WALTER J. GENSLER
1966 [CONTRIBUTION FROM
THE
Vol. 69
CHEMICAL LABORATORIES OF HARVARD UNIVERSITY]
Investigation of the Compound Described as Azacyclobutadiene BY WALTERJ. GENSLER Azacyclobutadiene’ (111) would be of interest as a compound vinylogous to pyridine and also as a compound related to the four-membered Nheterocyclic system in penicillin. The present work consists in the investigation of a compound synthesized by Abderhalden and Paquin2 and assigned the structure of azacyclobutadiene. These authors reported that a dry ethereal solution of 2,3-dibromopropylamine (I), on standing Br
Br
I
P\CHZRr --+ H-C P CHz \ru”z
I
CH-Br,HBr
f H2
+
..
\N/ H I1
I
was characterized by formation of the oxalic, picric and mandelic acid salts. Treatment with bromine resulted in the regeneration of 11. Consideration of these reported reactions suggests that compound I1 was not as shown but was probably the hydrobromide of the starting material I; and that compound I11 was not azacyclobutadiene but rather allylamine. The possibility is supported by a reexamination of the published analytical data which are found to contain a consistent error in calculation ; the corrected figures agree more closely with calculated values for the revised structures than with those based on I1 and I11 (see table). The following observations have been made which further indicate the validity of .this interpretation.
TABLEI CORRECTED ANALYSES OF REPORTED COMPOUNDS COMPARED TO CALCULATED VALUESFOR VISED STRUCTURES Compound reported? I1 hydrobromide
---Calcd.2C H N B r 12.3 1 . 4 1 . 8 81.8
I1 nitrate I1 sulfate I1 formate I1 oxalate I1 picrate Bz derivative of I1 Me-I1 hydrobromide I11 oxalate I11 picrate I11 mandelate (CIOHIO~N?) CsHsBr*N hydrobromide CsHbBrtN formate
13.1 13.8 18.5 19.8 24.5 38.0 15.6 42.0 37.9 63.5 21.7 28.3
1.5 10.2 58.0 1.5 5 . 4 61.2 1.9 5 . 4 61.8 1 . 7 4 . 6 82.3 1 . 4 12.7 36.3 1 . 9 4 . 4 50.7 2.0 4.6 78.0 3.5 9.8 , . 2 . 1 21.1 .. 3.7 7.4 .. 1.8 4.2 72.3 2 . 4 4 . 7 53.9
--Found C H 12.3 2 . 7 12.4 2 . 8 13.7 3.4 14.3 3 . 3 18.5 3 . 8 20.3 3.4 25.0 2 . 4 38.5 3 . 7 18.8 3.9 41.7 6 . 5 37.8 4.1 63.3 7.4 21.8 3.7 28.2 4 . 8
for several days, evolved hydrogen gas and deposited first a crystalline solid, m. p. 164’ after purification, and then an amorphous solid. Structure I1 was suggested for the crystalline material. Complete analysis of a number of salts of 11, as well as formation of the N-methyl, benzoyl, and benzenesulfonyl derivatives, was offered in support of this formulation.3 Treatment of an ethereal solution of the free base o f I1 with sodium yielded a volatile base, C3H3S,for which the structure of azacyclobutadiene (111) was proposed. The C3H3N compound r\’a CH. I1 Zz \cH
4
Brz
-~ ( 1 ) Ring Index No. 38.
\/ I11
Alternative names: azete or pyriculine: (2) Adberhalden and Paquin, Ber., SS, 1125 (1920). (3) Neither Hollins [“Synthesis of Nitrogen Ring’Compounds,” D. Van Nostrand, New York, N . Y . , 1924, p. 231 nor Degering [“Outline of Organic Nitrogen Compounds,” John S.Swift Co., Cincinnati, Ohio. 1942, p 2861 offers a satisfactory interpretation of the rmctinn
(cor.)*N B r 4 . 8 81.5 5 . 0 81.3 10.1 57.8 5 . 5 61.5 5.4 61.8 4 . 8 51.9 1 2 . 8 36.1 4 . 9 50.1 4.7 77.4 9.3 .. 19.7 ., 6.8 .. 4.2 72.3 3 . 8 55.6
THE
REPORTED AND
THE
RE-
C a 1 c d . F C H N B r 12.1 2 . 7 4 . 7 80.5
7 -
Revised structure I hydrobromide
I I I I
nitrate sulfate formate oxalate I picrate Bz derivative of I DiMe-I hydrobromide Allylamine oxalate Allylamine picrate Allylamine mandelate I V hydrobromide I V formate
12.9 13.6 18.3 19.6 24.2 37.4 18.4 40.8 37.8 63.1 21.3 27.7
2 . 9 10.0 3.0 5.3 3.5 5.3 3.0 4.6 2 . 3 12.6 3.5 4.4 3.7 4.3 6.2 9.5 3 . 5 19.6 7.2 6.7 3.6 4.2 4.3 4.6
57.1 60.1 60.8 52.1 35.8 49.8 73.6
.. ..
..
71. 52.O
8
In a repetition of the reported procedure, i t has been found possible to isolate a solid from the first-formed crystalline precipitate (from ethereal 2,3-dibromopropylamine) which is identical with 2,3-dibromopropylamine hydrobromide and which agrees in melting point with that reported for 11. No gas evolution is observed during the formation of the precipitate. The compound, in. p. 198’ dec., which was previously formed in the reaction of TI and dry acetone may be obtained from 2,3-dibromopropylamine hydrobromide and acetone. The reported instability and ease of hydrolysis to the starting material may now be explained on the basis of the Schiff base structure IV CH2-CH-C!H2--hT=C(
I
Br
1
CH&HBr
Br IV
The oxalate and the picrate of allylamine have been prepared; the melting points, 128-130.5 and 141-141.5°, respectively, agree with those re-
INVESTIGATION OF TEE COMPOUND DESCRIBED AS AZACYCLOBUTADIENE
Aug., 1947
1967
Fig. I.--S-Ray diffraction patterns: no. 4993, 2.3-rlibromopropylamine hydrobromide: no. 4994. material from ether solution of 2.3-dibroinopropyl;imi.e. Thc Debye-Schemer clkrgrams wwc taken isiw r:ulixlim from R copprr target i d nickel filter. The exposure was one and one-half hours at 20 milliarno.
ported for the corresponding saltsof 111 (m. p. 127 and 1419. Additional supporting evidence is found in the literature. The benzoyl derivative of 2,3-dibromopropylamine has been reported to melt a t 135'l; the value for the melting point of the benzoyl derivative of I1 was given as 130'. The hydrobromide of the monomethyl derivative of 11, reported m. p. 1SS' dec. was probably dimethyl?,:
