476 NOTES VOL.

32

A Simplified Synthesis Experimental Section

for msso-Tetraphenylporphinl Freshly distilled pyrrole (56 ml, 0.8 mole) and 80 ml(0.8 mole)
of reagent grade benzaldehyde are added to 3 1. of refluxing re-
ALANI). ADLER agent grade propionic acid. (Note: crystalline material is not
direct,ly obtained if acet,ic acid is used.) After refluxing for 30
min, the solut,ion is cooled to room teniperature and filtered, and
Chernislry and Biology Deparfnzents, University of Pennsylvnia, the filter cake is washed thoroughly with methanol. After a hot
Pli 1 larlelphia, Pennsylcania water wash, the resulting purple crystals are air dried, and finally
dried in vacuo to remove adsorbed acidla to yield 25 g (207, yield)
R. LOSGO,JOHNn. FINARELLI,
FREDERICK of TPP. Spectrophotometric analysis shows that only lY0 of
the TPP yield remains in the filtrate and also that the filtered
material is about 3y0 tetraphenylchloriii (TPC) by weight.
Clieinistru Depctrtmcni, Drexel Institute of Technology (Note that longer reaction times in propionic acid do not appre-
I'hi Inddp hia, Pennsylvania ciably improve the yield, but actually decrease the purity of the
products.)
JOEL ,r.iCCJUES ASSOUR,A S D LEONARD
GOJ,DMACHER, KORSAKOFF Anal. Calcd for CarH~oNa:C, 85.90; H, 4.92; N , 9.12.
Found: C, 85.16; H, 4.99; N, 9.60.
X . C . A . Laboratories, Princeton; X e w Jersey A study13 of previous chromatographic purification tech-
niq~ies~.~,l0Jlshows that the product obtained by the above pro-
cedure is easily purified by a simple batchwise technique.
Received .4ugust 4, 1966 TPP (1.0 g) and 100 g of fuller's earth (Florex) are stirred with
enough I ,l,l-trichloroet,hane to make about' 1 1. of mixture.
As a result of our mechanistic studies on porphyrin This is immediately passed through EX 0.25-in. bed of solvent-
synt,hesis,2 we have developed a modified synthesis washed fuller's earth on a 6-in. sintered-glass vacuum funnel.
The eluent is passed through a fresh bed of Florex t,hree or four
which represents : ~ nimprovement over previous litera- times. This eliminates the TPC contamination as indicated
ture methods3-" for meso-tctraphenylporphin (TPP), by the optical spectrum. Due to adsorption, there is a loss of
The yield and rate of the condensation of pyrrole and approximat,ely 80%, of the starting material in this purificat,ion
benzaldehyde to TPP have been found to depend on t,he procedure.
Another reliable purification method for the crude TPP was
acidit,y, the solvent, the temperature, the availability found to be entrainement sublimation using purified nitrogen gas
of atmospheric oxygen, and the initial concentration as the carrier. A horizontal furnace with one or two hot zones
of t,he reagents. Ilence, while the following procedure was used with the temperature of the hotter zoneadjusted to 325",
does not represent, the conditions for the highest yield, while the cooler zone was maintained at 230". During t'he sub-
it does represent the most convenient method for rapidly limation process, nitrogen gas was allowed to flow at a rate of
1 ftS/hr. against atmospheric pressure. In this method, large,
and reproducibly obt,aining a 20 f. 3% yield of crystal- single-crystal needles of TPP were obtained. Combustion anal-
line TPP of relatively high purity. I n addition, t'he ysis of the sublimed product gave good agreement with the theo-
T I T is in such a form as to facilitate further purifica- retical values, and the electronic adsorption spectrum of a solu-
t'ion. tion of this product in benzene was in excellent agreement with
that reported by other workers.10J1J4
This same procedure may also be adapted to t,he Anal. Calcd for C?rHaoh-'r: C, 83.90; 11, 4.92; N , 9.12.
ready preparatiort of several other nzeso-substituted Found: C, 86.10; H, 4.91; X , 9.12.
porphins (generally the aromatic derivatives) ; e.g., .4lternntively, the TPP can also be purified by vacuum subli-
substitution of p-chlorobenzaldehyde gives a 20% mation in a horizontal furnace using vacuum ion pumping and a
yicld of the meso-tetra-p-chlorophenylporphin. Kot all thermal gradient. The material is sublimed through a 12-in.
diffusion path (323-330" at position of initial material to 150-
condensations are successful. Although 70 different 200" a t the collection region) at a pressure which must be main-
aldehydes have all given porphyrins under these condi- tained a t less than 1 X lo-' torr. This method yields octahedral
tions, the increased solubility due t o the formation of or rhombohedral crystals, rather than needles.
the porphyrin acid salts for many of the other meso (12) A. D. Adler and J. L. Harris, Anal. Biochem., 14, 4 i 2 (1966).
derivatives prevents the use of this method as a con- (13) E. A . AIiller, M.S. Thesis, Drexel Institute of Technology, 1966.
venient procedure for the preparation of these types of (14) J. Mullins, A. D. Adler, and R . Hochstrasser. J . Chem. Phys., 48,
2548 (1965).
porphyrins. Isolation of product in these cases is not
as simple as above, but still may be achieved. As a
general rule, the a llcyl derivat'ives and those aromatic
derivatives which bear ionizable functional groups Liquid Crystals. I. Fluorinated Anils
have a greater tendency to form the porphyrin acid
salts. JOEL
GOLDMACHER
A N D LUCIANA. BARTON

