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Nitrosonium (NO+) Initiated O-Alkylation of Oximes with N-Vinylpyrrolidinone

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Nitrosonium (NO+) Initiated O-Alkylation of Oximes with N-Vinylpyrrolidinone Indian Journal of Chemistry Vol. 54B, May 2015, pp. 656-661 Nitrosonium (NO+) initiated O-alkylation of oximes with N-vinylpyrrolidinone Guai Li Wua,b*, Jian Liub, Yanli Weib, Yong Jiang Chenb & Long Min Wua aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China bJiangSu HengRui Medicine Co. Ltd., Jiangsu Lianyungang 222047, China E-mail:[email protected] Received 11 March 2014; accepted (revised) 27 February 2015 An efficient O-alkylation of oximes with N-vinylpyrrolidinone has been achieved using nitrosonium tetrafluoroborate as a catalyst, giving oxime ethers in good to excellent yields. Keywords: Oxime, N-vinylpyrrolidinone, alkylation, nitrosonium Oxime ethers are valuable nucleophilic reagents with consideration. The electron-withdrawing group at both nitrogen and oxygen atoms as nucleophiles. They oximes is favorable to O-alkylation of oximes, but the have been, in general, directly prepared from oximes reaction takes a longer time. Although the electron- with alkyl halides under basic conditions1. Acid donating group, such as methoxyl group, in 1g conditions, but, inevitably lead to byproducts of shortens the reaction time, a byproduct, probably a N-alkylation2. Therefore, it is desirable to develop a nitrone6, is produced. Similar results are also obtained in new synthetic protocol for the preparation of oxime substrate 1h and 1k. It is probably attributed to an ethers under neutral or acidic conditions. enhanced nucleophilicity of nitrogen atom caused by As reported, tris(4-bromophenyl)aminium cation electron-donating groups. +· - radical (TBPA SbCl6 ) or ammonium nitrate (CAN) Application of this procedure mentioned above to can efficiently initiate the O-alkylation of oximes with the reaction of thiophenols with N-vinylpyrrolidinone N-vinylpyrrolidinone, producing the corresponding in the presence of nitrosonium tetrafluoroborate (5 mol%) 3 oxime ethers . It inspires us to examine whether in CH2Cl2 affords the corresponding S-alkylation nitrosonium (NO+), on our interests in the synthetic adducts7 in 99% yields (Scheme II). potential of NO+ (Ref 4), is a good initiator for the A possible mechanism rationalization of the reaction of oxime 1 with N-vinylpyrrolidinone 2 O-alkylation of oximes or the S-alkylation of thiophenols (Scheme I) or not. The results are encouraging. Later, with N-vinylpyrrolidinone initiated by NO+ is presented this strategy was successfully applied to thiophenols in Scheme III. The stoichiometry study shows that a (Scheme II). very small NO+ amount of 5 mol% starts reactions. It is assumed that an electron transfer (ET) reaction Results and Discussion initially occurs between NO+ and the C–C double Initial experiment involved the reaction of 1a with bond of 2, forming cation radical 2+. (Ref 4a). A N-vinylpyrrolidinone 2 in the presence nitrosonium nucleophilic addition of oxime or thiophenol to 2+. tetrafluoroborate