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Synlett 2011(7): 1028-1032  
DOI: 10.1055/s-0030-1259730
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Green Chemistry Method for the Regeneration of Carbonyl Compounds from Oximes by Using Cupric Chloride Dihydrate as a Recoverable Promoter for Hydrolysis

Na Quan, Xiao-Xin Shi*, Liang-Deng Nie, Jing Dong, Rui-Heng Zhu
Department of Pharmaceutical Engineering, School of Pharmacy, East China University of Science and Technology, 130 Mei-Long Road, Shanghai 200237, P. R. of China
Fax: +86(21)64252052; e-Mail: xxshi@ecust.edu.cn;
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Publication History

Received 23 November 2010
Publication Date:
10 March 2011 (online)

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A Green Chemistry Method for the Regeneration of Carbonyl Compounds from Oximes by Using Cupric Chloride Dihydrate as a Recoverable Promoter for HydrolysisSynlett 2011; 2011(11): 1642-1642
DOI: 10.1055/s-0029-1260797

Abstract

A mild, efficient, general, and green method for the regeneration of carbonyl compounds from their corresponding oximes is described. Cupric salts promoted hydrolysis of oximes was studied, and the best reaction conditions for the hydrolysis have been found. Carbonyl compounds were obtained in 85-98% yields after the treatment of oximes with 2 molar equivalent of CuCl2˙2H2O at reflux (around 75 ˚C) in a mixed solvent of acetonitrile and water (4:1). In addition, cupric salt was readily recovered in an almost quantitative yield via the complete precipitation of Cu(OH)2˙2H2O.

