Abstract
A novel single-step preparation of free-base and metalloporphyrazines from maleonitriles was accomplished for the first time by treatment with metal salts, hexamethyldisilazane (HMDS) and p -toluene sulfonic acid (PTSA) in DMF at 120 °C. This reaction provides a new preparative method under mild conditions for direct synthesis of metalloporphyrazines having a variety of metals and substituted maleonitriles.
Key words
macrocycles - porphyrazines - maleonitrile - template - hexamethyldisilazane
References and Notes
1a Suslick KS.
Rakow NA.
Kosal ME.
Chou J.
J. Porphyrins Phthalocyanines
2000,
4:
407
1b Li YJ.
Fan Y.
Zhang LG.
Jiang DP.
Lu AD.
Wang S.
Leblanc RM.
J. Porphyrins Phthalocyanines
1998,
2:
527
1c Leznoff CC.
Lever ABP.
Phthalocyanines, Properties and Applications
Vol. 3:
VCH Publishers Inc;
New York:
1993.
1d Schultz H.
Lehmann H.
Rein M.
Hanack M.
Struct. Bond. (Berlin)
1991,
74:
41
2a Drain CM.
Hupp JT.
Suslick KS.
Wasielewski MR.
Chen X.
J. Porphyrins Phthalocyanines
2002,
6:
243
2b Sauer T.
Caseri W.
Wegner G.
Vogel A.
Hoffmann B.
J. Phys. D: Appl. Phys.
1990,
23:
79
3a Rao SV.
Rao DN.
J. Porphyrins Phthalocyanines
2002,
6:
233
3b Rao SV.
Srinivas NNKM.
Rao DN.
Giribabu L.
Maiya BG.
Philip R.
Kumar GR.
Optics Commun.
2001,
192:
123
3c Rao SV.
Srinivas NNKM.
Rao DN.
Giribabu L.
Maiya BG.
Philip R.
Kumar GR.
Optics Commun.
2000,
182:
255
4 Bonnet R.
Chem. Soc. Rev.
1995,
24:
19
5a Nazeeruddin MK.
Humphry-Baker R.
Officer DL.
Campbell WM.
Burrell AK.
Gratzel M.
Langmuir
2004,
20:
6515
5b Campbell WM.
Burrell AK.
Officer DL.
Jolley KW.
Coord. Chem. Rev.
2004,
248:
1363
5c Nazeeruddin MK.
Humphry-Baker R.
Gratzel M.
Murrer BA.
Chem. Commun.
1998,
719
6 Linstead RP.
Whalley M.
J. Chem. Soc.
1952,
4839
7 Makarova EA.
Korolyova GV.
Luk’yanets EA.
Zh. Obshch. Khim.
1999,
69:
1356
8 Donzello MP.
Dini D.
D’Arcangelo G.
Ercolani C.
Zhan R.
Ou Z.
Stuzhin PA.
Kadish KM.
J. Am. Chem. Soc.
2003,
125:
14190
9a Vesper BJ.
Salaita K.
Zhong H.
Mirkin CA.
Barrett AGM.
Hoffman BM.
J. Am. Chem. Soc.
2004,
126:
16653
9b Mitzel F.
FitzGerald S.
Beeby A.
Faust R.
Eur. J. Org. Chem.
2004,
1136
9c Jaung JY.
Bull. Korean Chem. Soc.
2004,
25:
1453
9d Montalban AG.
Baum SM.
Barrett AGM.
Hoffmann BM.
J. Chem. Soc., Dalton Trans.
2003,
2093
9e Goldberg DP.
Michael SLJ.
White AJP.
Williams DJ.
Barrett AGM.
Hoffmann BM.
Inorg. Chem.
1998,
37:
2100
9f Nalwa HS.
Engel MK.
Hanack M.
Pawlowski G.
Appl. Phys. Lett.
1997,
71:
2070
9g Gantchev TG.
Ali H.
vanLier JE.
Eur. J. Biochem.
1993,
217:
371
10a Uchida H.
Tanaka H.
Yoshiyama H.
Reddy PY.
Nakamura S.
Toru T.
Synlett
2002,
1649
10b Uchida H.
Reddy PY.
Nakamura S.
Toru T.
J. Org. Chem.
2003,
68:
8736
10c Uchida H.
Yoshiyama H.
Reddy PY.
Nakamura S.
Toru T.
Bull. Chem. Soc. Jpn.
2004,
77:
1401
11 3 ) directly tetramerizes to the corresponding porphyrazine. The direct conversion was not possible in Mg-propoxide method, where the maleonitrile was first converted to the pyrrolinediimine before tetramerization. See: Gan Q.
Xiong F.
Li S.
Wang S.
Shen S.
Xu H.
Yang G.
Inorg. Chem. Commun.
2005,
8:
285
12 Bauer EM.
Ercolani C.
Galli P.
Popkova IA.
Stuzhin PA.
J. Porphyrins Phthalocyanines
1999,
3:
371
13
Representative Procedure.
2 (220 mg, 1 mmol), PTSA (38 mg, 0.2 mmol) and DMF (1 mL) were taken in a sealed tube. The reaction mixture was heated at 120 °C for 24 h under Ar atmosphere. The reaction mixture was then evaporated to dryness under reduced pressure. The resultant solid material was subjected to neutral alumina column and eluted with hexane-EtOAc (9:1). The front running blue color band was collected and evaporated to dryness under reduced pressure to get Zn-porphyrazine 2b (160 mg) in 43%. Anal. Calcd: C, 53.22; H, 6.70; N, 31.03. Found: C, 53.70; H, 6.65; N, 31.30. UV/Vis (CH2 Cl2 ): λmax (log e) = 630 (4.27), 545 (sh), 330 (4.72) nm. 1 H NMR (CDCl3 ): δ = 3.70 (s) ppm. 13 C NMR (CDCl3 ): δ = 43.8, 137.7, 150.7 ppm. MS (MALDI-TOF): m/z = 722. All the compounds obtained are known and in agreement with the reported spectral and analytical data.
