Z. Zheng et al. / Tetrahedron 70 (2014) 9814e9818
9817
DCDMH was added by five times in 1 h, and the mixture was stirred
500 MHz)
d
6.68 (s, 1H, CHCl
2
), 7.50e7.41 (m, 3H, ArH), 7.64e7.61
ꢀ
12 h at 35 C. Afterward, solvent was distilled under reduced
(m, 2H, ArH), 7.72 (d, J¼8.4 Hz, 2H, ArH), 8.17 (d, J¼8.4 Hz, 2H, ArH);
13
pressure; 20 mL of ethyl acetate was added to the residue. Next, the
ethyl acetate layer was washed twice with water (20 mL), and dried
C NMR (CDCl
3
, 125 MHz)
d
67.8, 127.2, 127.4, 128.6, 129.0, 130.3,
139.3, 147.2, 185.5.
2 4
over anhydrous Na SO . After filtration, the solvent was removed
0
under reduced pressure, and the residue was purified by silica gel
chromatography (petroleum ether/ethyl acetate¼20/1, v/v) to give
the product.
4.2.12. 2,2-Dichloro-1-(4 -bromobiphenyl-4-yl)ethanone
ꢀ
1
(3k). Yield: 93%; white solid; mp 144e145 C; H NMR (CDCl
500 MHz) 6.70 (s, 1H, CHCl
), 7.52 (d, J¼8.5 Hz, 2H, ArH), 7.64 (d,
J¼8.5 Hz, 2H, ArH), 7.72 (d, J¼8.5 Hz, 2H, ArH), 8.20 (d, J¼8.5 Hz, 2H,
3
,
d
2
.2.1. 2, 2-Dichloro-1-phenylethanone (3a).19 Yield: 95%; 1H NMR
CDCl , 500 MHz) 6.69 (s, 1H, CHCl ), 7.52e7.53 (m, 2H, ArH),
.64e7.66 (m, 1H, ArH), 8.08e8.10 (m, 2H, ArH); C NMR (CDCl
ArH); C NMR (CDCl
130.5, 132.3, 138.3, 146.0, 185.5. Element Analysis: found: C, 48.71%;
H, 2.70%. Calculated for C14 BrCl O (344.03): C, 48.83%; H, 2.62%.
13
4
(
7
3
, 125 MHz) d 67.9, 123.2, 127.3, 128.9, 129.3,
3
d
2
13
3
,
H
9
2
1
25 MHz)
d
67.7, 128.8, 129.6, 131.2, 134.3, 185.5.
4
.2.13. Ethyl 2, 2-dichloroacetoacetate (3l).30 Yield: 98%; 1H NMR
(CDCl , 500 MHz) ), 2.45 (s, 3H, CH CO),
1.30 (t, J¼7 Hz, 3H, CH
4.28 (q, J¼7 Hz, 2H, CO ); C NMR (CDCl , 125 MHz) 14.0,
23.6, 64.8, 82.0, 163.5, 191.5.
2
9
4.2.2. 2, 2-Dichloro-1-(4-methylphenyl)ethanone (3b). Yield: 98%;
3
d
3
3
ꢀ
ꢀ
1
13
white solid; mp: 52e54 C (Lit.: 54e56 C); H NMR (CDCl
3
,
2
CH
2
3
d
5
2
d
00 MHz)
d
2.39 (s, 3H, CH
3
), 6.68 (s, 2H, CHCl
2
), 7.20 (d, J¼8.1 Hz,
13
H, ArH), 7.94 (d, J¼8.1 Hz, 2H, ArH); C NMR (CDCl
3
, 125 MHz)
27
22.0, 67.7, 128.7, 129.1, 131.7, 145.3, 184.9.
4.2.14. Diethyl 2-chloromalonate (4m). Yield: 58%; colorless oil;
1
H NMR (CDCl
J¼7 Hz, 4H, OCH
13.9, 55.6, 63.2, 164.5.
3
, 500 MHz) ), 4.31 (q,
d
1.33 (t, J¼7 Hz, 6H, CH
3
.2.3. 2, 2-Dichloro-1-(4-methoxyphenyl)ethanone (3c).19 Yield:
), 4.85 (s, 1H, CHCl); C NMR (CDCl , 125 MHz)
13
4
2
3
1
14%; H NMR (CDCl
3
, 500 MHz)
d
3.80 (s, 3H, OCH
3
), 6.67 (s, 2H,
d
1
3
CHCl
NMR (CDCl
2
), 6.97 (d, J¼8.2 Hz, 2H, ArH), 7.85 (d, J¼8.1 Hz, 2H, ArH);
C
, 125 MHz) 55.4, 67.7, 114.0, 123.7, 131.9, 164.4, 184.2.
d
4.2.15. 2-Chloropropiophenone (4n). Yield: 93%; colorless oil; 1
NMR (CDCl , 500 MHz) ), 5.28 (q, J¼7 Hz,
1.76 (d, J¼7 Hz, 3H, CH
1H, CHCl), 7.49e7.53 (m, 2H, ArH), 7.60e7.63 (m, 1H, ArH),
8.02e8.04 (m, 2H, ArH); C NMR (CDCl , 125 MHz) d 20.0, 55.6,
3
128.8, 129.0, 133.8, 134.1, 193.7.
