Download PDF
Synlett 2002(10): 1649-1652
DOI: 10.1055/s-2002-34237
LETTER
© Georg Thieme Verlag Stuttgart · New York

Novel Synthesis of Phthalocyanines from Phthalonitriles under Mild Conditions

Hitoshi Uchida, Hirokazu Tanaka, Hideyuki Yoshiyama, Paidi Yella Reddy, Shuichi Nakamura, Takeshi Toru*
Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
Fax: +81(52)7355217; e-Mail: toru@ach.nitech.ac.jp;
Further Information

Publication History

Received 26 July 2002
Publication Date:
23 September 2002 (online)

    Permissions and Reprints All articles of this category

Abstract

A convenient preparation of phthalocyanines from phthalonitriles was accomplished by treatment with metal salts and hexamethyldisilazane (HMDS) in DMF at 100 °C. This reaction provides a new preparative method under mild conditions for phthalocyanines having a variety of metals and substituted phthalocyanines as well as Zn-naphthalocyanine.

Key words

phthalocyanine - naphthalocyanine - phthalonitrile - hexamethyldisilazane - dye

    References

  • 2a Moser FH. In The Phthalocyanines: Properties   Vol. I:  Thomas AL. CRC Press; Boston: 1983. 
    Google Scholar
  • 2b Moser FH. In The Phthalocyanines: Properties   Vol. II:  Thomas AL. CRC Press; Boston: 1983. 
    Google Scholar
  • 2c Leznoff CC. In Phthalocyanines: Properties and Applications   Vol. 1:  Leznoff CC. Lever ABP. VCH; New York: 1989.  Chap. 1.
    Google Scholar
  • 2d Thomas AL. In The Phthalocyanines: Applications   CRC Press; Boston: 1990. 
    Google Scholar
  • 2e McKeown NB. In Phthalocyanine Materials: Synthesis, Structure and Function   Cambridge University Press; Cambridge: 1998. 
    Google Scholar
  • 2f Hanack M. Heckmann H. Polley R. In Methods of Organic Chemistry   Vol. E9d:  Schaumann E. Thieme; Stuttgart: 1998.  p.717 
    Google Scholar
  • 3 Arishima K. Hiratsuka H. Tate A. Okada T. Appl. Phys. Lett.  1982,  40:  279 
    CrossrefGoogle Scholar
  • 4a Wagner JR. Ali H. Langlois E. Brasseuseur N. van Lier JE. Photochem. Photobiol.  1987,  45:  587 
    Google Scholar
  • 4b Brasseur N. Langlois E. Ali H. van Lier JE. Photochem. Photobiol.  1987,  46:  739 
    Google Scholar
  • 4c Paquette B. Ali H. Langlois R. van Lier JE. Photochem. Photobiol.  1988,  47:  215 
    Google Scholar
  • 4d Brasseur N. Ali H. Langlois E. van Lier JE. Photochem. Photobiol.  1988,  47:  705 
    Google Scholar
  • 4e Ali H. Langlois E. Wagner JR. Brasseur N. Paquette B. van Lier JE. Photochem. Photobiol.  1988,  47:  713 
    Google Scholar
  • 5 Bott B. Jones TA. Sens. Actuators  1984,  5:  43 
    Google Scholar
  • 6 Jones TA. Bott B. Sens. Actuators  1986,  9:  27 
    Google Scholar
  • 7 Sauer T. Caseri W. Wegner G. Vogel A. Hoffmann B. J. Phys. D: Appl. Phys.  1990,  23:  79 
    CrossrefGoogle Scholar
  • 8a Wyler M. inventors; US. Pat. Appl.  2197458.  ; Chem. Abstr. 1941, 34, 37564
  • 8b Wyler M. inventors; US. Pat. Appl.  2197459.  ; Chem. Abstr. 1941, 34, 37564
  • 9a Tomoda H. Saito S. Ogawa S. Shiraishi S. Chem. Lett.  1980,  1277 
    CrossrefGoogle Scholar
  • 9b Tomoda H. Saito S. Shiraishi S. Chem. Lett.  1983,  313 
    CrossrefGoogle Scholar
  • 9c Edmondson SJ. Hill JS. Mitchell PCH. J. Chem. Soc., Dalton Trans.  1990,  1115 
    CrossrefGoogle Scholar
  • 9d Wöhrle D. Schnurpfeil G. Knothe G. Dyes Pigm.  1992,  18:  91 
    CrossrefGoogle Scholar
  • 9e Linssen TG. Dürr K. Hanack M. Hirsch A. J. Chem. Soc., Chem. Commun.  1995,  103 
    CrossrefGoogle Scholar
  • For example:
  • 10a Wöhrle D. Eskes M. Shigehara K. Yamada A. Synthesis  1993,  194 
    Google Scholar
  • 10b Leznoff CC. McArthur CR. Qin Y. Can. J. Chem.  1993,  71:  1319 
    Google Scholar
