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Molecules 2012, 17, 2464-2473; doi:10.

3390/molecules17032464
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molecules
ISSN 1420-3049 www.mdpi.com/journal/molecules Article

SnCl2/TiCl3-Mediated Deoximation of Oximes in an Aqueous Solvent
Mei-Huey Lin *, Han-Jun Liu, Cheng-Yu Chang, Wei-Cheng Lin and Tsung-Hsun Chuang Department of Chemistry, National Changhua University of Education, Changhua 50007, Taiwan * Author to whom correspondence should be addressed; E-Mail: mhlin@cc.ncue.edu.tw; Tel.: +886-4-723-2105 ext. 3543; Fax: +886-4-721-1190. Received: 30 January 2012; in revised form: 23 February 2012 / Accepted: 27 February 2012 / Published: 1 March 2012

Abstract: A simple procedure for SnCl2/TiCl3-mediated deoximation of ketoximes in an aqueous solvent is reported. Under the conditions developed in this effort, various ketones and aldehydes are produced in good to excellent yields. Keywords: deoximation; aqueous solvent; ketoxime; aldoxime; tin chloride; titanium trichloride

1. Introduction Oximes are often used in organic synthesis as protected forms of carbonyl compounds [1] or as carbonyl derivatives for purification and characterization purposes [2]. Furthermore, oximes can be prepared from noncarbonyl compounds, such as nitroalkanes [3–5], or primary amines [6], thus deoximation provides an alternative approach for the syntheses of aldehydes and ketones. A plethora of examples of procedures for the regeneration of carbonyl compounds from oximes have been reported. So far a good number of deoximation methods based on hydrolytic [7], reductive [8–12], oxidative [13–19], and transoximation [20–22] reactions have been developed. Among them some require strong acidic conditions; some take long reaction times, and give low product yields, while some are performed at higher temperatures. For example, regeneration of carbonyl compounds from oximes via direct hydrolysis usually involves strong acidic conditions due to the relatively high hydrolytic stability of oximes, and thus leads to the damage of acid-sensitive groups and the formation of amides as byproducts by Beckmann rearrangement [23,24]. Besides, most of reductive and

39% 4 h. However. expensive or not readily available.Molecules 2012. 23% 4 h. commercial availability and modestly low toxicity [25. It is reported that SnCl2 is prone to partial hydrolysis in water and generates an acidic solution [34]. Tin and tin-containing Lewis acids have been extensively used in organic chemistry owing to their low cost. Metal. harsh reaction conditions are applied such as reflux or microwave irradiation at high temperature [27.t. d Conditions: 1a (1. b conversion was determined by 1H-NMR.0 mmol) and indicated metal or metal halide (1. Deoximation of oximes by using SnCl2-SiO2 has been reported. Therefore.0 mmol) and indicated metal halide (3. we describe the results of a study which demonstrate that oximes serve as starting materials for tin promoted hydrolysis reactions. 2.t. 55% 4 h. 26% Conditions: 1a (1.26].0 mL) at r.0 mL) at r. 56% c 4 h. Below. we envisioned that deoximation of oximes by tin-mediated hydrolysis reactions under aqueous and mild conditions should be possible. 12% 4 h.0 mL)/ water (1.. which then undergo allylation in the presence of allyl anion equivalents. 99+% 4 h. Several examples of mild methods that use tin metal and stannic chloride to promote allylation reactions of protected carbonyls such as enol ethers and acetals in aqueous media have been described [29–32].0 mL)/water (1. the protected carbonyls are hydrolyzed to the corresponding aldehydes. 14% 4 h.28]. the results showed that the acidic conditions generated . 14% 4 h. a milder. Table 1.5 mmol) in THF (1. c Isolated yield. NOH Ph 1a Me metal H2O/THF Ph O Me 2a Entry 1 2 3 4 5 6 7 8 9 10 11 d 12 d a Metal TiCl3 SnCl2 SnCl2/TiCl3 SnCl2/KI Sn/TiCl3 Mn/TiCl3 In/TiCl3 Fe/TiCl3 Cu/TiCl3 Zn/TiCl3 TiCl3 SnCl2 Time. 17 2465 oxidative methods require reagents that are often hazardous or very toxic. entry 3).or metal halide-mediated aqueous deoximation of acetophenone oxime (1a). conversion b 4 h. The results show that SnCl2/TiCl3 serves as a superior reagent for the deoximation of acetophenone oxime (1a) in aqueous medium (Table 1.or metal halide-mediated deoximation of ketoxime a. 92% 4 h. high yielding. However.0 mmol) in THF (1. Apparently. 53% 4 h. In this regard. The conditions employed and the results of the reactions are presented in Table 1 [33]. 80% 4 h. and inexpensive method is still in demand. Results and Discussion The effort began with an investigation of metal.

