 m (6H, NCH3). The remaining
part of the reaction mixture (0.88 g) contained (GC–
MS) 81% of Me2NCOMe {[M]+ 87 (Irel 50%)}, 18% of
MeI {[M]+ 142 (48%)}, and 1% of MeN(COMe)2
{[M]+ 115 (10%)}.
Reaction of benzoyl iodide with N,N-dimethyl-
formamide. Benzoyl iodide, 5.0 g (0.022 mol), was
added dropwise to a solution of 0.79 g (0.011 mol) of
DMF in 6 ml of methylene chloride. The mixture was
kept for 10 h at room temperature, the solvent was
removed, and vacuum distillation gave 1.44 g (87%) of
Me2NCOPh, bp 89°C (1 mm), nD20 = 1.4370; published
Initial acetyl and benzoyl iodides were prepared by
reaction of the corresponding acyl chloride with anhy-
drous sodium iodide according to the procedure de-
scribed in [4].
data [7]: bp 280–282°C, nD20 = 1.4374. H NMR spec-
1
trum, δ, ppm: 2.91 s (3H, CH3), 3.18 s (3H, CH3), 7.05–
7.40 m (5H, Ph). 13C NMR spectrum, δC, ppm: 34.01
(CH3), 39.13 (CH3), 128.5, 132.6, 135.46 (Ph), 172.23
(C=O). Mass spectrum, m/z (Irel, %): 148 (51) [M]+,
119 (2), 105 (100), 77 (50), 44 (27), 51 (20), 15 (7).
Reaction of acetyl iodide with N,N-dimethyl-
formamide. Acetyl iodide, 1.7 g (0.01 mol), was
added dropwise to a solution of 0.73 g (0.01 mol) of
N,N-dimethylformamide in 10 ml of methylene
chloride. The mixture was kept for 10 h at room
temperature, the solvent was distilled off, and 0.25 g
(0.003 mol, 34%) of unreacted DMF was isolated
by distillation, bp 150–156°C; published data [5]:
Reaction of benzoyl iodide with N,N-dimethyl-
acetamide. Benzoyl iodide, 6.24 g (0.027 mol), was
added dropwise under stirring to a solution of 1.81 g
(0.021 mol) of DMA in 5 ml of benzene. The mixture
was stirred for 3 h at 65°C, the solvent was removed,
and vacuum distillation gave 2.6 g of a mixture con-
taining (according to the GLC and GC–MS data) 39%
of Me2NCOMe {[M]+ 87 (Irel 80%)}, 25% of PhCOOH
{[M]+ 122 (74%)}, 20% of MeN(COMe)COPh {[M]+
177 (4%)}, and 4% of Me2NCOPh {[M]+ 148 (74%)}.
bp 153°C, nD20 = 1.4305. H NMR spectrum, δ, ppm:
1
2.91 s (6H, CH3), 7.80 m (1H, CH). 13C NMR spec-
trum, δC, ppm: 34.01 (CH3), 167.23 (C=O). According
to the GC–MS data, a fraction (0.46 g) with bp 155–
160°C contained 54% of Me2NCHO {[M]+ 73
(Irel 100%)}, 14% of Me2NC(O)Me {[M]+ 87 (100%)},
31% of MeI {[M]+ 142 (48%)}, and 1% of
MeN(CHO)COMe {[M]+ 101 (47%)}.
This study was performed under financial support
by the Council for Grants at the President of the
Russian Federation (project no. NSh-255.2008.3) and
by the Presidium of the Siberian Division, Russian
Academy of Sciences (integration project no. 97).
Reaction of acetyl iodide with N,N-dimethylacet-
amide. Acetyl iodide, 4.05 g (0.024 mol), was added
dropwise to a solution of 1.6 g (0.018 mol) of DMA in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010