Preparation of N,N-Dimethyl Aromatic Amides from Aromatic
Aldehydes with Dimethylamine and Iodine Reagents

Haruka Baba; Katsuhiko Moriyama; Hideo Togo

doi:10.1055/s-0031-1290659

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Synlett 2012(8): 1175-1180
DOI: 10.1055/s-0031-1290659

LETTER

Preparation of N,N-Dimethyl Aromatic Amides from Aromatic Aldehydes with Dimethylamine and Iodine Reagents

Haruka Baba, Katsuhiko Moriyama, Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
e-Mail: togo@faculty.chiba-u.jp;

Further Information

Publication History

Received 20 January 2012
Publication Date:
28 March 2012 (online)

Abstract
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Abstract

Various N,N-dimethyl aromatic amides were obtained in good to moderate yields by the reaction of aromatic aldehydes with aqueous dimethylamine in the presence of molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) at room temperature. Under the same conditions and using the same procedure, treatment of aromatic aldehydes and morpholine in the presence of DIH also provided the corresponding N-aroyl morpholines in good to moderate yields.

Key words

amides - aldehydes - amines - iodine - synthetic methods

References and Notes

1a Carey JS. Laffan D. Thomson C. Williams MT. Org. Biomol. Chem. 2006, 4: 2337

Google Scholar
1b Constable DJC. Dunn PJ. Hayler JD. Humphrey GR. Leazer JL. Linderman RJ. Lorenz K. Manley J. Pearlman BA. Wells A. Zaks A. Zhang TY. Green Chem. 2007, 9: 411

Google Scholar
2a Humphrey JM. Chamberlin AR. Chem. Rev. 1997, 97: 2243

Google Scholar
2b Valeur E. Bradley M. Chem. Soc. Rev. 2009, 38: 606

Google Scholar
2c Schotten C. Ber. Dtsch. Chem. Ges. 1884, 17: 2544

Google Scholar
2d Baumann E. Ber. Dtsch. Chem. Ges. 1886, 19: 3218

Google Scholar
2e Wardrop DJ. Basak A. Org. Lett. 2001, 3: 1053

Google Scholar
3a Tamaru Y. Yamada Y. Yoshida Z. Synthesis 1983, 474

Google Scholar
3b Naota T. Murahashi S. Synlett 1991, 693

Google Scholar
3c Tillack A. Rudloff I. Beller M. Eur. J. Org. Chem. 2001, 523

Google Scholar
3d Yoo W. Li C. J. Am. Chem. Soc. 2006, 128: 13064

Google Scholar
3e Chan J. Baucom KD. Murry JA. J. Am. Chem. Soc. 2007, 129: 14106

Google Scholar
3f Suto Y. Yamagiwa N. Torisawa Y. Tetrahedron Lett. 2008, 49: 5732

Google Scholar
3g Seo SY. Marks TJ. Org. Lett. 2008, 10: 317

Google Scholar
3h Li J. Xu F. Zhang Y. Shen Q. J. Org. Chem. 2009, 74: 2575

Google Scholar
3i Wang J. Li J. Xu F. Shen Q. Adv. Synth. Catal. 2009, 351: 1363

Google Scholar
3j Allen CL. Davulcu S. Williams JMJ. Org. Lett. 2010, 12: 5096

Google Scholar
3k Allam BK. Singh KN. Tetrahedron Lett. 2011, 52: 5851

Google Scholar
4a Marko IE. Mekhalfia A. Tetrahedron Lett. 1990, 31: 7237

Google Scholar
4b Ishihara K. Yano T. Org. Lett. 2004, 6: 1983

Google Scholar
4c Ekoue-Kovi K. Wolf C. Org. Lett. 2007, 9: 3429

Google Scholar
4d Gao J. Wang G. J. Org. Chem. 2008, 73: 2955

Google Scholar
4e Vora HU. Rovis T. J. Am. Chem. Soc. 2007, 129: 13796

Google Scholar
4f Fang C. Qian W. Bao W. Synlett 2008, 2529

Google Scholar
4g Liang J. Lv J. Shang Z. Tetrahedron 2011, 67: 8532

Google Scholar
4h Kuwano S. Harada S. Oriez R. Yamada K. Chem. Commun. 2012, 48: 145

