In the Laboratory
A Phthalocyanine Synthesis Group Project
for General Chemistry
Darren K. MacFarland,* Christopher M. Hardin, and Michael J. Lowe
Department of Chemistry, Illinois College, Jacksonville, IL 62650; *dmacfar@hilltop.ic.edu
Phthalocyanines provide a colorful, interesting, and
research-relevant subject for an organic experiment in the
general chemistry curriculum (1). General chemistry courses
often include a token organic chemistry experiment. While
the aspirin synthesis (2) fills this niche nicely with a familiar
compound, students are sometimes discouraged with the
odors (acetyl chloride or anhydride) and the sense that one
white powder is being turned into…another white powder.
By contrast, phthalocyanines are brightly colored, so a white
powder is converted into an intense pigment. As phthalo-
cyanines are aromatic, historically interesting, commercially
important (3), and the subject of current research in a wide
variety of fields (4), a discussion of the importance of organic
chemistry easily follows. We report a simple, reliable synthesis
that will fill the need for an organic experiment in the general
chemistry curriculum with a compound known to most
students—a pigment.
Phthalocyanines (Pc’s) are macrocycles, a large class that
includes porphyrins (5), crown ethers, and cryptands among
many others. Each of these macrocycles has found biomedical
applications (6, 7) and is interesting for both size and un-
usual properties.1 Phthalocyanines are flat and insoluble in most
solvents 2 and are used most often commercially as blue or
green (when perhalogenated) pigments and dyes (8). Students
find the 2-dimensional nature of such a large molecule in-
teresting. In addition, Pc’s pose no health risk (8).
Both crown ethers and Pc’s are synthesized using tem-
plate metals (9). In this scheme, a metal ion coordinates
to starting materials and either positions or activates them
for cyclization around the metal center (10). The template
metal then remains in the “hole” at the center of the prod-
uct Pc, coordinated to four nitrogen atoms (see general
synthesis scheme for phthalocyanines from phthalonitriles,
below).
N N
N
CN M2+
N M2+ N
4 (DMAE)
CN heat N be checked visually, as the products are deep shades of blue
N N
Because the metal ion must fit in the “hole”, the size of the
ion is quite important. One that is too large or too small
will be less effective or entirely ineffective. Pc’s form a strong
bond with metals that are good templates, making their
removal difficult.3 Without templates to guide these syntheses,
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yields are either low or zero. Our procedure demonstrates
this effect.
Phthalocyanines have been synthesized from numerous
starting materials, with a variety of solvents and under vari-
ous conditions (11). Some reports include odd additives such
as ammonium molybdate (12). Perhaps this array of synthetic
strategies has discouraged the use of phthalocyanines in
teaching settings to this point (13). We utilize a simpler, more
modern synthesis involving commercially available compounds
and solvents.
In our experiment (see scheme), phthalonitrile (1,2-di-
cyanobenzene) is taken into N,N-dimethylaminoethanol
(DMAE) and heated to reflux. No reaction occurs because
no template is present. When a template metal is added, the
reaction proceeds rapidly. We have tested this procedure with
a variety of template metals and found a number to be quite
reliable (14 ).W Use of solvents other than DMAE is less
successful. An alternative synthesis simply heats CuCl2 and
phthalonitrile in the absence of solvent. This elicits two
responses from students. First, some are intrigued by the idea
of a solventless reaction, as their experience consists princi-
pally of solution-based reactions. Second, because some of
the phthalonitrile sublimes before the reaction is complete,
they observe (discover!) sublimation firsthand.
We have found this experiment to be suitable for group
work, using small groups usually of four students. Within a
group, student A demonstrates the need for a template by
performing the reaction without a metal salt (the reaction
will be unsuccessful), students B and C perform the same
reaction as student A but use metal salts as templates (these
reactions will be successful), and student D performs the
cyclization using the solvent-free procedure. The formulation
may be crafted to use metals that are more or less successful,
depending on the instructor’s wishes (see the experimental
procedure online for more information); larger groups may
be accommodated by further diversifying the metal salts
tested, or by having different groups within a class test
different metal salts.W The group (or class) then compares
results to develop an understanding of the need for a template
and the desirable size qualities of the template. Little analysis
need be done on the products; the success of the reaction can
and the starting solutions are not highly colored. However,
UV–vis spectra may be obtained (in pyridine) if analytical
proof of reaction is desired.
