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ARTICLE
Journal Name
reported in Hertz (Hz). Melting points were recorded with a costs for both volatile organic solvenDtOs I:a1n0.d103l9a/bCo6uRrAs00w43e3rDe
micro melting point apparatus. Infrared analyses (KBr pellet) reduced substantially. As it was easy to increase the two
were performed on a FTIR spectrometer. High resolution mass reaction scales, they would be beneficial in reducing
spectra (HRMS) were recorded on a QTOF mass analyzer with environmental pollution in industrial chemical processes.
electro spray ionization (ESI).
Procedure
I:
Typical
300
mg-scale
synthesis
of
Notes and references
chloroacetophenone (2a) using water as solvent
1
.
R. B. N. Baig and R. S. Varma, Chem. Soc. Rev., 2012, 41,
559-1584.
E. Boldyreva, Chem. Soc. Rev., 2013, 42, 7719-7738.
Bromoacetophenone (300 mg), PhSO Cl (8.0 equiv), TEBAC
2
1
(
0.5 equiv) and water (5.0 mL) were added to a 50-mL round-
2
3
.
.
bottom flask. After the mixture was stirred at rt for 1.5 h and
TLC indicated completion of the reaction, the reaction was
stopped and cooled in an ice-bath. Then saturated Na CO aq.
S.-E. Zhu, F. Li and G.-W. Wang, Chem. Soc. Rev., 2013, 42,
7
535-7570.
2
3
4
5
.
.
G.-W. Wang, Chem. Soc. Rev., 2013, 42, 7668-7700.
M. Ferguson, N. Giri, X. Huang, D. Apperley and S. L.
James, Green Chem., 2014, 16, 1374-1382.
(
10 mL) was added to the reaction mixture with stirring until
PhSO Cl disappeared. The mixture was then extracted with
2
ethyl acetate (3 x 10 mL), dried over Na SO and evaporated to
6. P. F. M. Oliveira, M. Baron, A. Chamayou, C. Andre-Barres,
B. Guidetti and M. Baltas, RSC Adv., 2014, 4, 56736-56742.
7. Y.-J. Tan, Z. Zhang, F.-J. Wang, H.-H. Wu and Q.-H. Li, RSC
Adv., 2014, 4, 35635-35638.
2
4
give a white product 2a (235 mg, >99%).
Synthesis of 2a in 10 g scale
The synthesis of 2a starting from 10 g of bromoacetophenone
was performed in a 250-mL round-bottom flask using the same
procedure as above to yield 2a (7.8 g, >99%, t: 1.5 h).
Procedure II: Typical 300 mg-scale synthesis of 2a using
acetonitrile as solvent
8
9
1
.
E. L. Smith, A. P. Abbott and K. S. Ryder, Chem. Rev., 2014,
14, 11060-11082.
V. I. Pârvulescu and C. Hardacre, Chem. Rev., 2007, 107,
615-2665.
0. T. Welton, Coord. Chem. Rev., 2004, 248, 2459-2477.
1
.
2
Bromoacetophenone (300 mg), PhSO Cl (6.0 equiv) and
2
11. J. Muzart, Adv. Synth. Catal., 2006, 348, 275-295.
12. B. C. Ranu and S. Banerjee, J. Org. Chem., 2005, 70, 4517-
4519.
acetonitrile (4.0 mL) were added to a 50-mL round-bottom
o
flask. After the mixture was stirred at 85 C for 2.5 h and TLC
indicated completion of the reaction, the reaction mixture was
concentrated under vacuum. Then saturated Na CO aq. (10 mL)
13. D. Vražič, M. Jereb, K. Laali and S. Stavber, Molecules,
2
012, 18, 74.
2
3
1
4. C.-J. Li, Chem. Rev., 2005, 105, 3095-3166.
was added to the concentrate in an ice bath, which was stirred
15. D. L. Aubele, C. A. Lee and P. E. Floreancig, Organic lett.,
until PhSO Cl disappeared. The mixture was then extracted
2
2
003, 5, 4521-4523.
with ethyl acetate (3 x 10 mL), dried over Na SO4 and
2
16. S. Narayan, J. Muldoon, M. G. Finn, V. V. Fokin, H. C. Kolb
evaporated to give a white product 2a (231 mg, >99%).
Typical 500 mg-scale synthesis procedure using the synthesis of 2-
chloro-3-hydroxy-1-phenyl-1-pentanone (4a) as an example
and K. B. Sharpless, Angew. Chem. Int. Ed. Engl., 2005, 44,
3275-3279.
17. M. B. Gawande, V. D. B. Bonifacio, R. Luque, P. S. Branco
In a 50-mL round-bottom flask, a mixture of trans-3-ethyl-2-
oxiranyl-1-phenylmethanone (3a) (500 mg), MsCl (6.0 equiv),
TEBAC (0.5 equiv) and water (4.0 mL) was stirred at rt for 5.5
h until TLC indicated completion of the reaction. Then the
mixture was washed with ice water until MsCl disappeared.
The product was then extracted with ethyl acetate (3 x 10 mL),
and dried over Na SO . The ethyl acetate was evaporated to
and R. S. Varma, Chem. Soc. Rev., 2013, 42, 5522-5551.
18. T. Sela and A. Vigalok, Org. Lett., 2014, 16, 1964-1967.
19. G. Giorgi, P. López-Alvarado, S. Miranda, J. Rodriguez and
J. C. Menéndez, Eur. J. Org. Chem., 2013, 2013, 1327-1336.
0. A. Chanda and V. V. Fokin, Chem. Rev., 2009, 109, 725-748.
1. R. N. Butler, A. G. Coyne and E. M. Moloney, Tetrahedron
Lett., 2007, 48, 3501-3503.
2
2
2
4
2
2. R. N. Butler and A. G. Coyne, Chem. Rev., 2010, 110, 6302-
give 4a (585 mg, 97% yield, anti/syn=7.3:1).
Synthesis of 1-(4-bromophenyl)-2-chloro-3-hydroxy-1-hexanone
6
337.
3. S. Feng and C. Li, J. Agric. Food Chem., 2015, 63, 5732-
739.
2
(
4d) in 10 g scale
The synthesis of 4d starting from 10 g of trans-1-(4-
bromophenyl)-3-propyl-2-oxiranylmethanone 3d was
5
24. B. Li and C. Li, J. Org. Chem., 2014, 79, 2242-2254.
25. T. Li, X. Cui, L. Sun and C. Li, RSC Adv., 2014, 4, 33599-
33606.
(
)
performed in a 250-mL round-bottom flask using the same
2
2
6. B. Li and C. Li, J. Org. Chem., 2014, 79, 8271-8277.
7. S. K. Tanielyan, N. Marin, G. Alvez and R. L. Augustine, Org.
Process Res. Dev., 2006, 10, 893-898.
procedure as above to yield 4d (11.3 g, >99%, t: 6.5 h).
2
8. Y. Liu, B. A. Provencher, K. J. Bartelson and L. Deng, Chem.
Sci., 2011, 2, 1301-1304.
Conclusions
In conclusion, water-mediated reactions promoted by sulfonyl
29. C.-L. Chang, M. P. Kumar and R.-S. Liu, J. Org. Chem., 2004,
69, 2793-2796.
chlorides
for
transforming
bromoacetophenones
to
chloroacetophenones and aroyl epoxides to aroylchlorohydrins
have been realized. Most probably due to the micellar
hydrophobic core effect, these reactions have resulted in pure
30. M. Hojo, A. Fujii, C. Murakami, H. Aihara and A. Hosomi,
Tetrahedron Lett., 1995, 36, 571-574.
6
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