Active-alkali metal-promoted reductive cleavage of chlorinated phenols
Each mixture was vigorously stirred at RT for 12 h,
605
2. Santana CM, Ferrera ZS, Padro
´
Molecules 14:298
3
n MET, Rodr ´ı guez JJS (2009)
after which time it was quenched by slow dropwise addi-
3
tion of 15 cm of H O. The organic solvent was evaporated
. Agency for toxic substances and disease registry, US Department
sed July 1999
4. Briois C, Ryan S, Tabor D, Touati A, Gullett BK (2007) Environ
Sci Technol 41:850
. Tuppurainen KA, Ruokoj a¨ rvi PH, Asikainen AH, Aatamila M,
Ruuskanen J (2000) Environ Sci Technol 34:4958
6. Czaplicka M (2006) J Hazard Mater B 134:45
2
in vacuo, and the resulting mixture was extracted with
3
CH Cl (3 9 10 cm ). The aqueous phase was acidified
2
2
3
with 1 N HCl, extracted with CH Cl (3 9 10 cm ), and
2
2
3
the organic phases were collected, washed with 10 cm of
5
3
H O and 10 cm of brine, and dried (Na SO ). After
2
2
4
evaporation of the solvent, the resulting mixture was ana-
1
lyzed by GC/MS and H NMR spectroscopy. Isolated
7. Zhao W, Ma W, Chen C, Zhao J, Shuai Z (2004) J Am Chem Soc
1
26:4782
. Antonaraki S, Androulaki E, Dimotikali D, Hiskia A, Papacon-
stantinou E (2002) J Photochem Photobiol A Chem 148:191
products were further analyzed by IR spectroscopy. Reac-
tion products 4, 5a, and 5b were characterized by
comparison with commercially available samples.
8
9. Oturan N, Panizza M, Oturan MA (2009) J Phys Chem A
13:10988
1
1
1
0. Patel UD, Suresh S (2008) Sep Purif Technol 61:115
1. Kranz O, Voss J (2003) Z Naturforsch 58b:1187
General procedure for catalytic reductive cleavage
of Na salt of chlorophenols 6a–6d and 6f
12. Wang S, Yang B, Zhang T, Yu G, Deng S, Huang J (2010) Ind
Eng Chem Res 49:4561
1
3. Lan Y, Yang L, Zhang M, Zhang W, Wang S (2010) Appl Mater
Interfaces 2:127
NaH (60% dispersion in mineral oil, 1.2 eq) was placed
3
under dry N in a 50-cm , two-necked flask equipped with a
2
1
4. Liu G-B, Zhao H-Y, Dai L, Thiemann T (2009) ARKIVOC
xiii:211
15. Choi J-H, Kim Y-H (2009) J Hazard Mater 166:984
reflux condenser and magnetic stirrer, washed with dry THF
3
3 9 5 cm ), and suspended in 5 cm of dry THF. The
3
(
1
6. Mitoma Y, Kakeda M, Simion AM, Egashira N, Simion C (2009)
Environ Sci Technol 43:5962
7. Patel UD, Suresh S (2007) J Hazard Mater 147:431
mixture was chilled to 0 °C, and a solution of the appropriate
phenol 1 (1 eq, 1.79 mmol) dissolved in 3 cm of THF was
added dropwise. The resulting mixture was stirred for 1 h at
3
1
18. Zhou T, Lu X, Lim T–T, Li Y, Wong F-S (2010) Chem Eng J
156:347
19. Liang J, Komarov S, Hayashi N, Kasai E (2007) Ultrason
Sonochem 14:201
RT, then slowly added to a deep green suspension of Na
3
metal in 10 cm of dry THF containing a catalytic amount of
C H (for the molar ratio see Table 2). After stirring over-
10 8
2
0. Gupta SS, Stadler M, Noser CA, Ghosh A, Steinhoff B, Lenoir D,
Horwitz CP, Schramm K-W, Collins TJ (2002) Science 296:326
night at RT, the mixture was filtered from the excess of the
metal under dry N , the recovered metal was washed with a
2
21. Zilouei H, Guieysse B, Mattiasson B (2006) Process Biochem
1:1083
4
minimal amount of dry THF and the organic phases were
2
2. Denizli A, Cihangir N, T u¨ zmen N, Alsancak G (2005) Bioresour
Technol 96:59
collected. The resulting mixture was quenched by dropwise
3
addition of 10 cm of H O, and the organic solvent was
2
23. Antonopoulos VT, Rob A, Ball AS, Wilson MT (2001) Enzyme
Microb Technol 29:62
24. Alonso F, Beletskaya IP, Yus M (2002) Chem Rev 102:4009
evaporated in vacuo. The resulting mixture was extracted
3
with CH Cl (3 9 10 cm ); the aqueous phase was acidified
2
2
2
2
5. Azzena U, Pittalis M (2011) Tetrahedron 67:3360
6. Azzena U, Dettori G, Pisano L, Pittalis M (2011) Tetrahedron
67:3470
3
with 1 N HCl and extracted with CH Cl (3 9 10 cm ); and
2
2
3
the organic phases were collected, washed with 10 cm of
3
H O and 10 cm of brine, and dried (Na SO ). After evap-
27. Azzena U, Dettori G, Mocci S, Pisano L, Cerioni G, Mocci F
2010) Tetrahedron 66:9171
2
2
4
(
oration of the solvent, the crude material was analyzed by
1
GC/MS and H NMR spectroscopy.
2
2
3
8. Hwu JR, Wein YS, Leu Y-J (1996) J Org Chem 61:1493
9. Pittman CU Jr, He J (2002) J Hazard Mater 92:51
0. Sun G-R, He J-B, Pittman CU Jr (2000) Chemosphere 41:907
Acknowledgments Financial support from the Universit a` di Sassari
31. Screttas CG, Micha-Screttas M (1978) J Org Chem 43:1064
32. Smith JG, Ho I (1972) J Org Chem 37:4260
33. Azzena U, Dettori G, Lubinu C, Mannu A, Pisano L (2005)
Tetrahedron 61:8663
34. Colon I, Kelsey DR (1986) J Org Chem 51:2627
35. Minzoni F, Nardelli M, Pelizzi C, Predieri G (1984) Gazz Chim
Ital 114:221
(
Fondo di Ateneo per la Ricerca) is gratefully acknowledged.
G.D. acknowledges financial support from the Regione Autonoma
della Sardegna (Italy), through the project ‘‘Master and Back-Percorsi
di rientro;’’ M.P. acknowledges financial support from the Regione
Autonoma della Sardegna (Italy), through the project ‘‘Promozione
della Ricerca Scientifica e dell’Innovazione Tecnologica in Sardegna.’’
3
6. Miyoshi K, Nishio T, Yasuhara A, Morita M, Shibamoto T
2004) Chemosphere 55:1439
7. Eisenbraun EJ, Hall H (1971) Chem Ind (London) 1158
(
3
References
1
. Ramamoorthy S, Ramamoorthy S (1997) Chlorinated organic
compounds in the environment. CRC Press, Boca Raton
123