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Solvent free imine formation: condensation of o-vanillin and 2-bromoaniline; (E)-2-(((2-bromophenyl)imino)methyl)-6-methoxyphenol

SyntheticPage 820
DOI: 10.1039/SP820
Submitted Jun 14, 2017, published Jun 21, 2017
Steven M. Kennedy (Steven.Kennedy@millersville.edu), Lauren Ostopowicz (laostopo@millersville.edu), Raquel Hernández (rahernan@millersville.edu)
A contribution from Kennedy Group, Millersville University


			Reaction Scheme: <img src="/images/empty.gif" alt="" />Solvent free imine formation<img src="/images/empty.gif" alt="" />:&nbsp;condensation of <em>o</em>-vanillin and 2-bromoaniline

Chemicals Used

o-Vanillin (99%, TCI America)
2-Bromoaniline (98%, TCI America)

Procedure

In a tared 250 mL beaker, o-vanillin (0.76 g, 5.0 mmol) and 2-bromoaniline (0.82 g, 5.0 mmol) were mixed (using a glass-stirring rod) until an orange oil was formed; after 25 min, 50 mL of hexanes was added to the reaction mixture, which was transfered into a 100 mL round-bottom flask. After 24 hours, small needles of crystals appeared in the flask. The hexanes was removed by rotary evaporation to provide the dark orange solid (E)-2-(((2-bromophenyl)imino)methyl)-6-methoxyphenol (1.39 g, 4.5 mmol, 91% yield).

Author's Comments

This compound was reluctant to become a solid. It was not recrystallized; all characterization was preformed on the crude product.

Data

1H NMR (400 MHz, CDCl3): δ 13.56 (s, 1H, ArOH), 8.62 (s, 1H, N=CH), 7.68 (d, 1H), 7.37 (t, 1H), 7.26 (d, 1H), 7.15 (t, 1H),  7.03 (t, 2H), 6.90 (t, 1H), 3.95 (s, 3H, ArOCH3).

13
C NMR
(100 MHz, CDCl3): δ  162.97, 151.38, 148.54, 146.36, 133.32, 128.42, 128.10, 123.86, 120.26, 118.90 (2), 118.66, 114.89, 56.16.
IR 
(cm–1): ν 3676, 2988, 2902, 1722, 1612, 1224
R
f 0.60 on SiO2 in 1:9 ethyl acetate:hexane
M.p. 109-112°C

Lead Reference

K.M. Touchette, J. Chem. Ed. 2006, 83 (6), 926. DOI: 10.1021/ed083p929

Other References

E. Hadjoudis, M. Vittorakis, I. Moustakali-Mavridis, Tetrahedron 1987, 43 (7), 1345. DOI: 10.1016/S0040-4020(01)90255-8

Supplementary Information

13C_NMR_Full_(E)-2-(((2-bromop (CNMR_Full.pdf)
13C_NMR_Zoom_(E)-2-(((2-bromop (CNMR_Zoom.pdf)
1H_NMR_Full_(E)-2-(((2-bromoph (HNMR_Full.pdf)
1H_NMR_Zoom_(E)-2-(((2-bromoph (HNMR_Zoom1.pdf)
Orange Solid (E)-2-(((2-bromop (IMG_3206.jpg)

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Get structure file (.cdx, .sk2, .mol)

Keywords: aldehydes, amines, imine formation

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