146
M. Shi, S.-C. Cui / Journal of Fluorine Chemistry 116 (2002) 143±147
reaction of N,N-dimethylaniline with acetic anhydride do
not give the Friedel±Crafts reaction product under the same
conditions. The Friedel±Crafts reaction of N,N-dimethy-
laniline with ethyl glyoxylate gave three products in the
presence of per¯uorinated catalysts.
N-[4-(4-Dimethylaminobenzyl)phenyl]-N-methylaceta-
mide 3. A blue solid; m.p. 104±106 8C. IR (CHCl3) n
1653 cmÀ1 (C=O). H NMR (300 MHz, TMS, CDCl3) d
1
1.86 (3H, s, CH3), 2.92 (6H, s, NCH3), 3.23 (3H, s, NCH3),
3.90 (2H, s, CH2), 6.70 (2H, d, J 8:4Hz, Ar), 7.07 (4H, d,
J 7:5 Hz, Ar), 7.21 ppm (2H, d, J 8:4Hz, Ar). MS (EI)
m/z 282 (M ). HRMS calc. for C18H22N2O requires M,
3. Experimental section
282.1732; found: 282.1750 (M ).
N,N,N0,N0-Tetramethyl-4,40-methylenedianiline 4. A blue
solid; m.p. 89±91 8C. 1H NMR (300 MHz, TMS, CDCl3) d
2.91 (12H, s, NCH3), 3.82 (2H, s, CH2), 6.71 (4H, d,
J 8:6 Hz, Ar), 7.08 ppm (4H, d, J 8:6 Hz, Ar). 13C
NMR (75 MHz, CDCl3): d 39.9, 41.0, 113.2, 129.4,
3.1. General
Melting points are uncorrected. 1H and 13C NMR spectra
were recorded at 300 and 75 MHz, respectively. Mass
spectra were recorded by EI method and HRMS was mea-
sured on a Finnigan MA mass spectrometer. Organic
solvents used were dried by standard methods when neces-
sary. Commercially available reagents were used without
further puri®cation. All reactions were monitored by TLC
with Huanghai GF254 silica gel coated plates. Flash column
chromatography was carried out using 200±300 mesh silica
gel. Ln(C8F17SO3)3 was prepared from the reaction of
C8F17SO3H with Ln2O3 according to the literature [8].
130.5, 149.0 ppm. MS (EI) m/z 254(M ). HRMS calc.
for C17H22N2 requires M, 254.1783; found: 254.1742 (M ).
N-{4-[4-(Acetylmethylamino)benzyl]phenyl}-N-methyla-
cetamide 5. A blue solid; m.p. 96±98 8C. IR (CHCl3) n
1654cm À1 (C=O). H NMR (300 MHz, TMS, CDCl3) d
1
1.82 (6H, s, CH3), 3.25 (6H, s, NCH3), 3.97 (2H, s, CH2),
7.07 (4H, d, J 8:2 Hz, Ar), 7.19 ppm (4H, d, J 8:2 Hz,
Ar). MS (EI) m/z 310 (M ). HRMS calc. for C19H22N2O2
requires M, 310.1681; found: 310.1708 (M ).
N-[4-(4-Dimethylaminobenzyl)phenyl]acetamide 6.
A
blue solid; m.p. 96±98 8C. IR (CHCl3) n 1656 cmÀ1
3.2. Friedel±Crafts reaction of anisole with
acetic anhydride
1
(C=O). H NMR (300 MHz, TMS, CDCl3): d 1.87 (3H, s,
CH3), 3.25 (3H, s, NCH3), 3.31 (3H, s, NCH3), 4.01 (2H, s,
To a solution of anisole (2 mmol, 0.22 ml) and acetic
anhydride (1.85 mg, 2 ml) was added Yb(C8F17SO3)3
(3.4mg, 0.002 mmol) and reaction mixture was stirred at
100 8C for 48 h. The reaction mixture was washed with
water (10 ml  2) and extracted with dichloromethane
(CH2Cl2). The solvent was removed under reduced pressure
and the residue was puri®ed by a silica gel column chro-
matongraph (eluent: petroleum ether/EtOAc 5/1) to give
the product 1 as a colorless liquid.