in dichloromethane led to the corres- provides cation radical [1+2]+., which then transfers a ponding 3a as our desired product. Various substituted proton to 2, forming [1+2]. and 2+, respectively. The conditions afforded the corresponding O-alkylation 2+ so produced will participate in the reaction. The [1+2]. product. abstracts a hydrogen atom from the solvent to give the All the products were identified by 1H and 13C NMR, corresponding oxime ether or sulfide. A mechanism FAB-MS or EIMS, IR, and HR-ESI-MS. The results suggested for byproducts is given in Scheme III by are listed in Table I. route 2. From the Table II, it can be seen that N-vinyl- Solvent effects were investigated using 1a as a pyrrolidinone exhibits very good to excellent reactivity substrate. Solvents examined were carbon tetrachloride, toward all the aldoximes and ketoximes5 under dichloromethane, methanol, tetrahydrofuran, and WU et al.: O-ALKYLATION OF OXIMES 657 Table I — O-Alkylation of oximes with N-vinylpyrrolidinone + 2 O + - initiated by NO R N N NO BF4 , 5 mol% OH + CH2Cl2, r.t Time 1 Yield of R Compd R1 R2 (hr) 3/4 (%)a 1 2 1a m-NO2-Ph H 1.5 96/0 O 1b p-Cl-Ph H 1.0 97/0 N 1c Ph H 1.3 98/0 O N 1d o-OH-Ph H 1.3 94/0 R2 N R2 N+ 1e p-NO -Ph H 2.6 88/0 O + 2 O- 1f PhCH2 H 1.0 86/0 R1 R1 1g p-MeO-Ph H 0.33 76/21 1h p-Me-Ph H 0.5 84/7 3 4 1i Ph CH3 0.67 98/0 1j p-Br-Ph CH3 1.0 90/0 Scheme I 1k p-MeO-Ph CH3 2.2 90/5 NOH O NO+BF -, 5 mol% N O 1l 0.83 95/0 R4SH + N 4 CH2Cl2, r.t R S NOH 5 2 6 1m 0.67 94/0 Scheme II acetonitrile. Among them, dichloromethane was found to be highly favorable for the O-alkylation of oximes 1n 1.5 94/0 NOH under consideration (Table III). aIsolated yield based on oxime. bAll the oximes are anti-configurations. Experimental Section Flash chromatography was carried out using silica Table II — S-alkylation of thiophenols with gel 60 (200-300 mesh, particle size 0.040-0.062 mm) N-vinylpyrrolidinone initiated by NO+ supplied by Qingdao Ocean Chemical Plant. Melting points were measured on a Yanagimoto melting point Compd R4 Time Yield (hr) of 6 (%)a apparatus and are uncorrected. IR spectra (KBr) were recorded on a Nicolet NEXUS 670 FT-IR spectro- 1 13 5o Ph 1.2 99 photometer. H and C NMR spectra were recorded 5p p-Cl-Ph 0.9 90 on a Varian Mercury Plus 300/400 NMR spectrometer. 5q p-OMe-Ph 1.0 86 1 Chemical shifts (δ) are reported relative to TMS ( H) 5r PhCH2 1.2 97 13 or CDCl3 ( C) as an internal standard. MS-EI (70 eV) 5s CH3CH2CH2 6.0 70 determinations were carried out on an HP 5985A aIsolated yield based on N-vinylpyrrolidinone. spectrometer. FAB-MS determinations were carried out on an ZAB-HS spectrometer. HRMS-ESI detections nitrosonium tetrafluoroborate (5 mol%), which was were run on a Bruker Daltonics APEX II 47e pasted onto a piece of glass. The resulting mixture spectrometer with an ESI. Chemicals were of highest was stirred for a required time (Table I). The completion grade commercially available and used as received, of reaction was indicated by TLC. Consequently, it unless otherwise sated. All reagents were weighed was diluted with water and extracted with 4 × 15 mL and handled in air at room temperature. of