NOTES
Sept. 20, 1952
4717
a FORM
8
FORM,
- XNOSTROMS.
INTERPLANAR DISTANCE Fig. 1.-X-Ray diffraction patterns of metal-free phthalocyanine.
study of the infrared spectrum4and X-ray diffraction pattern of this material revealed that this technique produces the a-form of a phthalocyanine. The average particle size appears to be of the order of a few microns as evidenced by low scattering losses a t wave lengths of 3 microns and above. Figure 1 illustrates the X-ray diffraction pattern o€ the 13form of metal-free phthalocyanine obtained as a powder, and superimposed on the same scale is that of the a-form deposited on a rock salt plate. The decrease in $he relative intensity of the diffraction line a t 12.6 A. as compared with the results of Ebert and Gottlieb5 may be attributed to partial orientation of the crystals produced by sublimation. The $-pattern agrees quite well with that calculated from the data of Robertson. X preliminary investigation of the pressure dependence of the phase change indicated that the alpha form of metal-free phthalocyanine is produced a t sublimation pressures up to 50 mm. The aform of copper phthalocyanine is produced a t pressures up to 0.1 mm.; above this pressure subliniation produces the @-form. German scientists discovered that an a- @-phase transition occurs for the metal-free and copper phthalocyanine a t temperatures above 200' .e (4) D. N. Kendall. 119th A.C.S. hIeeting, April, 1961, Abstracts Division of Phys. aRd Inorg. Chem., 2p. ( 5 ) A. A. Ehert, Jr., and H. R. Gottlieh, T H I S J O U R N A L , 74, 2806 ( I SR2).
(6) Fiat, F i n d Report 1313 Vol. I I J , U . S nept. of Critnmcrce, \Ya,*hinptoii. D.
C.,19.48, p p . 345-4:{!1,
Barrett's condensation temperature was 400°, which explains why the a-form of metal-free phthalocyanine was never produced by his procedure. CORVALLIS. ORECOS
The Dissociation of Certain Benzohydryl Ethers BY TI LI Loo RECEIVED MARCHZU, 1952
The report by Kaye' and by Harms and Nauta? of the dissociation of certain benzohydryl ethers to afford s-tetraphenylethane finds support from work performed by the present author in 1047 iii connection with other studies, first during preparation of the oxide of benzohydrylallyl ether, arid again during the reaction of 1-benzohydryl ether of 2chloro-1,%propanediol with piperidine. In the first instance, an unsuccessful attempt was made to prepare by the procedures of Brune13 and kiougault4 the oxide (111) from benzohydryl allyl ether (I),through the iodohydrin (11) (not isolated). Upon distilling in vacuo an ethereal solution containing the s u p p e d iodohydrin (XI), P small amount of s-tetraphenylethane (IV) was abtained. (1) I 4 €&.)e, ? H I 5 J U L K ~ A I 73, 74I)X 1431), I 4 k J q e 1 C . Kogon and C Parris rbid 1 4 , 406 ( l Y 5 2 ) (2) A P Harms a n d \V r S a u t a Re6 I i a v , i r i i ) 11, 4'31 14.52) f % ) 1 Ilrunel Coriipl rriid 180, 1 0 5 7 11902) I) I Iiollgdllit eo r i l l l l i m, 4 4 1 f i o n i )
m i
1-Benzohydryl Ether of 3-Chloro-1,Z-propanediol(V).iConcentrated sulfuric acid ( 2 ml.) was very carefully dropped into an equimolecular mixture of benzohydrol (18.4 g.) and cpic!ilorohydrin (9.3 g.). The mixture reacted very vigorously and soon turned dark. After six hours heating on the stwrri-bath, the solution was cooled, diluted with benzene -11 ml.), and carefully neutralized with barium carbonate g . ) . It was filtered, dried over magnesium sulfate and ctionated in 'JUCUO. The fraction boiling between 1501 W o (20 mm.1 was collected; it weighed 8 g. (27%). / -Ci{OfI- CII.L.1 1 I f \ ( - F l l r i + hydroxide solution, whereupon a light reddish, atnine-smell\ ing oil separated. This was extracted with benzene, antl IIC dried over anhydrous potassium carbonate. The benzenc ~ C ~ l 1 , ~ ~-0 C ' I-CHr--CHOHf C LI.--hCJI n -+ was distilled off leaving the free base as a residue. A color., less hydrochloride prepared from this base had an m.p. 245247" (darkening a t 238"), antl weighed 4 g. Upon mixing the piperidine hydrochloride, a depression of 45' in m.p. was observed. The product analyzed correctly for the hydrochloride of p-piperidopropylene oxide ( V I I). 21nul. Calcd. for CsH15?U'0,11C1: C , 54.i; H, 9.0; S , Most unexpectedly, 8-piperidopropylene oxide 7.9. Found: C, 53.5; H , 9 . 0 ; S , 8.1. 1
(VII) instead of the amme-ether (VI) was isolated. The fate of the rest of the molecule was not defined.