  • 10c Leznoff CC. Hu M. McArthur CR. Qin Y. van Lier JE. Can. J. Chem.  1994,  72:  1990 
    Google Scholar
  • 10d Gürek AG. Bekaroglu . Helv. Chim. Acta.  1994,  77:  1616 
    Google Scholar
  • 10e Witke GE. Feucht C. Dreßen M. Pohmer J. Hanack M. Chem. Ber.  1995,  128:  589 
    Google Scholar
  • 10f Hanack M. Knecht S. Polly R. Chem. Ber.  1995,  128:  929 
    Google Scholar
  • For example:
  • 11a Barrett PA. Frye DA. Linstead RP. J. Chem. Soc.  1938,  1157 
    CrossrefGoogle Scholar
  • 11b Oksengendler IG. Kondratenko NV. Luk’yanets EA. J. Org. Chem. USSR (Engl. Transl.)  1978,  14:  976 ; Zh. Obshch. Khim. 1978, 14, 1046
    CrossrefGoogle Scholar
  • 11c Wöhrle D. Meyer G. Wahl B. Makromol. Chem.  1980,  181:  2127 
    CrossrefGoogle Scholar
  • 11d Oliver SW. Smith TD. J. Chem. Soc., Perkin Trans. 2  1987,  1579 
    CrossrefGoogle Scholar
  • 11e Cook MJ. Dunn AJ. Howe SD. Thomson AJ. Harrison KJ. J. Chem. Soc., Perkin Trans. 1  1988,  2453 
    CrossrefGoogle Scholar
  • 11f McKeown NB. Chambrier I. Cook MJ. J. Chem. Soc., Perkin Trans. 1  1990,  1169 
    CrossrefGoogle Scholar
  • 11g Chambrier I. Cook MJ. Cracknell SJ. McMurdo J. J. Mater. Chem.  1993,  3:  841 
    CrossrefGoogle Scholar
  • 11h Iwase A. Harnoode C. Kameda Y. J. Alloys Compd.  1993,  192:  280 
    CrossrefGoogle Scholar
  • 11i Guyon F. Pondaven A. Guenot P. L’Her M. Inorg. Chem.  1994,  33:  4787 
    CrossrefGoogle Scholar
  • 11j Cook MJ. Hersans R. McMurdo J. Russell DA. J. Mater. Chem.  1996,  6:  149 
    CrossrefGoogle Scholar
  • 11k Lenzoff CC. Hu M. Nolan JM. Chem. Commun.  1996,  1245 
    CrossrefGoogle Scholar
  • 11l Terekhov DS. Nolan KLM. McAuthur CR. Leznoff CC. J. Org. Chem.  1996,  61:  3034 
    CrossrefGoogle Scholar
  • 11m Kobayashi N. Higashi R. Ishii K. Hatsusaka K. Ohta K. Bull. Chem. Soc. Jpn.  1999,  72:  1263 
    CrossrefGoogle Scholar
  • 11n Lenzoff CC. D’ascanio AM. Yildiz SZ. J. Porphyrins Phthalocyanines  2000,  4:  103 
    CrossrefGoogle Scholar
  • 12a Derkacheva VM. Luk’yanets EA. J. Gen. Chem. USSR (Engl. Transl.)  1980,  50:  986 ; Zh. Obshch. Khim. 1980, 50, 2313
    CrossrefGoogle Scholar
  • 12b Kitahara K. Asano T. Tokita S. Nishi H. J. Heterocycl. Chem.  1990,  27:  2219 
    CrossrefGoogle Scholar
  • 12c Nemykin VN. Kobayashi N. Mytsyk VM. Volkov SV. Chem. Lett.  2000,  546 
    CrossrefGoogle Scholar
  • 13a Hauxwell F, and Murton HR. inventors; Pat. GB  1374793.  ; Chem. Abstr. 1972, 78, 73660
  • 13b Piechocki C. Simon J. New J. Chem.  1985,  9:  159 
    Google Scholar
  • 13c Ford WT. Sumner L. Zhu W. Chang YH. Um P.-J. Choi KH. Heiney PA. Maliszewskyj NC. New J. Chem.  1994,  18:  495 
    Google Scholar
  • 14 Yao J. Yonehara H. Pac C. Bull. Chem. Soc. Jpn.  1995,  68:  1001 
    CrossrefGoogle Scholar
1

AISIN COSMOS R&D Co., Ltd.

15

Representative Procedure: A mixture of phthalonitrile (107 mg, 0.84 mmol), HMDS (0.35 mL, 1.66 mmol), ZnBr2 (50 mg, 0.22 mmol), and DMF (0.21 mL) was heated at 100 °C under Ar atmosphere. The mixture was separated into two phases. After heating for 10 h, the reaction mixture was subjected to evaporation under reduced pressure. The resultant solid was washed successively with MeOH (50 mL) and with water (50 mL). The obtained crude product was further purified by extraction with chloroform (50 mL) using Soxhlet’s extractor, and dried under reduced pressure, affording Zn-phthalocyanine 7a (91 mg) in 78% yield. Anal. Found: C, 66.21; H, 2.88; N, 19.59. Calcd: C, 66.50; H, 2.79; N, 19.39. IR (KBr):1608, 1486, 1456, 1412, 1331, 1285, 1167, 1118, 1090, 1061, 887, 778, 752, 727 cm-1. TOF MS (MALDI): 576.2 (M+). All the compounds obtained are known and in agreement with the spectral and analytical data.