Google Scholar
For reviews, see:
5a Togo H. Iida S. Synlett 2006, 2159

Google Scholar
5b Togo H. J. Synth. Org. Chem., Jpn. 2008, 66: 652

Google Scholar
5c Mori N. Togo H. Synlett 2004, 880

Google Scholar
5d Mori N. Togo H. Synlett 2005, 1456

Google Scholar
5e Mori N. Togo H. Tetrahedron 2005, 61: 5915

Google Scholar
5f Ishihara M. and Togo H. Synlett 2006, 227

Google Scholar
5g Iida S. Togo H. Synlett 2006, 2633

Google Scholar
5h Ishihara M. Togo H. Tetrahedron 2007, 63: 1474

Google Scholar
5i Iida S. Togo H. Tetrahedron 2007, 63: 8274

Google Scholar
5j Iida S. Togo H. Synlett 2007, 407

Google Scholar
5k Iida S. Togo H. Synlett 2007, 407

Google Scholar
5l Ishihara M. Togo H. Synthesis 2007, 1939

Google Scholar
5m Iida S. Togo H. Synlett 2008, 1639

Google Scholar
5n Iida S. Ohmura R. Togo H. Tetrahedron 2009, 65: 6257

Google Scholar
5o Moroda A. Furuyama S. Togo H. Synlett 2009, 1336

Google Scholar
5p Takahashi S. Togo H. Synthesis 2009, 2329

Google Scholar
5q Ushijima S. Togo H. Synlett 2010, 1065

Google Scholar
5r Ushijima S. Togo H. Synlett 2010, 1562

Google Scholar
5s Ushijima S. Moriyama K. Togo H. Tetrahedron 2011, 67: 958

Google Scholar
6 Colombeau L. Traore T. Compain P. Martin OR.
J. Org. Chem. 2008, 73: 8647

Google Scholar
8 Hanada S. Tsutsumi E. Motoyama Y. Nagashima H. J. Am. Chem. Soc. 2009, 131: 15032