CH2), 7.12 (4H, d, J 8:3 Hz, Ar), 7.22±7.27 (4H, m, Ar),
8.46 ppm (1H, s, NH). MS (EI) m/z 268 (M ). HRMS calc.
for C17H20N2O requires M, 268.1576; found: 268.1534
(M ).
3.4. Friedel±Crafts reaction of N,N-dimethylaniline
with ethyl glyoxylate
To N,N-dimethylaniline (0.5 mmol, 60 mg, 0.05 ml) in
Schlenk tube was added Yb(C8F17SO3)3 (9 mg, 0.005 mmol)
and ethyl glyoxylate (255 mg, 2.5 mmol) and the reaction
mixture was stirred at the RT for 24h. The reaction solution
was washed with water (10 ml  2) and extracted with
dichloromethane (CH2Cl2). The solvent was removed under
reduced pressure and the residue was puri®ed by a silica gel
column chromatongraph (eluent: petroleum ether/EtOAc
5/1) to give the products 7±9.
3.3. Friedel±Crafts reaction of N,N-dimethylaniline
with acetic anhydride
To a solution of N,N-dimethylaniline (242 mg, 2 mmol,
0.23 ml) and acetic anhydride (1.85 mg, 2 ml) was added
Yb(C8F17SO3)3 (3.4mg, 0.002 mmol) and reaction mixture
was stirred at 100 8C for 48 h. The reaction mixture was
washed with water (10 ml  2) and extracted with dichlor-
omethane (CH2Cl2). The solvent was removed under
reduced pressure and the residue was puri®ed by a silica
gel column chromatongraph (eluent: petroleum ether/
EtOAc 1/2) to give products 2±6.
(4-Dimethylaminophenyl)hydroxyacetic acid ethyl ester
1
7. A colorless liquid. H NMR (300 MHz, TMS, CDCl3) d
1.24(3H, t, J 7:1 Hz, CH3), 2.95 (6H, s, NCH3), 3.26 (1H,
d, J 6:0 Hz, OH), 4.18±4.12 (1H, m, CH2), 4.30±4.24(1H,
m, CH2), 5.07 (1H, d, J 5:7 Hz, CH), 6.71 (2H, d,
J 8:8 Hz, Ar), 7.26 ppm (2H, d, J 8:8 Hz, Ar). MS
N-Methyl-N-phenylacetamide 2.
A colorless solid;
m.p. 72±74 8C. IR (CHCl3) n 1654cm À1 (C=O). 1H
NMR (300 MHz, TMS, CDCl3) d 1.89 (3H, s, CH3), 3.29
(3H, s, NCH3), 7.20±7.23 (2H, m, Ar), 7.36±7.47 ppm (3H,
m, Ar). 13C NMR (75 MHz, CDCl3) d 22.4, 37.2, 127.1,
127.7, 129.7, 144.7, 170.5 ppm (C=O). MS (EI) m/z 149
(EI) m/z 223 (M ). HRMS calc. for C12H17NO3 requires
M, 223.1208; found: 223.1212 (M ).
Bis-(4-dimethylaminophenyl)acetic acid ethyl ester 8. A
1
colorless liquid. H NMR (300 MHz, TMS, CDCl3) d 1.24
(3H, t, J 7:1 Hz, CH3), 2.91 (12H, s, NCH3), 4.17 (2H, d,
J 7:1 Hz, CH2), 4.83 (1H, s, CH), 6.68 (4H, d,
J 8:8 Hz, Ar), 7.17 ppm (4H, d, J 8:8 Hz, Ar). MS
(M ). HRMS calc. for C9H11NO: requires M, 149.0841;
found: 149.0808 (M ).