Abstract
A simple, efficient, scaleable process has been developed for
the N-formylation amines in water. Treatment of amines with triethyl
orthoformate in water at reflux under neutral conditions without
any additives gives the corresponding N -formyl
derivatives in good yields.
Key words
N-formylation - amines - organic reactions
in water - triethyl orthoformate
References and Notes
1 Jackson A.
Meth-Cohn O.
J. Chem. Soc., Chem. Commun.
1995,
1319
2 Chen B.-C.
Bednarz MS.
Zhao R.
Sundeen JE.
Chen P.
Shen Z.
Skoumbourdis AP.
Barrish JC.
Tetrahedron Lett.
2000,
41:
5453
3a Kobayashi K.
Nagato S.
Kawakita M.
Morikawa O.
Konishi H.
Chem. Lett.
1995,
575
3b Kakehi A.
Ito S.
Hayashi S.
Fujii T.
Bull. Chem. Soc. Jpn.
1995,
68:
3573
4 Han Y.
Cai L.
Tetrahedron Lett.
1997,
38:
5423
5 Mahmoud KF, and Newtown SP. inventors; US 5,155,267.
6 Dieter A, and Gerhard K. inventors; US 4,419,297.
7 Downie IM.
Earle MJ.
Heaney H.
Shuhaibar KF.
Tetrahedron
1993,
49:
4015
8a Kobayashi S.
Nishio K.
J.
Org. Chem.
1994,
59:
6620
8b Clayden J.
Organic Chemistry
Oxford
University Press;
Oxford:
2001.
p.276-296
8c Kobayashi S.
Yasuda M.
Hachiya I.
Chem.
Lett.
1996,
407
9a Green TW.
Wuts PGM.
Protective Groups in Organic
Synthesis
3rd ed.:
Wiley-Interscience;
New
York:
1999.
9b Sheehan JC.
Yang DDH.
J.
Am. Chem. Soc.
1958,
80:
1154
9c Strazzolini P.
Giumanini AG.
Cauci S.
Tetrahedron
1990,
46:
1081
9d Blicke FF.
Lu C.-J.
9e Waki J.
Meienhofer J.
J. Org. Chem.
1977,
42:
2019
9f Chen FMF.
Benoiton NL.
Synthesis
1979,
709
9g Yale HL.
J. Org. Chem.
1971,
36:
3238
9h Kisfaludy L.
Laszlo O.
Synthesis
1987,
510
9i Neveux M.
Bruneaum C.
Dixneuf PH.
J.
Chem. Soc., Perkin Trans. 1
1991,
1197
10 Duezek W.
Deutsch J.
Vieth S.
Nicolas H.-J.
Synthesis
1996,
37
11 Mihara M.
Ishino Y.
Minakata S.
Komatsu M.
Synthesis
2003,
2317
12 Reddy PG.
Kumar GDK.
Baskaran S.
Tetrahedron
2000,
41:
9149
13 Luca LD.
Giacomelli G.
Porcheddu A.
Salaris M.
Synlett
2004,
2570
14 Desai B.
Danks TN.
Wagner G.
Tetrahedron
Lett.
2005,
46:
955
15a Hosseini-Sarvari M.
Sharghi J.
J.
Org. Chem.
2006,
71:
6652
15b Khazaei A.
Mehdipour E.
Iran Polym. J.
1999,
8:
257
15c Bao K.
Zhang W.
Bu X.
Song Z.
Zhang L.
Cheng M.
Chem.
Commun.
2008,
5428
15d Tumma H.
Nagaraju N.
Reddy KV.
J.
Mol. Catal. A: Chem.
2009,
310:
121
15e Brahmachari G.
Laskar S.
Tetrahedron Lett.
2010,
51:
2319
16 Ishida T.
Haruta M.
Chem. Commun.
2009,
538
17a Chancellor T.
Morton C.
Synthesis
1994,
1023
17b Roberts R.
Vogt P.
J. Am. Chem. Soc.
1956,
78:
4778
17c Swaringen R.
Eaddy J.
Henderson T.
J.
Org. Chem.
1980,
45:
3986
18a Grieco PA.
Organic
Synthesis in Water
Blackie Academic and Professional;
London:
1998.
18b Demko
ZP.
Sharpless KB.
J.
Org. Chem.
2001,
66:
7945
18c Li C.-J.
Chem.
Rev.
2005,
105:
3095
18d Azizi N.
Aryanasab F.
Torkiyan L.
Ziyaei A.
Saidi MR.
J.
Org. Chem.
2006,
71:
3634
18e Kaboudin B.
Sorbiun M.
Tetrahedron Lett.
2007,
48:
9015
19a Balakrishna MS.
Kaboudin B.
Tetrahedron
Lett.
2001,
42:
1127
19b Kaboudin B.
Navaee K.
Heterocycles
2001,
55:
1443
19c Kaboudin B.
Navaee K.
Heterocycles
2003,
60:
2287
19d Kaboudin B.
Saadati F.
J. Heterocycl. Chem.
2005,
42:
699
19e Kaboudin B.
Saadati F.
Heterocycles
2005,
65:
353
19f Kaboudin B.
Rahmani A.
Synthesis
2003,
2705
19g Kaboudin B.
Saadati F.
Synthesis
2004,
1249
19h Kaboudin B.
Rahmani A.
Org. Prep. Proced. Int.
2004,
36:
82
19i Kaboudin B.
Moradi K.
Tetrahedron Lett.
2005,
46:
2989
19j Kaboudin B.
Haghighat H.
Tetrahedron Lett.
2005,
46:
7955
19k Kaboudin B.
Haghighat H.
Yokomatsu T.
J.
Org. Chem.
2006,
71:
6604
19l Kaboudin B.
Karimi M.
Bioorg. Med. Chem. Lett.
2006,
16:
5324
19m Kaboudin B.
Farjadian F.
Beilstein J. Org. Chem.
2006,
2:
4
19n Yamagishi T.
Kusano T.
Kaboudin B.
Yokomatsu T.
Sakuma C.
Shibuya S.
Tetrahedron
2003,
59:
767
19o Kaboudin B.
Haruki T.
Yamaghishi T.
Yokomatsu T.
Tetrahedron
2007,
63:
8199
19p Kaboudin B.
Haruki T.
Yamagishi T.
Yokomatsu T.
Synthesis
2007,
3226
19q Kaboudin B.
Haghighat H.
Yokomatsu T.
Tetrahedron:
Asymmetry
2008,
19:
862
19r Kaboudin B.
Saadati F.
Tetrahedron Lett.
2009,
50:
1450
20 The amine (3 mmol) and triethyl orthoformate
(12 mmol) was added to H2 O (8 mL), and the solution was
stirred for 3-48 h at reflux or 2-3 h under microwave
irradiation at 90 ˚C at ambient pressure in a
microwave reactor (a Milestone, Micro SYNTH Microwave Labstation
for Synthesis, microwave reactor was used for all experiments).
After stirring for the requisite period (Table
[¹ 2 O (3 × 50
mL). The resulting mixture was subjected to column chromatography
on silica gel with EtOAc-n -hexane
(2:8) and evaporation of the solvent under reduced pressure to give
pure products in ¹5