Google Scholar
9 Allais A. Nomine G. Ger. Offen 1969, 57

Google Scholar
10 Oscar BL. J. Chem. Soc. 1929, 2267

Google Scholar
11 Vasilieva NV. J. Phys. Org. Chem. 2008, 21: 73

Google Scholar
12 McEvoy FJ. J. Org. Chem. 1979, 44: 4597

Google Scholar
13 Gryko DT. J. Porphyrins Phthalocyanines 2003, 7: 239

Google Scholar
14 Huisgen R. Chem. Ber. 1965, 98: 1138

Google Scholar

7

Preparation of N , N -Dimethyl-4-bromobenzamide; Typical Procedure: 4-Bromobenzaldehyde (1.0 mmol, 185 mg), aq dimethylamine (50%, 3.0 mmol, 0.32 mL), 1,3-diiodo-5,5-dimethylhydantoin (1.0 mmol, 380 mg), and K₂CO₃ (1.0 mmol, 138 mg) were added to CCl₄ (3 mL).
The mixture was stirred at r.t. for 24 h under an argon atmosphere. Upon completion, the mixture was poured into sat. aq sodium sulfite solution and extracted with chloroform (3 × 20 mL). The organic layer was dried over Na₂SO₄. After filtration and removal of the solvent under reduced pressure, the residue was subjected to short column chromatography on silica gel (hexane/ethyl acetate, 3:2) to give N,N-dimethyl-
4-bromobenzamide in 72% yield.
Mp 73 ˚C (Lit.⁸ 76-79 ˚C); IR (neat): 1626 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.97 (s, 3 H), 3.10 (s, 3 H), 7.30 (d, J = 8.6 Hz, 2 H), 7.54 (d, J = 8.6 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.4, 39.5, 123.8, 128.8, 131.6, 135.1, 170.5; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₁ONBr: 228.0019; found: 228.0021.
N , N -Dimethyl- p -chlorobenzamide: Oil; IR (neat): 1640 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.97 (s, 3 H), 3.10 (s, 3 H), 7.37 (br s, 4 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.2, 39.4, 128.1, 128.5, 134.5, 135.4, 170.3; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₁ONCl: 184.0524; found: 184.0526.
N , N -Dimethyl- p -fluorobenzamide: Oil (Lit.⁹ mp 64 ˚C); IR (neat): 1633 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.99 (s, 3 H), 3.10 (s, 3 H), 7.10 (t, J = 8.8 Hz, 2 H), 7.43 (dd, J = 8.8, 5.5 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.4, 39.5, 115.3 (J = 21.9 Hz), 129.2 (J = 8.6 Hz), 132.2, 163.2 (J = 249.9 Hz), 170.6; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₁ONF: 168.0819; found: 168.0821.
N , N -Dimethyl- p -nitrobenzamide: Mp 89-93 ˚C (Lit.⁸
99-103 ˚C); IR (Nujol): 1377, 1514, 1643 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.98 (s, 3 H), 3.15 (s, 3 H), 7.60 (d, J = 7.3 Hz, 2 H), 8.28 (d, J = 7.3 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.3, 39.3, 123.7, 128.0, 142.4, 148.2, 169.2; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₁O₃N₂: 195.0764; found: 195.0768.
N , N -Dimethyl- m -nitrobenzamide: Mp 76-77 ˚C (Lit.^¹0 81 ˚C); IR (Nujol): 1377, 1533, 1635 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.01 (s, 3 H), 3.15 (s, 3 H), 7.61 (td, J = 7.7, 1.0 Hz, 1 H), 7.77 (dt, J = 7.7, 1.4 Hz, 1 H), 8.27-8.30 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.5, 39.5, 122.2, 124.3, 129.7, 133.1, 137.8, 147.9, 168.9; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₁O₃N₂: 195.0764; found: 195.0768.
N , N -Dimethyl- p -cyanobenzamide: Oil (Lit.⁸ mp 100-105 ˚C); IR (neat): 1631, 2230 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.96 (s, 3 H), 3.13 (s, 3 H), 7.52 (d, J = 8.2 Hz, 2 H), 7.71 (d, J = 8.2 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS):
δ = 35.2, 39.2, 113.2, 118.0, 127.6, 132.2, 140.5, 169.4; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₁₁ON₂: 175.0866; found: 175.0869.

