Abstract
Treatment of N-substituted formamides with chlorophosphate compounds
such as PhOPOCl2 , EtOPOCl2 , Me2 NPOCl2 , and
(PhO)2 POCl and tertiary amines such as triethylamine,
pyridine, and N ,N -diisopropylethylamine
produced the corresponding isocyanides in high yields. This method
can be used to prepare various alkyl and aryl isocyanides.
Key words
isocyanide - isonitrile - formamide - dehydration - dichlorophosphate - monochlorophosphate
References
<A NAME="RF54011SS-1">1 </A>
Passerini M.
Gazz.
Chim. Ital.
1921,
51:
126
<A NAME="RF54011SS-2">2 </A>
Ugi I.
Betz W.
Fetzer U.
Offerman K.
Chem. Ber.
1961,
94:
2814
<A NAME="RF54011SS-3A">3a </A>
Ugi I.
Isonitrile
Chemistry
Academic Press;
New York (NY):
1971.
<A NAME="RF54011SS-3B">3b </A>
Dömling A.
Ugi I.
Angew. Chem.
Int. Ed.
2000,
39:
3168
<A NAME="RF54011SS-3C">3c </A>
Ugi I.
Dömling A.
Combinatorial Chemistry
Fenniri H.
Oxford University
Press;
Oxford:
2000.
p.287
<A NAME="RF54011SS-3D">3d </A>
Dömling A.
Curr. Opin. Chem. Biol.
2000,
4:
318
<A NAME="RF54011SS-3E">3e </A>
Ugi I.
Werner B.
Dömling A.
Targets Heterocycl.
Syst.
2000,
1
<A NAME="RF54011SS-4A">4a </A>
Fusetani N.
Nat. Prod. Rep.
2004,
21:
94
<A NAME="RF54011SS-4B">4b </A>
Garson MJ.
Simpson JS.
Nat.
Prod. Rep.
2004,
21:
164
<A NAME="RF54011SS-5A">5a </A>
Kitano Y.
Ito T.
Suzuki T.
Nogata Y.
Shinshima K.
Yoshimura E.
Chiba K.
Tada M.
Sakaguchi I.
J. Chem. Soc., Perkin Trans. 1
2002,
2251
<A NAME="RF54011SS-5B">5b </A>
Kitano Y.
Yokoyama A.
Nogata Y.
Shinshima K.
Yoshimura E.
Chiba K.
Tada M.
Sakaguchi I.
Biofouling
2003,
19:
187
<A NAME="RF54011SS-5C">5c </A>
Nogata Y.
Kitano Y.
Yoshimura E.
Shinshima K.
Sakaguchi I.
Biofouling
2004,
20:
87
<A NAME="RF54011SS-5D">5d </A>
Kitano Y.
Nogata Y.
Shinshima K.
Yoshimura E.
Chiba K.
Tada M.
Sakaguchi I.
Biofouling
2004,
20:
93
<A NAME="RF54011SS-5E">5e </A>
Kitano Y.
Akima C.
Yoshimura E.
Nogata Y.
Biofouling
2011,
27:
201
<A NAME="RF54011SS-6A">6a </A>
Baldwin JE.
O’Neil IA.
Synlett
1990,
603
<A NAME="RF54011SS-6B">6b </A>
Launay D.
Booth S.
Clemens I.
Merritt A.
Bradley M.
Tetrahedron
Lett.
2002,
43:
7201
<A NAME="RF54011SS-6C">6c </A>
Porcheddu A.
Giacomelli G.
Salaris M.
J.
Org. Chem.
2005,
70:
4218
<A NAME="RF54011SS-6D">6d </A>
Kim S.
Yi KY.
Tetrahedron Lett.
1986,
27:
1925
<A NAME="RF54011SS-6E">6e </A>
Creedon SM.
Crowley HK.
McCarthy DG.
J. Chem. Soc., Perkin Trans.
1
1998,
1015
<A NAME="RF54011SS-6F">6f </A>
Bose DS.
Goud PR.
Tetrahedron
Lett.
1999,
40:
747
<A NAME="RF54011SS-7">7 </A>
Chemicals whose acute toxicity by the
oral absorption is 50 mg/kg or less are defined as specific
controlled poisonous substances under the Poisonous and Deleterious
Substances Control Law by National Institute of Health Sciences
in Japan. Acute toxicities of POCl3 , EtOPOCl2 ,
and PhOPOCl2 are the following according to MSDS of Tokyo
Chemical Industry Co., Ltd. and Wako Pure Chemical Industries, Ltd.; POCl3 36
mg/kg (orl-rat), EtOPOCl2 220 mg/kg
(orl-rat), PhOPOCl2 850 mg/kg (orl-mam).
<A NAME="RF54011SS-8">8 </A>
Kuo C.-W.
Zhu J.-L.
Wu J.-D.
Chu C.-M.
Yao C.-F.
Shia K.-S.
Chem. Commun.
2007,
301
<A NAME="RF54011SS-9">9 </A>
Claremon DA.
Phillips BT.
Tetrahedron Lett.
1988,
29:
2155
<A NAME="RF54011SS-10">10 </A>
Minozzi M.
Nanni D.
Walton JC.
Org.
Lett.
2003,
5:
901
<A NAME="RF54011SS-11">11 </A>
Kitano Y.
Chiba K.
Tada M.
Synthesis
2001,
437
<A NAME="RF54011SS-12">12 </A>
Kitano Y.
Nogata Y.
Matsumura K.
Yoshimura E.
Chiba K.
Tada M.
Sakaguchi I.
Tetrahedron
2005,
61:
9969
<A NAME="RF54011SS-13">13 </A>
Cai L.
Han Y.
Ren S.
Huang L.
Tetrahedron
2000,
56:
8253
<A NAME="RF54011SS-14">14 </A>
Kobayashi K.
Nakashima T.
Mano M.
Morikawa O.
Konishi H.
Chem.
Lett.
2001,
40:
602
<A NAME="RF54011SS-15">15 </A>
Guirado A.
Zapata A.
Gómez JL.
Trabalón L.
Gálvez J.
Tetrahedron
1999,
55:
9631
<A NAME="RF54011SS-16">16 </A>
Porcheddu A.
Giacomelli G.
Salaris M.
J.
Org. Chem.
2005,
70:
2361
<A NAME="RF54011SS-17">17 </A>
Maya F.
Tour JM.
Tetrahedron
2004,
60:
81
<A NAME="RF54011SS-18">18 </A>
Hosseini-Sarvari M.
Sharghi H.
J. Org. Chem.
2006,
71:
6652