83% 3 h.0 mL) at r.5 mmol) and TiCl3 (1. Thus. The intervention and effect of this reduction process are seen by comparing the rates of reactions promoted by using various low-valent titanium reagents (Table 1.5 mmol) in THF (1. 96% Entry 9 Substrate NOH 1i Time. 91% NOH Br 1f 14 NOH 1n 7 MeO NOH 1g 3 h. Table 2. 98% 13 NOH 9 h. 94% 15 1o 7 h. 89% NOH NOH 1b 2 6 h. 84% 12 OMe O 1l 9 h. 92% 10 1j 9 h. The reduction of oximes to form imines. yield 5 h. using trivalent titanium reductant or utilizing a low-valent titanium reagent generated from TiCl4/SnCl2 has been described [35–38]. 17 2466 are not sufficient to promote regeneration of carbonyl compounds from ketoxime in aqueous solvent (Table 1. However. entries 2. It is important to note that the deoximation process was deteriorated by using low-valent titanium generated from zinc (Table 1. 92% 8 a NOH HO 1h Conditions: ketoxime 1 (1. Herein.0 mmol). 3 and 5–11). entry 10). a commercially available titanium trichloride 20% in 3% hydrochloric acid was employed in this study. yield 4 h. . these reactions are performed under anhydrous conditions and excess amounts of reagents are employed. SnCl2/TiCl3-mediated deoximation of ketoximes a. 92% 11 NOH NOH 1k 6 h. 97% 4 MeO NOH 1d 4 h. 99% 5 6 AcHN NOH 1m NOH 1e 9 h.5 h. we envisaged that imines formed in this manner would be susceptible to rapid hydrolysis to produce ketones. 4 and 12). SnCl2 (1.Molecules 2012. 97% 3 NC NOH 1c 9 h.0 mL)/ water (1. 82% 9 h. NOH R 1 R' SnCl2/TiCl3 H2O/THF R 2 O R' Entry 1 Br Substrate NOH 1a Time. entries 1.t. 95% 2.

1q. b Conversion was determined by 1H-NMR. THF is added to boost the reaction to complete (entry 9 vs. the substrate scope of the deoximation reactions of ketoximes was probed under the SnCl2/TiCl3-mediated conditions (Table 2). 6 and 9.0 mL) at r. entry 8) do not alter the efficiency of the reaction. Table 3) and deoximation products were obtained in excellent yields under this mild condition.0 mmol) and indicated metal halide (1. Table 3.0 mmol) in solvent (2.5 equivalents each) as a general procedure for deoximation of various ketoximes shown in Table 2. 17 2467 Next.0 equivalent) was able to deoximate acetophenone oxime (1a) but at least one equivalent of TiCl3 was required to deoximate oxime 1k. aromatic halogen (1b. For example. In addition. 1f). entry 10. Metal halide-mediated deoximation of aldoxime a. With the excellent results from deoximation of ketoximes. entries 1–13) and aliphatic (Table 2. the yields of these processes starting with both aromatic (Table 2. nitrile (1c).. Therefore. we chose fixed amounts of SnCl2 and TiCl3 (1. It is found that the amount of TiCl3 could be lowered but it depends on the substrate.t. Due to poor solubility of aldoxime 1r in water.Molecules 2012. c Isolated yield of 2. entries 14 and 15) oximes. Deoximation worked well for aldoximes 1p. the presence of an amide group that is present in 1e (Table 2. and alkoxyl (1d. 1l) as well as olefin (1o) were tolerated under this mild condition. are good to excellent. As can be seen by viewing the results displayed in Table 2. Table 3). and 1r with the SnCl2/TiCl3 system (entries 3. . a catalytic amount of TiCl3 (0. 1g.25 equivalent) accompanied with SnCl2 (1. Interestingly. NOH Ar 1 H metal solvent Ar 2 O H Entry 1 2 3 4 Cl Substrate NOH H 1p Metal TiCl3 SnCl2 SnCl2/TiCl3 TiCl3 SnCl2 SnCl2/TiCl3 TiCl3 Solvent H2O H2O H2O H2O H2O H2O THF/H2O (1/3) Time 2h 2h 2h 5h 5h 5h 4h Conversion b (%) 33 4 99 (96) c 12 <1 99 (93) c 17 1p 1p NOH H 1q 5 6 7 1q 1q MeO NOH H 1r OMe 8 9 10 a 1r 1r 1r SnCl2 SnCl2/TiCl3 SnCl2/TiCl3 THF/H2O (1/3) THF/H2O (1/3) H2O 4h 4h 6h 9 99 (97) c 71 Conditions: aldoxime 1 (1. entry 5) and a free phenol group that is present in 1h (Table 2. we turned our attention to deoximation of aldoximes with the same approach and the results are shown in Table 3.