Key words

carbonyl compounds - oxime - hydrolysis - cupric chloride - green chemistry

    References and Notes

  • 1a Corsaro A. Chiacchio MA. Pistara V. Curr. Org. Chem.  2009,  13:  482 
    Google Scholar
  • 1b Corsaro A. Chiacchio U. Pistara V. Synthesis  2001,  1903 
    Google Scholar
  • 2 Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  John Wiley; New York: 1999. 
    Google Scholar
  • 3 Shriner RL. Fuson RC. Curtin DY. Morrill TC. The Systematic Identification of Organic Compounds   6th ed.:  John Wiley; New York: 1980. 
    Google Scholar
  • 4a Wang K. Qian X. Cui J. Tetrahedron  2009,  65:  10377 
    Google Scholar
  • 4b Domingo LR. Picher MT. Arroyo P. Sez JA. J. Org. Chem.  2006,  71:  9319 
    Google Scholar
  • 4c Czekelius C. Carreira EM. Angew. Chem. Int. Ed.  2005,  44:  612 
    Google Scholar
  • 4d Kabalka GW. Pace RD. Wadgaonkar PP. Synth. Commun.  1990,  20:  2453 
    Google Scholar
  • 4e Baran J. Mayr H. J. Org. Chem.  1989,  54:  5012 
    Google Scholar
  • 4f Barton DH. Beaton JM.
    J. Am. Chem. Soc.  1961,  83:  4083 
    Google Scholar
  • 4g Barton DHR. Beaton JM. Geller LE. Pechet MM. J. Am. Chem. Soc.  1961,  83:  4076 
    Google Scholar
  • 5a De S K. Tetrahedron Lett.  2003,  44:  9055 
    Google Scholar
  • 5b Shirini F. Zolfigol MA. Safari A. Mohammadpoor-Baltork I. Mirjalili BF. Tetrahedron Lett.  2003,  44:  7463 
    Google Scholar
  • 5c Shirini F. Zolfigol MA. Mallakpour B. Mallakpour SE. Hajipour AR. Baltork IM. Tetrahedron Lett.  2002,  43:  1555 
    Google Scholar
  • 5d Lee SY. Lee BS. Lee C.-W. Oh DY.
    J. Org. Chem.  2000,  65:  256 
    Google Scholar
  • 5e Curini M. Rosati O. Pisani E. Costantino U. Synlett  1996,  333 
    Google Scholar
  • 5f Ranu BC. Sarkar DC. J. Org. Chem.  1988,  53:  878 
    Google Scholar
  • 5g Donaldson RE. Saddler JC. Byrn S. McKenzie AT. Fuchs PL. J. Org. Chem.  1983,  48:  2167 
    Google Scholar
  • 5h Cava MP. Little RL. Napier DR. J. Am. Chem. Soc.  1958,  80:  2257 
    Google Scholar
  • 6a Majireck MM. Witek JA. Weinreb SM. Tetrahedron Lett.  2010,  51:  3555 
    Google Scholar
  • 6b Martin M. Martinez G. Urpi F. Vilarrasa J. Tetrahedron Lett.  2004,  45:  5559 
    Google Scholar
  • 6c Lukin KA. Narayanan BA. Tetrahedron  2002,  58:  215 
    Google Scholar
  • 6d Watanabe Y. Morimoto S. Adachi T. Kashimura M. Asaka T. J. Antibiot.  1993,  46:  647 
    Google Scholar
  • 6e Akazome M. Tsuji Y. Watanabe Y. Chem. Lett.  1990,  635 
    Google Scholar
  • 6f Curran DP. Brill JF. Rakiewicz DM. J. Org. Chem.  1984,  49:  1654 
    Google Scholar
  • 6g Barton DHR. Motherwell WB. Simon ES. Zard SZ. J. Chem. Soc., Chem. Commun.  1984,  337 
    Google Scholar
  • 6h Olah GA. Arvanaghi M. Prakash GKS. Synthesis  1980,  220 
    Google Scholar
  • 6i Pojer PM. Aust. J. Chem.  1979,  32:  201 
    Google Scholar
  • 6j Timms GH. Wildsmith E. Tetrahedron Lett.  1971,  12:  195 
    Google Scholar
  • 6k Corey EJ. Richman JE. J. Am. Chem. Soc.  1970,  92:  5276 
    Google Scholar
  • 6l Pines SH. Chemerda JM. Kozlowski MA. J. Org. Chem.  1966,  31:  3446 