N , N -Dimethyl- p -(trifluoromethyl)benzamide: Mp 75 ˚C (Lit.⁹ 65-75 ˚C); IR (Nujol): 1337, 1625 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.97 (s, 3 H), 3.13 (s, 3 H), 7.53 (d, J = 7.9 Hz, 2 H), 7.68 (d, J = 7.9 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.2, 39.3, 123.7 (J _C-F = 272.8 Hz), 125.5, 127.4, 131.4 (J _C-F = 32.4 Hz), 140.0, 170.2; HRMS (ESI): m/z
[M + H]⁺ calcd for C₁₀H₁₁ONF₃: 218.0787; found: 218.0788.
N , N -Dimethylbenzamide: Oil (commercial); IR (neat): 1625 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.98 (s, 3 H), 3.12 (s, 3 H), 7.41 (br s, 5 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.3, 39.5, 126.9, 128.3, 129.4, 136.2, 171.6.
N , N -Diimethyl- p -methylbenzamide: Oil; IR (neat): 1625 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.37 (s, 3 H), 2.99 (s, 3 H), 3.10 (s, 3 H), 7.19 (d, J = 7.9 Hz, 2 H), 7.31 (d, J = 7.9 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 21.3, 35.4, 39.6, 137.2, 128.9, 133.4, 139.6, 171.8; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₁₄ON: 164.1070; found: 164.1071.
N , N -Dimethyl- p -methoxybenzamide: Oil; IR (neat): 1252, 1610 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.06 (s, 6 H), 3.83 (s, 3 H), 6.90 (d, J = 8.8 Hz, 2 H), 7.40 (d, J = 8.8 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.5, 39.7, 55.2, 113.4, 128.2, 129.0, 160.5, 171.5; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₁₄ O₂N: 180.1019,; found: 180.1021.
N , N -Dimethyl-1-naphthalenecarboxamide: Oil (Lit.^¹¹
mp 61-62 ˚C); IR (neat): 1615 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.82 (s, 3 H), 3.26 (s, 3 H), 7.42 (dd, J = 7.1, 1.2 Hz, 1 H), 7.46-7.54 (m, 3 H), 7.78-7.80 (m, 1 H), 7.84-7.88 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 34.8, 38.8, 123.8, 124.8, 125.1, 126.3, 126.9, 128.3, 128.9, 129.4, 133.4, 134.7, 170.8; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₄ON: 200.1070; found: 200.1070.
N , N -Dimethyl-2-thiophenecarboxamide: Oil; IR (neat): 1619 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.19 (s, 6 H), 7.05 (dd, J = 5.0, 3.7 Hz, 1 H), 7.36 (dd, J = 3.7, 1.2 Hz, 1 H), 7.45 (dd, J = 5.0, 1.2 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS):
δ = 35.2, 39.2, 126.6, 128.7, 129.1, 137.8, 164.4; HRMS (ESI): m/z [M + Na]⁺ calcd for C₇H₉ONNaS: 178.0297; found: 178.0299.
N , N -Dimethyl-3-pyridinecarboxamide: Oil; IR (neat): 1633 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.02 (s, 3 H), 3.14 (s, 3 H), 7.36 (ddd, J = 7.8, 4.8, 0.9 Hz, 1 H), 7.77 (dt, J = 7.8, 2.0 Hz, 1 H), 8.66 (dd, J = 4.8, 2.0 Hz, 1 H), 8.69 (dd,
J = 2.0, 0.9 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 35.4, 39.5, 123.3, 132.0, 134.9, 147.9, 150.5, 168.9; HRMS (ESI): m/z [M + H]⁺ calcd for C₈H₁₁ON₂: 151.0866; found: 151.0867.
N , N -Dimethyl-1-benzothiophene-2-carboxamide: Mp 105 ˚C; IR (Nujol): 1615 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.22 (s, 6 H), 7.38-7.41 (m, 2 H), 7.53 (s, 1 H), 7.80-7.84 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 36.2, 39.0, 122.3, 124.6, 124.6, 125.4, 125.7, 137.5, 138.7, 140.2, 164.8; HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₁₁ONNaS: 228.0454; found: 228.0454.
N , N -Dimethylbenzofuran-2-carboxamide: Mp 71-73 ˚C; IR (Nujol): 1642 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.16 (s, 3 H), 3.36 (s, 3 H), 7.26-7.31 (m, 2 H), 7.40 (t, J = 8.0 Hz, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.66 (d, J = 8.0 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 36.2, 38.1, 111.7, 111.8, 122.2, 123.5, 126.3, 127.0, 149.3, 154.6, 161.0; HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₁₁O₂NNa: 212.0682; found: 212.0682.