Discussions of experimental design may be structured
around a number of aspects of this reaction. Parameters such
as solvent choice, the use of an excess of template (or the use
of a template at all), choice of metal salt, and temperature of
reaction may be explored. If the group approach described
above is utilized, any or all of these variables may be isolated
and tested.

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Supplemental Material
Supplemental material for this article is available in this
issue of JCE Online. It includes more detailed information on
experimental procedures and a list of successfully tested metals.
Notes
1. For example, crown ethers are used as phase-transfer catalysts.
In a classic demonstration, KMnO4 dissolves in benzene with the
help of 18-crown-6.
2. For cleanup purposes, concentrated sulfuric acid does dissolve
residual Pc’s by sulfonating the ring to give a water-soluble species;
they are also somewhat soluble in pyridine.
3. To make a metal-free Pc, a metal that activates the phthalo-
nitrile but is not a good fit must be used. To this end, lithium
alkoxides are used. Two lithium cations occupy the “hole” of the
Pc and are removed by reaction with water to leave H2Pc.
Literature Cited
1. For a broad review, see Phthalocyanines: Properties and Appli-
cations Leznoff, C. C.; Lever, A. B. P., Eds.; VCH: New York,
1989, Vol. I; 1992, Vol. II; 1993, Vol. III; 1996, Vol. IV.
2. See for example, Williamson, K. L.; Little, J. G. Microscale
Experiments for General Chemistry; Houghton Mifflin: Boston,
1997; pp 329–336.
3. Copper phthalocyanine was discovered in 1907 by von Braun:
von Braun, A.; Tcherniak, J. Chem. Ber. 1907, 40, 2709.
Copper phthalocyanine is sold as Pigment Blue 15.
4. For example, phthalocyanine complexes have been used in ca-
talysis: Sorokin, A.; Meunier, B. Eur. J. Chem. 1998, 1269–
1281, and references therein. See also biomedical references
below. For a review, see: Hanack, M.; Deger, S.; Lange, A.
Coord. Chem. Rev. 1988, 83, 115.
5. For examples of porphyrins in undergraduate laboratories see:
Falvo, R. E.; Mink, L. M.; Marsh, D. F. J. Chem. Educ. 1999,
JChemEd.chem.wisc.edu • Vol. 77 No. 11 November 2000 • Journal of Chemical Education
In the Laboratory
76, 237; Beeston, R. F.; Stitzel, S. E.; Rhea, M. A. J. Chem.
Educ. 1997, 74, 1468; Marsh, D. F.; Mink, L. M. J. Chem.
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6. For a recent review containing both cryptands and crown
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R. M. Chem. Rev. 1999, 99, 2293–2352. For cryptands only:
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7. For a recent review containing porphyrins and phthalocya-
nines, see: Ali, H.; van Lier, J. E. Chem. Rev. 1999, 99, 2379–
2450.
8. Loebbert, G. In Encyclopedia of Chemical Technology, 4th ed.;
Kroschwitz, J. I.; Howe-Grant, M., Eds.; Wiley: New York,
1996; Vol. 18, pp 1043–1058.
9. For use of sodium as a crown ether template: Maeda, H.;
Furuyoshi, S.; Nakatsuji, Y.; Okahara, M. Bull. Chem. Soc. Jpn.
1983, 56, 212–218. For phthalocyanine templates: Metz, J.;
Schneider, O.; Hanack, M. Inorg. Chem. 1984, 23, 1065–1071.
10. A discussion of the template effect can be found in Shriver,
D.; Atkins, P. W. H. Inorganic Chemistry, 3rd ed.; Freeman:
New York, 1999; pp 222–223. Sheeran, D. J.; Mertes, K. B.
J. Am. Chem. Soc. 1990, 112, 1055–1061, and references con-
tained therein.
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1065–1071. See also Ali, H.; van Lier, J. E. Chem. Rev. 1999,
99, 2379–2450.
12. Ruf, M.; Lawrence, A. M.; Noll, B. C.; Pierpont, C. G. Inorg.
Chem. 1998, 37, 1992–1999.
13. The only J. Chem. Educ. references to phthalocyanines are
Joesten, M. D.; Higgins, M. M. J. Chem. Educ. 1986, 63,
1097–1098. Moser, F. H.; Thomas, A. L. J. Chem. Educ. 1964,
41, 245–249.
14. This general procedure is derived from work of the Hanack
group. For references see: Hanack, M.; Schmid, G.;
Sommerauer, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 1422–
1424. Rager, C.; Schmid, G.; Hanack, M. Chem. Eur. J. 1999,
5, 280–288.
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