(1) This research wns partially sponsored by the U. S. Army Research R.C.A . Laboratories, Princeton, X e w Jersey
Office, Grant 1 ~ ~ ~ - ~ 1 ~ 1 2 ~ ~ -and ~ \ by
~ ~ the
~ ~ Air
~ 1 Force
~ ~ - 1Arionics
0 1 ,
Lnl,orntnr>,, Rcsr:irr,li ai181 'I'ri~linology Ilivision, Air Force Systems Com-
Received September 1, 1966
m;inrl, \\'ri)(l~t-l'atle~son Air Force Iinse. Ohio, Contract No. A F 33(615)-
2658.
(2) A . D. Adler, F. R . Longo, and IT. Shergalis, J . A m . Chem. Soc., 86, The presence of mesomorphism in 2,2',6,6'-tetra-
3145 (1964). A second paper on further studies is in preparation.
(3) P. Rothemund, ibia!., 67, 2010 (1935).
fluoro - 4,4' - di(p - n - alkoxybenzy1idenamino)biphenyls
(4) R . H . Ball, G. D. I)orough, and M. Calvin, ibid., 68, 2278 (1946). has been deemed to be "extremely doubtful."' This
( 5 ) D. I3. Sharp, U. S. Patent 3,076,813 (1963); Chem. Abstr., 59, 1593 assumption was based on the fact that the corresponding
(1963).
(6) P. Rotliemund and .I . Mennotti, J . A m . Chem. Soc., 68, 267 (1941).
R. tetrachloro derivatives were not mesomorphic.
(7) 8 . Aronoff and M. Calvin, J . Org. Chem., 8, 205 (1943). We wish to report that we have prepared dianils of
(8) G. n. Dorough, J . R. >filler, and F. M. Huennekens, J . Am. Chem.
Soc., 73, 4315 (1961).
2,2',3,3',5,5',6,6'-octafluorobenzidine and have found
(9) C. D. Dorough and 17. M . Huennekens, ibid., 74, 3974 (1952). them to be liquid crystals. Specifically, dianisylidene-
(10) D. IY. Thomas and A . E. Martell, ibid., 1 8 , 1335 (1956).
(11) G. hl. Badger, R. A. Jones, and R . L. Laslett, Australian J . Chem., (1) G. \V. Gray, "Molecular Structure and the Properties of Liquid
17, 1028 (1964). Crystals," Academic Press Inc.. New York, N. Y., 1962, p 290.