    Google Scholar
  • Numerous methods for the oxidative deoximation have been reported, recent examples are as follows:
  • 7a Zhou X.-T. Yuan Q.-L. Ji H.-B. Tetrahedron Lett.  2010,  51:  613 
    Google Scholar
  • 7b Shaabani A. Farhangi E. Appl. Catal., A  2009,  371:  148 
    Google Scholar
  • 7c Ganguly NC. Barik SK. Synthesis  2008,  425 
    Google Scholar
  • 7d Gupta PK. Manral L. Ganesan K. Synthesis  2007,  1930 
    Google Scholar
  • 7e Gogoi P. Hazarika P. Konwar D. J. Org. Chem.  2005,  70:  1934 
    Google Scholar
  • 7f Shaabani A. Naderi S. Rahmati A. Badri Z. Darvishi M. Lee DG. Synthesis  2005,  3023 
    Google Scholar
  • 7g Khazaei A. Manesh AA. Synthesis  2005,  1929 
    Google Scholar
  • 7h Jain N. Kumar A. Chauhan SMS. Tetrahedron Lett.  2005,  46:  2599 
    Google Scholar
  • 7i Li Z. Ding R.-B. Xing Y.-L. Shi S.-Y. Synth. Commun.  2005,  35:  2515 
    Google Scholar
  • 7j Khazaei A. Manesh AA. Synthesis  2004,  1739 
    Google Scholar
  • 7k Yang Y. Zhang D. Wu L.-Z. Chen B. Zhang L.-P. Tung C.-H. J. Org. Chem.  2004,  69:  4788 
    Google Scholar
  • 7l Arnold JN. Hayes PD. Kohaus RL. Mohan RS. Tetrahedron Lett.  2003,  44:  9173 
    Google Scholar
  • 7m Krishnaveni NS. Surendra K. Nageswar YVD. Rao KR. Synthesis  2003,  1968 
    Google Scholar
  • 7n Narsaiah AV. Nagaiah K. Synthesis  2003,  1881 
    Google Scholar
  • 7o Bose DS. Reddy AVN. Das APR. Synthesis  2003,  1883 
    Google Scholar
  • 7p Chandrasekhar S. Gopalaiah K. Tetrahedron Lett.  2002,  43:  4023 
    Google Scholar
  • 7q Khazaei A. Vaghei RG. Tetrahedron Lett.  2002,  43:  3073 
    Google Scholar
  • 7r Hosseinzadeh R. Tajbakhsh M. Niaki MY. Tetrahedron Lett.  2002,  43:  9413 
    Google Scholar
  • 7s Blay G. Benach E. Fernandez I. Galletero S. Pedro J. Ruiz R. Synthesis  2000,  403 
    Google Scholar
  • 8a Chavan SP. Soni P. Tetrahedron Lett.  2004,  45:  3161 
    Google Scholar
  • 8b Maynez SR. Pelavin L. Erker G. J. Org. Chem.  1975,  40:  3302 
    Google Scholar
  • 8c DePuy CH. Ponder BW. J. Am. Chem. Soc.  1959,  81:  4629 
    Google Scholar
  • 8d Hershberg EB. J. Org. Chem.  1948,  13:  542 
    Google Scholar
  • Carbonyl compounds can also be regenerated from oximes via photochemical and electrochemical methods, but only a few examples have been reported:
  • 9a de Lijser HJP. Fardoun FH. Sawyer JR. Quant M. Org. Lett.  2002,  4:  2325 
    Google Scholar
  • 9b Haley MF. Yates K. J. Org. Chem.  1987,  52:  1817 
    Google Scholar
  • 9c Mandic Z. Lopotar N. Electrochem. Commun.  2005,  7:  45 
    Google Scholar
  • 10 Gawly RE. Org. React.  1988,  35:  1 ; and references cited therein
    Google Scholar
  • 11 Jiang N. Ragauskas AJ. Tetrahedron Lett.  2010,  51:  4479 
    CrossrefGoogle Scholar
  • 12 Corey EJ. Knapp S. Tetrahedron Lett.  1976,  41:  3667 
    Google Scholar
  • 14 Stutz P. Stadler PA. Org. Synth., Coll. Vol. VI  1988,  109 
    Google Scholar
  • 15a Horvath IT. Anastas PT. Chem. Rev.  2007,  107:  2167 
    Google Scholar
  • 15b Horvath IT. Acc. Chem. Res.  2002,  35:  685 
    Google Scholar
13