N , N , N -Trimethyl-1 H -indol-2-carboxamide: Oil; IR (neat): 1630 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.19 (s, 6 H), 3.85 (s, 3 H), 6.64 (s, 1 H), 7.14 (t, J = 8.1 Hz, 1 H), 7.29
(t, J = 8.1 Hz, 1 H), 7.36 (d, J = 8.1 Hz, 1 H), 7.63 (d, J = 8.1 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 31.0, 35.1, 39.5, 103.9, 109.7, 120.0, 121.4, 123.2, 126.3, 131.9, 137.7, 164.3; HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₂H₁₄ON₂Na: 225.0998; found: 225.0999.
N -( p -Bromobenzoyl)morpholine: Oil; IR (neat): 1114, 1623 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.32-3.98 (m, 8 H), 7.29 (d, J = 8.3 Hz, 2 H), 7.56 (d, J = 8.3 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.7, 48.5, 66.7, 124.2, 128.8, 131.8, 134.0, 169.3; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₁H₁₃O₂NBr: 270.0124; found: 270.0127.
N -( p -Chlorobenzoyl)morpholine: Mp 69-70 ˚C (Lit.^¹²
76-77 ˚C); IR (Nujol): 1110, 1627 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.36-3.98 (m, 8 H), 7.36 (d, J = 8.7 Hz, 2 H), 7.40 (d, J = 8.7 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.9, 48.0, 66.8, 128.6, 128.8, 133.6, 136.0, 169.3; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₁H₁₃O₂NCl: 226.0629; found: 226.0628.
N -( p -Fluorobenzoyl)morpholine: Oil; IR (neat): 1115, 1636 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.84-3.99 (m, 8 H), 7.11 (t, J = 8.8 Hz, 2 H), 7.43 (dd, J = 8.8, 5.5 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.7, 48.2, 66.8, 115.7 (J = 21.9 Hz), 129.4 (J = 8.6 Hz), 131.3, 163.5 (J = 249.9 Hz), 169.4; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₁H₁₃O₂NF: 210.0925; found: 210.0920.
N -( p -Nitrobenzoyl)morpholine: Mp 97-99 ˚C; IR (Nujol): 1107, 1350, 1509, 1622 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.29-3.95 (m, 8 H), 7.59 (d, J = 8.8 Hz, 2 H), 8.29 (d, J = 8.8 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.5, 48.0, 66.7, 123.9, 128.1, 141.4, 148.4, 168.0; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₁H₁₃N₂O₄: 237.0870; found: 237.0873.
N -( m -Nitrobenzoyl)morpholine: Mp 86-87 ˚C (Lit.^¹³ 87-88 ˚C); IR (neat): 1115, 1354, 1535, 1650 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.38-3.95 (m, 8 H), 7.64 (t, J = 7.8 Hz, 1 H), 7.76 (dt, J = 7.8, 1.3 Hz, 1 H), 8.27-8.32 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.5, 48.1, 66.7, 122.3, 124.7, 129.9, 133.1, 136.9, 148.1, 167.7; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₃O₄N₂: 237.0870; found: 237.0870.
N -( p -Cyanobenzoyl)morpholine: Mp 138 ˚C (Lit.^¹³ 141-142 ˚C); IR (Nujol): 1109, 1621, 2224 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.30-3.91 (m, 8 H), 7.52 (d, J = 8.5 Hz, 2 H), 7.73 (d, J = 8.5 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS):
δ = 42.5, 47.9, 66.6, 113.6, 117.9, 127.7, 132.4, 139.5, 168.2; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₃O₂N₂: 217.0972; found: 217.0971.
N -( p -Trifluorobenzoyl)morpholine: Oil; IR (neat): 1112, 1326, 1633 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.30-3.98 (m, 8 H), 7.53 (d, J = 8.1 Hz, 2 H), 7.70 (d, J = 8.1 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.6, 48.1, 66.8, 123.6 (J _C-F = 272.7 Hz), 125.7, 127.4, 131.7 (J _C-F = 32.5 Hz), 138.9, 168.9; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₃O₂NF₃: 260.0893; found: 260.0893.