84%). 1.96 mL. 1H).58 (s. Flash chromatography was performed using silica gel (70–230 mesh). J = 7.07–7. 7. the title compound was obtained (183 mg.84 (m. TLC (EtOAc/hexanes (1:4)) Rf = 0. 2H). (0.5 mmol. Mass spectra and high-resolution mass spectra were recorded under electron spray interface (ESI) conditions (Finnigan/Thermo Quest MAT). Data are in good agreement with the literature [40]. 1H-NMR (CDCl3):  2. Oximes were prepared according to the reported procedures [39].8 Hz.21 (m. 8.59 (d.06 (d. 20% in 3% hydrochloric acid) were added successively to a solution of oxime 1 (1. the title compound was obtained (145 mg. J = 7.t.14–8.91 (d. 3H). 7.24. 8. TLC analyses were run on a glass plate (Silica gel 60 F254) and were visualized using UV or a solution of phosphomolybdic acid in ethanol (5 wt%) or p-anisaldehyde stain. 1H-NMR (CDCl3):  2. 3H).1. 1-(3-Methoxyphenyl)ethanone (2d). the title compound was obtained (126 mg.2 Hz. Data are in good agreement with the literature [43]. J = 7.33 (t. J = 7. 7.58 (s.62 (s. 1H). J = 7.84 (s. 1H). 3H). J = 7. 3.8 Hz.68.Molecules 2012.8 Hz.85 (s.53 (m. Following the general procedure. 1H).8 Hz. 1H). 1H).54 (m. filtered.35 (t. J = 2.69 (m. 1H and 13 C-NMR spectra were recorded on a 300 MHz spectrometer (Bruker AV-300).33 (t. 1H). TLC (Et2O/hexanes (1:2)) Rf = 0. 92%). 7. 7. Following the general procedure.75. . N-(3-Acetylphenyl)acetamide (2e).59 (t.87 (m. Oil.8 Hz. 7. 96%). Following the general procedure. the solution was extracted with Et2O (3 × 5 mL). Data are in good agreement with the literature [41]. 82%). 3H). The mixture was stirred at ambient temperature until all the starting material was consumed.52 (s. Acetophenone (2a).41–7.65–7. 3H). and concentrated in vacuo. Oil. J = 8. 2. 3-Acetylbenzonitrile (2c). Following the general procedure. 1-(3-Bromophenyl)ethanone (2b). 1H-NMR (CDCl3):  2.5 mmol) and titanium(III) chloride. 1H). C (central line) 77. 2H). 3H).25. 1H). Oil. The combined organic layers were dried over MgSO4.80–7.4. Following the general procedure. 7. 1. 1H). General Information and Materials 2468 All commercially available chemicals were used without further purification.17 (s.8 Hz.93 (dd. 1H). 3H). General Procedure for SnCl2/TiCl3-Mediated Deoximation of Ketoximes in an Aqueous Solvent Tin chloride dihydrate (345 mg.0].84–7.58. TLC (EtOAc/hexanes (1:2)) Rf = 023. the title compound was obtained (115 mg. Oil. 17 3. 7.0 mmol) in THF (1 mL)/ water (1 mL) at r.1 Hz. TLC (EtOAc/hexanes (1:2)) Rf = 0. Data are in good agreement with the literature [44]. Oil. 8. 8. giving a residue which was subjected to silica gel chromatography to furnish the pure ketone 2.2. 3H). 7. 3. 1. Chemical shifts are reported relative to CHCl3 [H 7.46–7. 7. 7. 2H).57 (s. 1H). 1H-NMR (CDCl3):  2. 1H-NMR (CDCl3):  2. 1H). 7. TLC (EtOAc/hexanes (1:4)) Rf = 0. the title compound was obtained (134 mg. 7.05 (s. 92%). Data are in good agreement with the literature [42]. Experimental 3.11 (m.

2H).42–7. 89%). 3 H). Following the general procedure. 1H).8 Hz.85–8.61 (d. J = 6. 94%). Propiophenone (2i).86 (d. 8. Oil.Molecules 2012. Following the general procedure. 2.97 (q.25–7. 2. 1-(4-Hydroxyphenyl)ethanone (2h). 1H-NMR (CDCl3):  2.8 Hz. 2H). 1H-NMR (CDCl3):  2. Data are in good agreement with the literature [45]. Data are in good agreement with the literature [51]. Data are in good agreement with the literature [45]. J = 7. 5H).24 (d. 6. the title compound was obtained (195 mg.24 (m. 1H-NMR (CDCl3):  1. 3H). 2. 4H). 7.71 (s. 1H-NMR (CDCl3):  1.45. the title compound was obtained (89 mg. J = 7. 2H). 2H).8 Hz. TLC (Et2O/hexanes (1:2)) Rf = 0. Data are in good agreement with the literature [50]. 2. 3H).30. the title compound was obtained (133 mg. J = 7. 1H).28–2. TLC (Et2O/hexanes (1:2)) Rf = 0.5 Hz. Data are in good agreement with the literature [40].03 (m. J = 7.59 (s. J = 7.53.87 (m.8 Hz.64–1. 98%). Data are in good agreement with the literature [49]. J = 2.81 (s.88 (m. 97%).4-dihydronaphthalen-1(2H)-one (2l).57 (d. the title compound was obtained (143 mg. TLC (Et2O/hexanes (1:2)) Rf = 0. 1H). 2H).84 (s. TLC (Et2O/hexanes (1:4)) Rf = 0. 92%). 91%).87 (t.5 Hz.87 (d. 7.1 Hz. 3. 3H). J = 8. 1. 1H).4 Hz. 4H). TLC (Et2O/hexanes (1:2)) Rf = 0. 3H). 7. Cyclohexanone (2n). Oil.57 (m. the title compound was obtained (119 mg. 1H).53 (m. J = 7.45.28 (s. 99%).8 Hz. 2H). 2H).4 Hz. 8. 1-(4-Methoxyphenyl)ethanone (2g). Oil. 7. 1-(Naphthalen-2-yl)ethanone (2k). 6. 1H-NMR (CDCl3):  2. 6H). J = 7. TLC (Et2O/hexanes (1:2)) Rf = 0. 17 2469 1-(4-Bromophenyl)ethanone (2f).3 Hz. the title compound was obtained (128 mg. Oil. 1H-NMR (CDCl3):  2. Oil.58.8 Hz.54–7. 2H). 6.56 (s. 7. 7.67–7. the title compound was obtained (174 mg. 83%).58. TLC (EtOAc/hexanes (1:9)) Rf = 0. J = 8.58–1. 3.19–2. the title compound was obtained (190 mg. 2H). 2.54 (s. 95%). J = 7.65 (m. 2H). 1-(Benzofuran-2-yl)ethanone (2m).40. 3H). Following the general procedure. Following the general procedure.61 (m. Data are in good agreement with the literature [47]. 1H-NMR (CDCl3):  2. J = 7.20 (t. 3H). 1H). 1H).89 (d. 7.49 (m. TLC (Et2O/hexanes (1:2)) Rf = 0. 4H). 7. 7.85–6. 6. 7. 2. 7.53.32 (m. Data are in good agreement with the literature [46]. Oil. 1-Cyclohexenylethanone (2o). 2H).01 (d. Following the general procedure.43.24–7.78 (d. 3H). 1H-NMR (CDCl3):  4. 7.8 Hz. 1H).45 (s. 3H). Oil. 5-Methoxy-3.58 (m.00 (t. . 1H-NMR (CDCl3):  1.08 (s. 1H).59 (m.25 (s. Oil. 7. 7. 1H-NMR (CDCl3):  2. 2H).93 (d. Data are in good agreement with the literature [48]. Oil.8 Hz. 3H).54–7. the title compound was obtained (165 mg.45–7.63. 3H). 7.61–2.87 (d. the title compound was obtained (114 mg. Data are in good agreement with the literature [45].35 (m. TLC (EtOAc/hexanes (1:4)) Rf = 0.32 (m.40–7. 2H). 2H). Following the general procedure. Following the general procedure. 97%).15 (m. Following the general procedure. 2H). Following the general procedure. TLC (Et2O/hexanes (1:2)) Rf = 0. J = 7.52 (s.71 (m.05–2. Following the general procedure. 7. 4H). 7.2-Diphenylethanone (2j). Oil.

