May 5 , 1960 [JOINT
2341
ADDITIONREACTIONS OF eXO-TRIMETHYLENE-2-NORBORNENE
CONTRIBUTION FROM OF
THE NAVAL ORDNANCE LABORATORY, THEDEPARTMENT OF CHEMISTRY OF DELAWARE, AXD THE FRICK CHEMICAL LABORATORY OF PRINCETON UNIVERSITY]
THE
UNIVERSITY
Addition Reactions of exo-Trimethylene-2-norbornene BY L. K A P L A NH, .~KWART'~ ~ AND P. VON R. SCHLEYER~~ RECEIVED JULY 8, 1959 The reactions of exo-trimethylene-2-norbornene (VI) with a variety of addition reagents have been studied. By bromination in carbon tetrachloride solution, the 2,3-trans addition product has been identified as predominant. When this reaction is conducted in a pyridine medium small amounts of a 2,7-rearranged dibromide and a nortricyclenic monobromide have been isolated and characterized alongside the 2,3-trans product. Hydroxylation by means of performic acid yields entirely a 2,7-rearranged diol structure. These are the first cases in the dicyclopentadiene series of exo to endo rearrangement of the substituent five-membered ring. The equilibrium between onium ion X X I and bridged ion XXII is postulated as a dominant factor in determining the structures of products of addition reactions of bicyclic olefins. This equilibrium in turn can be influenced by many factors including substituents on the bicyclic ring and the nature of the addition reagent.
A number of polar reagents, XY, have been added to norbornene (I) heterolytically, under a variety of experimental conditions. In those cases where neither fragment X nor Y is hydrogen, it has been possible to determine the structural and stereochemical disposition of both the groups in the product.2 These reactions can be generalized in the following manner. If the attack of the electrophilic species X + was followed by ejection of a proton, the nortricyclene derivative I1 formed as well as the protonic acid HY. In a competing side reaction, the latter could add to I in the usual manner to give a norbornyl derivative 111. If, however, the attack of X + was followed by reaction with Y-, either unrearranged product IV or rearranged material V resulted. Inspection of Table I, summarizing the course of the reported additions, indicates that a full spectrum of results has been obtained. ,X
I1
I
I
t
IV Y
V
111
(1) (a) Naval Ordnance Laboratory, White Oak, hId. Present address: Convair Research Labs., S a n Diego, Calif. (b) Department of Chemistry, University of Delaware, h-ewark, Del. Paper VI11 of a series o n Addition Reactions in Bicyclic a n d Alicyclic Systems; paper V I I , see reference 2j. (c) Department of Chemistry, Princeton University, Princeton, N. J. Paper I1 of a series on Bridged R i n g Systems. Paper I , P . von R . Schleyer, THIS JOURNAL,60, 1700 (1958). ( 2 ) (a) J. D . Roberts, E . R . T r u m b u l l , R'. Bennett and R . Arm(b) H. K w a r t and L. Kaplan. strong, i b i d . , 72, 3116 (1950); ibid., 76, 4072 (1954); (c) L. K a p l a n , Thesis, University of Delaware, of J. L. Nyce, Thesis, University of 1955, and unpublished results Delaware, 1959; (d) H . K w a r t and R . K . Miller, THISJOURNAL, 7 8 , 5678 (1956); (e) S. J . Cristol and G. D. Erindell, Abstracts, Am. Chem. Soc. Mtg., Cincinnati, Ohio, April, 1955, p. 3 5 - N ; S. J. Cristol, R . P. Arganbright, G. D . Brindell a n d R . 31. Heitz, THISJ O U R N A L , 7 9 , 6035 (1957); ( f ) J. D . Roberts, F. 0. Johnson and R. A. Carboni, ibid., 7 6 , 5692 (1954); (g) H . K w a r t a n d W. G. Vosburgh, i b i d . , 76, 5400 (1954); (h) H . M. Walborsky and D . F. Loncrini, i b i d . , 76, 5396 (1954); (i) L. Schmerling, U. S. P a t e n t 2,500,385, March 14. 1950 (C. A . , 44, 5391 (1950); ( j ) H . K w a r t , R . K. Miller and J . I,. Nyce, THISJOURNAL, 80, 887 (1958); (k) H. Krieger, Sziomen Kernistilehti, B31, 340 (19.58); f l ) G . F. Wright, et a t . , C a n . J. Chem., 37, 1328 (195!4J; [In)R. I*. R < i w l a n d THISj O L ' R X A I , , 73, 2881 ( 1 9 5 1 ) .