H
3
3
d
3
19-
4
.2.4. 2, 2-Dichloro-1-(3-chloro-4-methoxyphenyl)ethanone.
ꢀ
ꢀ
1
13
Yield: 76%; white solid; mp: 99e101 C (Lit.: 99.8e100.9 C); H
NMR (CDCl , 500 MHz) 4.00 (s, 3H, OCH ), 6.57 (s, 1H, CHCl ), 7.02
d, J¼8.8 Hz,1H, ArH), 8.05 (dd, J¼8.8 Hz, J¼2.3 Hz, 1H, ArH), 8.14 (d,
3
d
3
2
(
13
4.2.16. 1, 1-Dichloro-3,3-dimethylbutanone (3o).24 Yield: 92%;
white solid; mp: 50e51 C (Lit.: 50e51). H NMR (CDCl
J¼2.3 Hz, 1H, ArH); C NMR (CDCl
3
, 125 MHz)
d
70.0, 114.3, 124.6,
ꢀ
1
127.0, 132.5, 133.1, 161.9, 185.7.
3
3
, 500 MHz)
, 125 MHz)
13
d
1.28 (s, 9H, CH
3
), 6.45 (s, 1H, CHCl
2
); C NMR (CDCl
21
4.2.5. 2, 2-Dichloro-1-(4-bromophenyl)ethanone (3d). Yield: 95%;
d
26.5, 44.1, 52.8, 201.2.
ꢀ
ꢀ
1
white solid; mp: 59e61 C (Lit.: 61e62 C); H NMR (CDCl
00 MHz) 6.68 (s, 2H, CHCl
), 7.60 (d, J¼8.50 Hz, 2H, ArH), 7.88 (d,
, 125 MHz) 67.6, 129.7, 129.9,
3
,
5
d
2
Acknowledgements
13
J¼8.5 Hz, 2H, ArH). C NMR (CDCl
3
d
131.1, 133.1, 184.8.
The authors thank the Education Department of Anhui Province
and Huangshan University for financial support (No. kj2013B275,
2013xkjq005).
21
4.2.6. 2, 2-Dichloro-1-(4-chlorophenyl)ethanone (3e). Yield: 98%;
ꢀ
ꢀ
1
white solid; mp: 56e58 C (Lit.: 58e59 C); H NMR (CDCl
00 MHz) 6.71 (s, 2H, CHCl
), 7.40 (d, J¼8.4 Hz, 2H, ArH), 7.92 (d,
, 125 MHz) 67.8, 129.2, 129.4,
3
,
5
d
2
Supplementary data
13
J¼8.4 Hz, 2H, ArH); C NMR (CDCl
3
d
131.2, 141.1, 184.6.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
4
.2.7. 2, 2-Dichloro-1-(4-fluorophenyl)ethanone (3f).12 Yield: 94%;
1
colorless oil, H NMR (CDCl
3
, 500 MHz)
d
6.58 (s, 1H, CHCl
2
),
1
3
3
7.15e7.26 (m, 2H, ArH), 8.13e8.21 (m, 2H, ArH); C NMR (CDCl ,
125 MHz)
d
67.8, 116.1, 127.4, 132.6, 166.3, 184.4.
References and notes
4
.2.8. 2,2-Dichloro-1-(4-(trifluoromethyl)phenyl)ethanone
9
1
(
3g). Yield: 91%; colorless oil, H NMR (CDCl
H, CHCl
), 7.31 (d, J¼8.3 MHz, 2H), 7.98 (d, J¼8.3 MHz, 2H);
NMR (CDCl , 125 MHz) 67.7, 125.8, 130.1, 134.0, 135.3, 135.7, 184.1.
3
, 500 MHz) d 6.71 (s,
13
1
2
C
3
d
1
2
4
.2.9. 2, 2-Dichloro-1-(4-nitrophenyl)ethanone (3h). Yield: 86%;
5
ꢀ
1
colorless oil (Lit.: 26.8e27.8 C). H NMR (CDCl
3
, 500 MHz)
), 8.16 (d, J¼8.2 Hz, 2H, ArH), 8.55 (d, J¼8.2 Hz, 2H, ArH);
C NMR (CDCl , 125 MHz) 67.7, 123.8, 130.9, 135.8, 150.7, 184.3.
d 6.72 (s,
2
H, CHCl
2
1
3
3
d
8
2
1
4
.2.10. 2, 2-Dichloro-1-(3-nitrophenyl)ethanone (3i). Yield: 90%;
ꢀ
ꢀ
1
white solid; mp: 50e51 C (Lit.: 52.5e54 C). H NMR (CDCl
00 MHz) 6.73 (s, 2H, CHCl ), 7.72e7.74 (m, 1H, ArH), 8.45e8.47
3
,
5
d
2
(
m, 1H, ArH), 8.52e8.53 (m, 1H, ArH), 8.99e9.01 (m, 1H, ArH).
1
1
9
4
.2.11. 2,2-Dichloro-1-(biphenyl-4-yl)ethanone (3j). Yield: 92%;
ꢀ
2
ꢀ
1
3
white solid; mp 86e88 C (Lit. 85e87 C); H NMR (CDCl ,