Typical Procedure for the CuCl 2 ˙2H 2 O-Promoted Regeneration of Carbonyl Compounds from Various Oximes
Oxime 1a (1.01 g, 5.12 mmol) was dissolved in MeCN (20 mL), CuCl2˙2H2O (1.73 g, 10.15 mmol) and H2O (5 mL) were added. When the suspension was heated to reflux, the mixture became a bluish clear solution. The resulting reaction solution was then stirred at reflux (75 ˚C) for around 2 h and monitored by TLC (EtOAc-hexane, 1:6). After the reaction was complete, the solvents were removed by vacuum distillation. The residue was partitioned between EtOAc (50 mL) and H2O (30 mL), the organic and aqueous phases were separated. Organic phase was washed with brine (5 mL) and dried over anhyd MgSO4. Concentration of the organic solution gave crude product, which was purified by flash chromatography to afford benzophenone (2a, 0.914 g, 5.02 mmol) in 98% yield. To the above-mentioned aqueous phase was added an aq solution of NaOH (11.0 mL, 2 M, 22.00 mmol). After vigorous stirring for 1 h, the bluish solid was collected on a Buchner funnel by suction. After being dried in a warm air at around 50 ˚C for 12 h until the weight of the solid kept constant, Cu(OH)2˙2H2O (1.34 g, 10.03 mmol) was recovered in 99% yield.
Spectral analysis showed that compounds 2a-e,i-l,n-s,v obtained from the above hydrolysis are identical with the commercially available authentic samples. Characterization data of compounds 2f-h,m,t,u are as follows:
Compound 2f: ¹H NMR (400 MHz, CDCl3): δ = 3.89 (s, 3 H), 7.35 (d, J = 7.9 Hz, 1 H), 7.48-7.57 (m, 4 H), 7.62-7.69 (m, 1 H), 8.18-8.24 (m, 2 H), 9.98 (s, 1 H). MS (EI): m/z (%) = 256 (4) [M+], 217 (18), 182 (2), 155 (2), 105 (100), 77 (17). IR (KBr): ν = 3005, 2885, 1735, 1680, 1600, 1505, 1450, 1400, 1255, 1190, 1140, 1120, 1060, 1025, 850, 805, 730, 700 cm-¹.
Compound 2g: ¹H NMR (400 MHz, CDCl3): δ = 1.30 (t, J = 7.1 Hz, 3 H), 4.30 (q, J = 7.1 Hz, 2 H), 4.71 (s, 2 H), 7.02 (d, J = 6.9 Hz, 2 H), 7.85 (d, J = 6.9 Hz, 2 H), 9.90 (s, 1 H). IR (neat): ν = 2980, 2835, 2770, 1755, 1690, 1600, 1510, 1440, 1380, 1310, 1280, 1205, 1160, 1080, 1025, 835, 715, 610 cm-¹. HRMS (EI): m/z calcd for C11H12O4 [M+]: 208.0736; found: 208.0730.
Compound 2h: ¹H NMR (400 MHz, CDCl3): δ = 1.30 (t, J = 7.1 Hz, 3 H), 3.96 (s, 1 H), 4.28 (q, J = 7.1 Hz, 2 H), 4.79 (s, 2 H), 6.84 (d, J = 8.1 Hz, 1 H), 7.41-7.46 (m, 2 H), 9.87 (s, 1 H). IR (KBr): ν = 2980, 2940, 2910, 1750, 1680, 1590, 1510, 1470, 1430, 1395, 1270, 1200, 1140, 1070, 1030, 870, 810, 780, 735, 640 cm-¹. HRMS (EI): m/z calcd for C12H14O5 [M+]: 238.0841; found: 238.0839.
Compound 2m: ¹H NMR (400 MHz, CDCl3): δ = 7.52 (dd, J 1 = 1.6 Hz, J 2 = 8.6 Hz, 1 H), 7.67 (d, J = 1.6 Hz, 1 H), 8.29 (d, J = 8.6 Hz, 1 H), 10.07 (s, 1 H), 10.58 (s, 1 H). IR (KBr): ν = 3255, 3085, 2870, 1700, 1620, 1585, 1530, 1480, 1450, 1315, 1255, 1165, 1140, 1080, 985, 850, 760, 705, 540 cm-¹. MS (EI): m/z (%) = 167 (100) [M+], 166 (44), 151 (1), 136 (3), 119 (7), 109 (4), 92 (3), 81 (3), 63 (6).
Compound 2t: ¹H NMR (400 MHz, CDCl3): δ = 2.28 (s, 3 H), 3.50-3.69 (m, 2 H), 4.88 (dd, J 1 = 6.1 Hz, J 2 = 8.1 Hz, 1 H), 7.03 (d, J = 7.9 Hz, 2 H), 7.13-7.26 (m, 5 H), 7.28-7.35 (m, 2 H), 7.37-7.44 (m, 2 H) 7.48-7.55 (m, 1 H), 7.82-7.89 (m, 2 H). MS (EI): m/z (%) = 332(4) [M+], 209 (5), 179 (2), 123 (13), 105 (100), 91 (6), 77 (59). IR (KBr): ν = 3035, 2920, 1685, 1595, 1490, 1450, 1420, 1335, 1220, 980, 810, 745, 700, 685, 550 cm-¹.
Compound 2u: ¹H NMR (400 MHz, CDCl3): δ = 2.05 (s, 3 H), 2.29 (s, 3 H), 2.92-3.08 (m, 2 H), 4.63 (dd, J 1 = 6.8 Hz, J 2 = 7.8 Hz, 1 H), 7.03 (d, J = 8.0 Hz, 2 H), 7.18 (d, J = 8.0 Hz, 2 H), 7.19-7.26 (m, 5 H). MS (EI): m/z (%) = 270 (32) [M+], 213 (2), 147 (43), 124 (100), 103 (5), 91 (12), 77 (7), 43 (43). IR (neat): ν = 3030, 2940, 1720, 1490, 1455, 1410, 1360, 1150, 1020, 810, 700, 535, 500 cm-¹.

16

When the pH value was kept higher than 9.5, the precipitation of Cu(OH)2˙2H2O was complete, which was determined by adding 2 drops of an aq solution of Na2S into the filtrate. No black CuS appeared.

17

Conversion of Cu(OH) 2 ˙2H 2 O into CuCl 2 ˙2H 2 O
The above Cu(OH)2˙2H2O was first heated at 150 ˚C for around 6 h, and the resulting brown anhyd CuO was then treated with 2.2 molar equivalent of aq HCl at reflux for 2 h. Removal of H2O under vacuum at 45 ˚C gave blue crystalline CuCl2˙2H2O in a nearly quantitative yield.