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Synlett 2010(3): 441-444  
DOI: 10.1055/s-0029-1219172
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Oxidative Conversion of Imines into 2-Azadienes

Julien Capra, Thierry Le Gall*
CEA Saclay, iBiTecS, Service de Chimie Bioorganique et de Marquage, Bât. 547, 91191 Gif-sur-Yvette Cedex, France
Fax: +33(1)69087991; e-Mail: thierry.legall@cea.fr;
Further Information

Publication History

Received 8 October 2009
Publication Date:
07 January 2010 (online)

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Abstract

Several 2-azadienes were prepared by treatment of im­ines derived from diphenylmethanamine and ketones with sodium hydride in DMF under an air atmosphere.

Key words

imines - oxygen - azadienes - oxidations - heterocycles

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9

Analytical Data for N -(Diphenylmethylene)-1-(pyrrolidin-1-yl)ethenamine (3) IR (KBr pellet): 3450, 3059, 2972, 2877, 1715, 1628 (s), 1490, 1445, 1341, 1317, 1278, 1239, 1183, 1157, 1074, 1030, 969, 919, 872, 783, 765, 699, 639 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.68 (d, 2 H, ArH), 7.50-7.30 (m, 8 H, ArH), 4.94 (s, 1 H, =CHH), 4.70 (s, 1 H, =CHH), 3.51 (m,
2 H, NCH2), 3.29 (m, 2 H, NCH2), 1.81-1.76 (m, 4 H, NCH2CH 2). ¹³C NMR (100 MHz, CDCl3): δ = 169.1, 166.1, 151.5, 139.2, 136.2, 132.6, 131.0, 130.2, 129.5, 129.2, 129.0, 128.4, 128.3, 128.1, 126.1, 105.8 (C=CHH), 48.9 (NCH2), 46.0 (NCH2), 26.4 (NCH2 CH2), 24.2 (NCH2 CH2). MS (ESI-TOF): m/z = 305.2 [M + H]+.

11

Analytical Data for 2,2,4-Triphenyl-2,5-dihydro-oxazole (7) IR (KBr pellet): 3058, 3027, 2925, 2850,, 2603, 2359, 1817, 1726, 1662, 1631 (C=N), 1578, 1550, 1531, 1490, 1446, 1363, 1313, 1285, 1230, 1209, 1065, 1028, 963, 941, 919, 869, 799, 758, 692, 643, 561, 535 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.87-7.84 (m, 2 H, ArH), 7.61-7.57 (m, 4 H, ArH), 7.49-7.42 (m, 3 H, ArH), 7.36-7.31 (m, 4 H, ArH), 7.29-7.24 (m, 2 H, ArH), 5.19 (s, 2 H, CH2). ¹³C NMR (100 MHz, CDCl3): δ = 166.9 (C=N), 144.2, 131.7, 131.1, 128.9, 128.3, 128.2, 127.8, 126.4, 113.9 (CPh2), 74.2 (CH2). MS (ESI-TOF): m/z = 300.2 [M + H]+.

15

Typical Experimental Procedure for the Synthesis of 2-Azadienes: Benzhydrylidene-[1-(4-methoxyphenyl)-vinyl]amine (6d)
A solution of imine 4d (200 mg, 0.634 mmol, 1 equiv) in anhyd DMF (6.3 mL) was placed under a dry air atmosphere. A suspension of NaH (84 mg of a 60% dispersion in mineral oil, 2.1 mmol, 3.3 equiv) in anhyd DMF (2.1 mL) was added, and the reaction mixture was stirred at r.t. for 2 d. Cold H2O was then added, the aqueous layer was extracted three times with CH2Cl2 and the combined organic layers dried over MgSO4. After filtration and concentration under vacuum, the residue obtained was purified by column chromatography (silica gel, 96:4 cyclohexane-EtOAc containing 4% Et3N), to give 2-azadiene 6d as an off-white solid (129 mg, 65%); mp 137-139 ˚C. IR (KBr pellet): 3052, 3021, 2965, 2929, 2837, 2046, 1960, 1901, 1820, 1660, 1622, 1604, 1569, 1509, 1443, 1414, 1312, 1291, 1249, 1178, 1150, 1121, 1094, 1073, 1028, 998, 966, 938, 834, 812, 788, 770, 746, 700, 670, 647, 615, 579, 553 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.79-7.75 (m, 2 H, ArH), 7.46-7.44 (m, 3 H, ArH), 7.42-7.38 (m, 2 H, ArH), 7.34-7.27 (m, 3 H, ArH), 7.13-7.09 (m, 2 H, ArH), 6.86-6.82 (m, 2 H, ArH), 4.70 (s, 1 H, CHH), 4.03 (s, 1 H, CHH), 3.80 (s, 3 H, OCH3). ¹³C NMR (100 MHz, CDCl3): δ = 167.5 (C=N), 159.6, 154.4, 139.4, 136.2, 130.9, 130.8, 130.2, 129.4, 128.8, 128.6, 128.5, 128.4, 128.3, 128.3, 127.9, 126.9, 113.7, 94.0 (CH2), 55.4 (OCH3). HRMS (ESI-TOF): m/z calcd for C22H20NO [M + H]+: 314.1545; found: 314.1547.