Acknowledgment.-This work was done in 1947 during the tenure of a research assistantship a t the Department of Pharmacology, University of Osford, England.
Experimental6 (7) E. Fourneau anrl I. Ribas. Bull soc. chim., 39, 1584 (lY2tij: 41, Benzohydryl Allyl Ether (I).-Diphenylchloromethane 1046 (1927! (16 g.) was carefully added to allyl alcohol (14 9.) in potassium hydroxide solution (5 g. dissolved in 15 ml. of water). T H E CHRIST I I O S P I T A L I N S T I T U T E O F h1EL)ICAL RESEARCH When the reaction had subsided, the mixture was then re138 AUBURNAVESUE fluxed on the steam-bath for five hours, cooled, diluted with 2CIYCXSNATI 19, OHIO water (100 ml.) and extracted three times with 50 ml. of ether. The ethereal extract was dried over calcium chloride and distilled under reduced pressure. The fraction distilling between 172-176" (18 mn1.1, weighed 16.5 g . (.'30.5%, The Separation of Catechol from Steam Distillates hued on allyl alcohol) and Reaction Mixtures Anal. Cakd. for C161111jO:C , 85.7; 11: 7 . 2 . 1;nuticI: C. 85.0; H , 1 . i . 13'i \\-. \\~RKSEKZOKLI.ICII hSn j.E L L I O T T \\'EHEK Attempted Preparation of the Benzohydryl Ether of 1,2R R C l i l V E I ~i\I'RII. 2 I , i R j 2 Epoxy ropanol (III).-To a solution of benzohydryl allyl ether [Il.2 g.) in ether (110 ml.) was added yellox mercuric During experiments designed to determine yields oside (6 g . ) and a little water (10 m1.1. While the rnisturit iii the conversion of o-aniinophenol to catechol, it \vas vigorously stirred, iodine (14 9.) was added in small portions. The stirring LYas continued for half an'hour after was found that the product could easily be removed the addition of all the iodine. The mixture was filtered and from the bulky stenrn distillate by precipitating as washed first with potassium iodide solution and then with a the barium salt,:! thus rendering unnecessary tedisolution of sodium hyposulfite to remove the unreacted iodine. The clear ethereal solution was next shaken vigor- ous extraction procedures. Some difficulty, howously with 50 ml. of a 20% aqueous potassium hydroxide ever, was encountered in attempts to regenerate the solution. The ethereal layer was dried over magnesium catechol in organic solvents by means of hydrogen sulfate, then distilled in vucuo. It became dark red upon heating, with the visible liberation of iodine. The distilla- chloride, but this was overcome by substituting tion was subsequently discontinued, and the solution again lead for barium. In 'contradistinction, the lead subjected to the treatment with sodium hyposulfite, v x - salt3 was readily decomposed in benzene with hytracted with ether, and the ethereal extract again shakcn drogen chloride to yield catechol and lead chloride. with concentrated potassium hydroxide. Upon redistilling the dried ethereal extract under reduced pressure, iodine Although this procedure proved quite satisfactory, was liberated as described before. When all volatile frac- the over-all yields from the reaction were found to tions, b.p. below 180' (18 mm.) (unidentified) were distilled be of a low order. off, an almost colorless crystalline residue remained, m.p. Applying further this property of catechol to 211', after recrystallizing from acetone. I t was shown to be s-tetraphenylethane by elementary analyses and also by form insoluble salts with heavy metals, a convenient and rapid method was found for the separation comparison with an authentic sample. ,5) J. Y. $. G l a u a n d C . S . iiinshel,rood,
J. Cirrin
S o c . , 1812
(I!tQOJ.
(6) .411 boiling points a n d melting points are not corrcctcii. atialynes done by Dr. G. A'eilrr of Oxford, England.
>Iiuo-
of this substance formed in the hydrogen peroxide
!,
I Soci4t6 Chimiqur d e s L'sines tils Khorie, D 1i.P. 107,?l I I l!lOli). (2) 13. Elsner, M o w n t ~ h . ,40, 361 (1919). (:3 C. Znexiwr, Aiin., 37, 332 (1841).