CH2Cl2, and dried over anhydrous Na2SO4. The solvent was evaporated and the residue purified by Typical procedure for the preparation of 3a column chromatography on silica gel (200-300 mesh, In a typical experiment procedure, to a mixture of ethyl acetate/hexane) to afford product 3a as a colorless 1a (0.5 mmol) and N-vinylpyrrolidinone (0.75 mmol ) liquid in good yield (96%). Other compounds were in 10 mL of dichloromethane (CH2Cl2) at RT was added obtained by the same procedure. 658 INDIAN J. CHEM., SEC B, MAY 2015 Table III — Solvent effects on the O-alkylation of 1a with N-vinylpyrrolidinone Solvent Time (hr) Yield of 3a (%)a Dichloromethane 1.5 96 Tetrahydrofuran 12 85 Acetonitrile 24 52 Methanol 24 0 Carbon tetrachloride 48 0 aIsolated yield based on 1a. Hz), 2.04 (m, 2H, J =7.2 Hz, J = 7.5 Hz, J = 8.1Hz, J = 8.4 Hz), 1.51(d, 3H, J = 6.3 Hz); 13C NMR (75 MHz, CDCl3): δ 175.5, 148.3, 147.2, 133.7, 132.3, 129.7, 124.4, 122.1, 80.8, 41.6, 31.5, 17.9, 16.8; FAB-MS: m/z (%) 278 ((M+H)+, 41), 168 (17), 113 (100); HR- ESI-MS: m/z Calcd for C13H15N3O4 + H: 278.1135. Found: 278.1136. 4-Chloro-benzaldehyde O-[1-(2-oxo-pyrrolidin- 1-yl)-ethyl]-oxime, 3b: Yield 97%, 129 mg, Known compound (lit.3a), Colorless prisms, m.p. 72-73°C; IR (KBr): 2986.6, 2947.5, 1698.5, 1491.2, 1418.3, 1281.7, 1268.9, 1087.8, 949.8 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.02 (s, 1H), 7.51 (d, 2H, J = 8.7 Hz), 7.32 (d, 2H, J = 8.4 Hz), 6.14(m, 1H, J = 6.3 Hz, J = 6.6 Hz, J = 12.5 Hz), 3.43 (m, 2H, J = 6.9 Hz, J = 10.5 Hz), 2.43 (m, 2H, J = 7.5 Hz, J = 8.4 Hz, J = 8.0 Hz), 2.01 (m, 2H, J = 7.5 Hz, J = 10.9 Hz, J = 11.3 Hz), 1.47 (d, 13 3H, J = 6.3 Hz); C NMR (75 MHz, CDCl3): δ 175.9, 148.5, 136.1, 130.7, 129.2, 128.6, 80.7, 41.8, 31.9, 18.3, 17.2; FAB-MS: m/z (%) 267 ((M+H)+, 99), 155 (48), 113 (100); HR-ESI-MS: m/z Calcd for C13H15N2O2Cl + H: 267.0983. Found: 267.0985. Benzaldehyde O-[1-(2-oxo-pyrrolidin-1-yl)-ethyl]- oxime 3c: Yield 98%, 114 mg, Known compound (lit.3a), Colorless liquid, IR (KBr): 2986.2, 2946.2, -1 1698.0, 1418.0, 1284.4, 1268.7, 1087.7, 947.7cm ; 1 H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 7.58 (m, Scheme III 2H, J = 2.4 Hz, J = 2.8 Hz, J = 3.2 Hz), 7.36 (m, 3H), Characterization Data for Products 6.11 (m, 1H, J = 6.0 Hz, J = 6.4 Hz, J = 12.7 Hz), 3-Nitro-benzaldehyde O-[1-(2-oxo-pyrrolidin-1-yl)- 3.40 (m, 2H, J = 6.4 Hz, J = 6.8 Hz, J = 7.2 Hz), 2.40 ethyl]-oxime, 3a: Yield 96%, 133 mg, Known compound (m, 2H, J =7.6 Hz, J = 8.0 Hz, J = 8.4Hz), 1.97 (m, (lit.3c), Colorless liquid, IR (KBr): 2988.1, 2956.0, 2H, J =7.2 Hz, J = 7.6 Hz, J = 8.4 Hz), 1.44 (d, 3H, 13 1697.4, 1532.1, 1418.3, 1351.9, 1281.9, 1269.5, 1087.0, J =5.6 Hz); C NMR (100MHz, CDCl3): δ 175.5, 149.4, -1 1 957.6 cm ; H NMR (300 MHz, CDCl3): δ 8.34 (dd, 131.8, 129.9, 128.6, 127.1, 80.4, 41.5, 31.6, 18.0, 1H, J = 1.2 Hz, J = 2.4 Hz), 8.23 (dd, 1H, J = 1.2 Hz, 16.9; FAB-MS: m/z (%) 233 ((M+H)+, 16), 113 (100), J = 1.8Hz, J = 8.3 Hz), 8.14 (s, 1H), 7.99 (dd, 1H, J = 1.2 56 (79); HR-ESI-MS: m/z Calcd for C13H16N2O2 + H: Hz, J = 8.7 Hz), 7.57 (t, 1H, J = 2.1 Hz, J = 2.4 Hz, 233.1282.
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