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Synlett 2005(16): 2465-2468  
DOI: 10.1055/s-2005-872702
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Reinvestigation into the Reaction of NH4OAc with Acetyl Derivatives of Baylis-Hillman Adducts: Formation of Tertiary and Secondary Allyl Amines Instead of Primary Allyl Amines [1]

Vijay Singha, Richa Pathaka, Sanjeev Kanojiyab, Sanjay Batra*a
a Medicinal Chemistry Division, Central Drug Research Institute, Lucknow 226001, India
Fax: +91(522)2623405, +91(522)2623938; e-Mail: batra_san@yahoo.co.uk;
b SAIF Division, Central Drug Research Institute, Lucknow 226001, India
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Publication History

Received 17 June 2005
Publication Date:
21 September 2005 (online)

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Abstract

A reinvestigation into the reaction between ammonium acetate and the acetyl derivatives of Baylis-Hillman adducts has led us to conclude that the products obtained are tertiary and secondary allyl amines and not the primary allyl amines. The unambiguous ­assignment of the structure of products using chemical and spectroscopic methods is described.

Key words

Baylis-Hillman - ammonium acetate - stereoselective - allyl amine

1

CDRI communication no. 6790.

1

CDRI communication no. 6790.

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Representative Data.2-({Bis-[3-(2-chlorophenyl)-2-methoxycarbonyl-allyl]amino}methyl)-3-(2-chlorophenyl)-acrylic Acid Methyl Ester ( 4c).
1H NMR (200 MHz, CDCl3): δ = 3.12 (s, 6 H, 3 × CH2N), 3.74 (s, 9 H, 3 × CO2Me), 7.12-7.25 (m, 6 H, 3 × 2 ArH), 7.35 (d, 3 H, J = 7.7 Hz, 3 × 1 ArH), 7.46 (d, 3 H, J = 7.1 Hz, 3 × 1 ArH), 7.92 (s, 3 H, 3 × =CH). 13C NMR (50 MHz, CDCl3): δ = 50.0, 52.4, 127.0, 129.9, 130.3, 131.6, 131.9, 133.9, 134.4, 140.2, 168.8. Anal. Calcd. for C33H30Cl3NO6: C, 61.65; H, 4.70; N, 2.25. Found: C, 61.54; H, 4.79; N, 2.18.
2-({Bis-[3-(2-bromophenyl)-2-methoxycarbonyl-allyl]amino}methyl)-3-(2-bromophenyl)-acrylic Acid Methyl Ester ( 4d).
1H NMR (200 MHz, CDCl3): δ = 3.07 (s, 6 H, 3 × CH2N), 3.76 (s, 9 H, 3 × CO2Me), 7.15-7.23 (m, 6 H, 3 × 2 ArH), 7.39-7.44 (m, 3 H, 3 × 1 ArH), 7.52-7.57 (m, 3 H, 3 × 1 ArH), 7.85 (s, 3 H, 3 × =CH). 13C NMR (50 MHz, CDCl3): δ = 49.8, 52.5, 124.4, 127.6, 130.3, 131.7, 133.0, 135.8, 142.3, 168.8. Anal. Calcd for C33H30Br3NO6: C, 51.06; H, 3.90; N, 1.80. Found: 51.33; H, 4.21; N, 2.05.
2-[(2-Cyano-3-phenylallylamino)methyl]-3-phenyl-acrylonitrile ( 6a).
1H NMR (300 MHz, CDCl3): δ = 3.66 (s, 4 H, 2 × CH2NH), 7.17 (s, 2 H, 2 × =CH), 7.36-7.50 (m, 6 H, 2 × 3 ArH), 7.77-7.79 (m, 4 H, 2 × 2 ArH). Anal. Calcd for C20H17N3: C, 80.24; H, 5.72; N, 14.04. Found: C, 79.95; H, 5.59; N, 14.14.
3-(4-Chloro-phenyl)-2-{[3-(4-chloro-phenyl)-2-cyanoallylamino]methyl}acrylonitrile ( 6f). 1H NMR (200 MHz, CDCl3): δ = 3.64 (s, 4 H, 2 × CH2NH), 7.14 (s, 2 H, 2 × =CH), 7.40 (d, 4 H, J = 8.4 Hz, 2 × 2 ArH), 7.71 (d, 4 H, J = 8.4 Hz, 2 × 2 ArH). 13C NMR (50 MHz, CDCl3): δ = 52.5, 110.6, 118.5, 129.6, 130.5, 131.9, 136.9, 143.5. Anal. Calcd for C20H15Cl2N3: C, 65.23; H, 4.11; N, 11.41. Found: 65.33; H, 4.49; N, 11.08.

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The products of series 4 were poorly soluble in MeOH, therefore we did not attempt to compare their HPLC with the corresponding amine.

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The electrospray mass spectra were recorded on a MICROMASS QUATTRO II triple quadrupole mass spectrometer. The samples (dissolved in MeOH) were introduced into the ESI source through a syringe pump at the rate of 5 µL/min. The ESI capillary was set at 3.5 kV and the cone voltage was variable (10 V, 25 V, 40 V, 90 V). The spectra were collected in 6 average scans.