TABLE I
SUMMARY OF THE COURSE OF ADDITION REACTIONS OF SORBORNENE Reagent x- Y AcOHg-OAc ArS-Clb ArS-Clc ArSCld ArS-Bre ArS-Cle Br-Br Br-Br
CI-C1 CI-OH HO-OOCH
Solvent HOAC CClr or pyridine CzH4Brz CzH4Brz C?HdCIz CzHrBre CClr CClr 1 mole pyridine Pentane (Hz0) HCOOH
+
Temp., OC. Room
20
Product compositions, a I1 IV 100
. ..
21,m
...
100 100 100 93 87 15
...
2d,e 2j 2j 2d 2d 2a,b,c
16
57 39-46 63 100
..
25
...
50
V. small
15-20 50 -1
13' 35g
0 -70 10-20
27 54-61 37
40-45
7
. ..
.. .. ..
R V
... ... ... ... 26
Ref
2a,b,c 2f,i
2f 2g,h,k
a ilpproximate; based upon the reported relative amounts of products actually isolated. * p-Toluenesulfenyl-Ar. 2-iXitrobenzenesulfeny1-Ar. 4-Nitrobenzenesulfenyl-Ar. e 2,4-Dinitrobenzenesulfenyl-Ar. f The presence of moisture or the use of acetic acid as the solvent increased the amount of this material. 0 The product contained 2474 of 111.
In addition to variations in the nature of the reactant and in the experimental conditions, we would expect that structural modification of the olefin should influence the course of these addition reactions. \Vith the exception of certain carboxylic acid derivatives of norbornene3 and certain structural analogs, such possibilities have not been thoroughly examined.3f We should like to report the effect that a substituent on the carbocyclic ring has upon the course of some of these addition reactions. The compound (3) (a) H . K w a r t a n d L. Kaplan, ibid., 76, 3356 (1953); (b) 76, 4078 (1954); (c) J . A. Berson and R . Swidler, ibid., 7 6 , 4060 (1954); (d) J. A. Berson, i b i d . , 76, 4069 (1954); (e) 76, 5748 (1954). Furthermore, t h e halogenation of norbornene carboxylate anions in basic solution gave rise t o lactones and other products. Earlier work has been summarized, E . Josephy and F. R a d t , Eds., "Elsevier's Encyclopaedia of Organic Chemistry," Vol. 12A, Elsevier Publ. Co., I n c . , New York, h-,Y., 1948. For more recent examples, see t h e following references: C. D. Ver Nooy and C. S. Rondestvedt, THIS J O U R N A L , 77, 3583, 4878 (1955); E. T . hlcBee, C. G. Hsu and C . W. Roberts, i b i d . , 7 8 , 3389 (1956); M. Mousseron, F . Winternitz and G. Rouzier, Compl. rend., 236, 1661 (1954); B u l l . soc. chirn. France, 170 (1955); J. S. Meek and W. B. T r a p p , THISJ O U R N A L , 7 9 , 3900 (1957); P. Wilder, Jr., and C. F . Culberson, ibid., 81, 2027 (1959); ( f ) M. Gates and S. P. Malchick, i b i d . , 76, 1378 (19541, have studied t h e reaction between performic acid a n d dicyclopentadiene. T h e product, a f t e r saponification, was not characterized, b u t was assigned t h e rearranged 2,7-diol structure on t h e basis of t h e failure t o cleave with Pb(OAc)r or HIOa. A similar result has been observed b y E . L. Eliel and C. Pillar, i b i d . , 7 7 , 3600 (1965), with a compound quite analogous in structure t o dicyclopentadiene; cf. J. hleinwald and G . W. Wiley. ibid., 60, 3607 (1058).
L. KAPLAN, H. KWART AND P.vox I
