DAVTJ) TARRR, NORMAN PICUS, E. I. BECKER ANI) P. E.
1010
[CONTRIBUTION FROM THE CHEMICAL
LABORATORIES O F THE
Vol. 77
SPORRRI
POLYTECHNIC INSTITUTE O F BROOKLYN]
Syntheses for 6-Substituted-1,2,3,4-tetraphenylfulvenes1 BY DAVID TABER,~ NORMAN PICUSJ3 ERNEST I. BECKER4 AND PAUL E. RECEIVED AUGUST27, 1954
SPOERRI
p-Nitro- and p-chlorobenzaldehydes, cinnamaldehyde p-dimethylaminocinnamaldehyde, 1-naphthaldehyde, furfural, quinoline-2-, quinoline-4- and quinoline-6-aldehydes, and benzothiazole-%aldehyde have been condensed with 1,2,3,4tetraphenylcyclopentadiene to give the corresponding 6-substituted fulvenes. 2-Methylmercapto-3-ethylbenzothiazolinium, 3-ethyl-2-(0-acetanilidovinyl) -benzoxazolium, -benzothiazolium and -benzoselenazolium and l-ethyl-2-(P-acetanilidovinyl) quinolinium iodides have been condensed with the same hydrocarbon to give the corresponding 6,6-disubstituted fulvenes.
In connection with studies of the ultraviolet spectra of cross-conjugated systems and the relationship of structure to photoconductive behavior of organic compounds, it was pf interest to prepare a series of &substituted fulvenes A and B, where Ar is an aryl ring and 2 is a heterocyclic systetn. The
/-\/
/%/
\
\
A
been prepared by the base-catalyzed condensation of tetraphenylcyclopentadiene (I) with aldehydes (equation 1); compounds of type B have been synthesized by the alkoxide-catalyzed condensation of I with quaternized heterocyclic compounds containing a potential aldehyde group (equation 2 ) .
n
general preparative methods have been reviewcd.j In this investigation compounds of type A h a w /
R B (XVII to XXI) \
The base-catalyzed condensation of I with aro-
A
TABLE I ~-ARYI,-SUBSTITUTBD FULVEXES
Quarit
Ar-
Cmpd. no.
I1 111 11.
1’ \‘I VI1 \’I11
IX
g
CeHj2.0 p CH30CeH4- 0 5 p-(CH3)2XCaH,- 2 . 0 p-NO2CeH41 0 p-ClCsH41 5 CeHbCH=CI-I1.O /)-(CHJ)~XCI II,CH=CHO 0.70 I-Naphthyl1 , 1,5
Reflux time, hoursb
li p , ‘C ,
Solv for recryqtn.
dec.
4.0 2 . 0 Petrcleum etherd 3 . 0 Petroleum etherd ? 0 Ilenz.-pet. eth.’ 2 . 0 Petroleum ethrrd 2 0 hlethaX1Ol
203-204c 199-199.5e 253-255’ 227-228 176-177 1!>3.-191
4 , 0 Benz.-pet. eth.d 1 0 Acetic acid
229-241 209-2 11
Yield,
c/o
73 88 71 3a
50 27 IO 49
Cnrbon, 76 Calcd. Found
90.98 8 . i . 87.69 94.18
Hydrogen, % Nitrogen, ?4 Calcd Found Calcd. F o u n d
90.94 6 . 2 3 5.00 87.48 5.11 94.43 L 8 2
~80.33
91 n 6 90.72 G 70 9 4 . 4 5 94.41 5.65
6.31 2.79 2 . 7 6 S,OO 2.7s 2.88 5.21 5.98 8 T,G 2 . 6 5 2 . w 5.51
4 One gram of the diene was taken. It] methanol. Footnote 6 reported m.p. 200-201O. B.p. 90-100°. FootFootnote 6 reported 213-210°. 0 This aldehyde was prepared according to the procedure of note 0 reported 197-198”. footnote 7, modifying that of footnote 8. __ __ __
’
~
(1) T h i s work was supported by t h e Photographic Branch of t h e Signal Corps Engineering Laboratories of t h e U . S . Army, C o n t r a c t W’RO 039 SC44483, Signal Corlis Project So.39-195B, Dept. of t h e Army project N o , 3-99.04-052 and C o n t r a c t D A 36-1339 SC-15826, SigllaI Corps Project N O . 30-1958-0(080401.1), D e p t . of t h e A r m y ~ r o j e c tNO. 3-99-0-i-052. I t was reported in p a r t in t h e Division of Organic Chemistry a t t h e 118th bfeeting of t h e American Chemical Soriety, Chicago, I l l . , September, 1950, Abstracts, p. 71 N. ( 2 ) T a k e n from a portion of t h e Dissertation presented t o t h e C r a d u a t e Facultv of t h e Polytechnic I n s t i t u t e of Brooklyn in partial f u l f i l l rnent of t h e degree of Doctor of Philosophy, 1‘153 ( 3 ) Deceased. J a n u a r y 7 , 1950 (1) T o whom inquiries should be sent. ( 5 ) J H . D a y , Chem. R e v s , 63, 167 (1953).
matic aldehydes has been described by Dilthey and Huchternann.6 With a more extended series of than those used previously, no particular difficulty was encountered. Table 1 summarizes the results. In an entirely similar fashion a number of heterocyclic aldehydes were found to give the (see ‘I)’ and (6) W. Diltliey a n d P. N u c h t e m a n n , J . p r a k l . Chem., 154, 238 (1940). (7) S. Gister, M.S. Thesis, Polytechnic I n s t i t u t e of Brooklyn,
1950. ( 8 ) W Kbuig, W. Sclirarnrk a n d C.. Rosch, B c r . . 61, 2074 (19%).
Feb. 20, 1955
SYNTHESIS FOR 6-SUBSTITUTED-1,2,3,4-TETRAPHENYLFULVENES
1011
TABLE I1 6-HETEROCYCLE-SUBSTITUTED
FULVENES
/
3- RCHO A NaOCH3 &>=CHR \A
)