N -( p -Methylbenzoyl)morpholine: Oil; IR (neat): 1115, 1631 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 2.38 (s, 3 H), 3.36-3.92 (m, 8 H), 7.21 (d, J = 8.2 Hz, 2 H), 7.31 (d, J = 8.2 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 21.3, 43.2, 48.3, 66.8, 127.1, 129.1, 132.2, 140.0, 170.6; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₆O₂N: 206.1176; found: 206.1177.
N -( p -Methoxybenzoyl)morpholine: Oil; IR (neat): 1115, 1260, 1602 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.59-3.79 (m, 8 H), 3.84 (s, 3 H), 6.92 (d, J = 8.8 Hz, 2 H), 7.39 (d, J = 8.8 Hz, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 43.1, 48.7, 55.3, 66.8, 113.7, 127.2, 129.2, 160.8, 170.4; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₆O₃N: 222.1125; found: 222.1125.
N -Benzoylmorpholine: Oil (Lit.^¹4 mp 72-73 ˚C); IR (neat): 1115, 1630 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.36-3.93 (m, 8 H), 7.38-7.52 (m, 5 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.2, 48.3, 66.9, 127.1, 128.5, 129.9, 135.3, 170.4; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₁H₁₄O₂N: 192.1019; found: 192.1014.
N -(1-Naphthalenylcarbonyl)morpholine: Oil; IR (neat): 1115, 1630 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.14-3.28 (m, 2 H), 3.46-3.59 (m, 2 H), 3.82-4.07 (m, 4 H), 7.41-7.58 (m, 4 H), 7.83-7.91 (m, 3 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.2, 47.6, 67.0, 123.9, 124.6, 125.1, 126.5, 127.1, 128.5, 129.3, 129.5, 133.4, 133.6, 169.5; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₆O₂N: 242.1176; found: 242.1172.
N -(2-Thiophenylcarbonyl)morpholine: Oil; IR (neat): 1115, 1615 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.71-3.80
(m, 8 H), 7.05 (dd, J = 5.0, 3.6 Hz, 1 H), 7.29 (dd, J = 3.6, 1.1 Hz, 1 H), 7.46 (dd, J = 5.0 Hz, 1.1 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.2, 47.6, 66.8, 126.7, 128.8, 128.9, 136.6, 163.6; HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₁₂O₂NS: 198.0583; found: 198.0583.
N -(3-Pyridinylcarbonyl)morpholine: Oil; IR (neat): 1114, 1630 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.40-3.92 (m 8 H), 7.38 (ddd, J = 7.8, 4.8, 0.9 Hz, 1 H), 7.77 (dt, J = 8.0, 2.0 Hz, 1 H), 8.67-8.70 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.3, 48.2, 66.8, 123.5, 131.1, 135.1, 148.0, 151.0, 167.8; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₀H₁₃O₂N₂: 193.0972; found: 193.0970.
N -(Benzothiophene-2-carbonyl)morpholine: Mp 90-92 ˚C; IR (Nujol): 1112, 1600 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.73-3.82 (m, 8 H), 7.38-7.44 (m, 2 H), 7.49 (s, 1 H), 7.79-7.88 (m, 2 H); ^¹³C NMR (CDCl₃, TMS): δ = 40.5, 40.5, 66.6, 122.2, 124.5, 124.7, 125.2, 125.7, 136.0, 138.4, 140.0, 163.7; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₄O₂NS: 248.0740; found: 248.0737.
N -(Benzofuran-2-carbonyl)morpholine: Mp 92 ˚C;
IR (Nujol): 1108, 1609 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.76-3.82 (m, 4 H), 3.82-4.00 (m, 4 H), 7.30 (t, J = 7.7 Hz, 1 H), 7.35 (s, 1 H), 7.41 (t, J = 7.7 Hz, 1 H), 7.52 (d, J = 7.7 Hz, 1 H), 7.66 (d, J = 7.7 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 42.5, 46.5, 66.8, 111.7, 112.3, 122.2, 123.6, 126.5, 126.8, 148.7, 154.5, 159.6; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₄O₃N: 232.0968; found: 232.0964.
N -( N -Methyl-1 H -indol-2-carbonyl)morpholine: Mp 109-112 ˚C; IR (Nujol): 1111, 1643 cm^-¹; ^¹H NMR (CDCl₃, TMS): δ = 3.71-3.84 (m, 8 H), 3.86 (s, 3 H), 6.60 (s, 1 H), 7.15 (t, J = 8.2 Hz, 1 H), 7.31 (t, J = 8.2 Hz, 1 H), 7.37 (d, J = 8.2 Hz, 1 H), 7.62 (d, J = 8.2 Hz, 1 H); ^¹³C NMR (CDCl₃, TMS): δ = 25.0, 31.1, 67.0, 103.9, 109.9, 120.4, 121.6, 123.5, 126.3, 131.1, 138.0, 163.2; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₇O₂N₂: 245.1285; found: 245.1278