P.G. J. Benzaldehyde (2p). 96%). 2H). Morrill. John Wiley: New York.99 (s. Following the general procedure. 1H). 93%). 9.4 Hz.51 (d.mdpi. Shriner.70 (s. T. and concentrated in vacuo.87 (m. Cui.. 65. TLC (Et2O/hexanes (1:2)) Rf = 0. Curtin. 1H-NMR (CDCl3):  3.. Data are in good agreement with the literature [52]. 17 2470 3..65 (s. TLC (Et2O/hexanes (1:2)) Rf = 0. (0. John Wiley: New York. we report a simple. 2H).C. 4th ed. 3. 2H). 2H). X.64 mL. General Procedure for SnCl2/TiCl3-Mediated Deoximation of Aldoximes in an Aqueous Solvent Tin chloride dihydrate (230 mg. References and Notes 1. R. 97%). D.81 (d. Data are in good agreement with the literature [52]. TLC (Et2O/hexanes (1:2)) Rf = 0.48 (d. 6. One step from nitro to oxime: A convenient preparation of unsaturated oximes by the reduction of the corresponding vinylnitro compounds. 3. The Systematic Identification of Organic Compounds. Data are in good agreement with the literature [53]. 3H).0 mmol) and titanium(III) chloride. 20% in 3% hydrochloric acid) were added successively to a solution of aldoxime 1 (1. Supplementary Materials Supplementary materials can be accessed at: http://www. J = 2.0 Hz. 3.0 Hz. Following the general procedure. Wang. The mixture was stirred at ambient temperature until all the starting material was consumed. R. reaction conditions. USA. Oil.0 mmol) in H2O (2 mL) or THF/water (1/3. 1H).0 mmol. mild and inexpensive method for deoximation of oximes in an aqueous solvent.com/1420-3049/17/3/2464/s1.. 6th ed. 1H).L.45.80 (d. The combined organic layers were dried over MgSO4. 9. T. J = 9.C.. 9. 6. Conclusions In summary.57–7. USA. 1H). Acknowledgments Financial support from the National Science Council of the Republic of China. Wuts. the solution was extracted with Et2O (3 × 5 mL).64 (s. giving a residue which was subjected to silica gel chromatography to furnish the pure aldehyde 2. Fuson. NY. 4. the title compound was obtained (102 mg. Following the general procedure. Taiwan (NSC100-2113-M-018-004-MY2) is gratefully acknowledged.. NY. 3H).63. 2 mL) at rt. 1H). Protective Groups in Organic Synthesis.43.5-Dimethoxybenzaldehyde (2r).M. 2H).47–7. This procedure appears to be advantageous in terms of chemical yield. 1H-NMR (CDCl3):  7. J = 9. pp. the title compound was obtained (131 mg. Oil.52 (m. J = 2. 7..3. 1. 1980. . 7. Greene. filtered. Qian.Y.. the title compound was obtained (161 mg. 2.4 Hz. Oil. 2007. 10377–10382.W. K.83–7. 1. Tetrahedron 2009. and functional group compatibility.Molecules 2012. 506–527. 7.63 (m. 4-Chlorobenzaldehyde (2q).96 (s. 1H-NMR (CDCl3):  7.

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