463 1,4-Dianions of Phenylhydrazones Having an a-Hydrogen’ Sir: Acetophenone phenylhydrazone has recently been converted to the monoanion I’ by 1 equiv of potassium amide in liquid ammonia, as evidenced by N-benzylation with benzyl chloride to form II.2 CH3
CHs CHzCas
casL --“cas ‘
CeH5LNfiCaa I’
I1
This phenylhydrazone has now been converted to the dianion I” by 2 equiv of the alkali amide in liquid ammonia, as evidenced by preferential C-benzylation with 1 equiv of benzyl chloride to afford 111, which was independently synthesized from benzylacetophenone and phenylhydrazine. -
CHz
CsH5CHzCHz
C&bC“NC& I -
I11
Similarly, phenylacetaldehyde phenylhydrazone was N-benzylated through its monoanion and C-benzylated through its dianion IV” to form V and VI, respectively. Also, dianion IV” underwent dibenzylation with 2 equiv of benzyl chloride to give VII.
CJ-I~CHCH=NNC~H~
Fred E. Henoch, K. Gerald Hampton, Charles R. Hauser Department of Chemistry, Duke University Durham, North Carolina 27706 Received December 5 , 1966
Relative Contributions of Hyperconjugation and Nonbonded Interactions to Secondary Isotope Effects Sir : Solvolytic rate constants and isotope effects for compounds 1-111’ are summarized in Table I. The
x
Ca&=N-CsHa
I”
apparent exclusion of N-condensations. However, Cand N-condensations might be realized to form cyclic products with appropriate electrophilic compounds. Work is in progress on condensations of dianions I” and IV” with other electrophilic compounds and on similar studies with various other phenylhydrazones including osazones and related compounds.
8
COCl
&
Ia, X = CHs b, X = CD3
c,X=H d,X = D
IIa, X = CH3 b, X = CD3 b’, (-CDKI, X = CHs)
c,X = H d,X = D d’, (-CDICl), X = H
CeH5CHz C&I5CHzCH=NI!ICeHs
IV“
V
“”T
CeH5CHz
I
CHzCeHs IIIa, X = CH3
C~H~CHCH=NNHC~HSCsH5 HCH=NIk& VI1 VI
Likewise, dianion IV” underwent an addition reaction with benzophenone and benzoylation, accompanied by cyclization with methyl benzoate, to afford VI11 and IX, respectively. )&OH I C~H~CHCH=”HC~HS
c 6 C6HS
H
5
N*N
~
~
I c$I,
W I
Ix
x).
The yields of all of these products were good (50-76 The structures of the new compounds 111, V, VI, VII, and VI11 were supported by analyses and infrared and nmr spectra. Cyclic structure IX was supported by infrared and by essential agreement of melting point with the values reported previously. The present method not only affords a better yield but also appears more convenient. These results represent a significant advance in our studies of dianions, the two anionic portions of which are in r e ~ o n a n c e . ~Dianions I ” and IV“ are to be distinguished from ordinary 1,4-dianions in which the two anionic portions are not in resonance. Because the carbanion portion of I ” or IV” is much more nucleophilic, C-condensations can be effected to the
(1) Supported by the Petroleum Research Fund, administered by the American Chemical Society, and the National Science Foundation, (2) W. G. Kenyon and C. R. Hauser, J . Org. Chem., 30, 292 (1965). (3) W. Wislicenus and A. Ruthing, Ann., 379, 229 (1911); 3. Matti and M. Perrier, Bull. SOC.Chim. Frunce, 2 2 , 525 (1955); H. 0. House and D. Ryerson, J . Am. Chem. SOC.,83,979 (1961). (4) Several 1,3-dianions, such as that of acetylacetone, have previously been prepared; see C. R. Hauser and T. M. Harris, J. Am. Chem. SOC.,80, 6360 (19%).
c,X=H d,X=D
absence of formal hyperconjugative structures involving the isotopically labeled group X dictated the study of these compounds as a probe into the still debated question of the relative contributions of hyperconjugation and nonbonded interactions to secondary isotope effects. Since kIalIc is about 10, whereas the nucleophilic ~ I I I ~ / ~isI less I I ~ than l e 3 , Ia must solvolyze by a limiting mechanism. As judged from kIIa/kIIcof about 30 and an a-isotope effect kIIa/kIIbf of 1.32, IIa also solvolyzes by a limiting mechanism. That in formic acid IIc solvolyzes by a limiting mechanism has been established2 and supported here bythea-isotope effectkIIc/kIId~of 1.35. From currently available potential function^,^^^ V(r), and using Bartell’s p r o c e d ~ r ewe , ~ have calculated and summarized in Table I1 the nonbonded isotope effect (kIa/kIb)for IV -P V as a function of the dihedral
IV
V
(1) Isotopic purity for d1 compounds: 98% d1, 2 % do; for da compounds: 97.3% d3, 2.7% dz. We thank S. Meyerson of the American Oil Co., Whiting, Ind., for the mass spectral analyses. (2) M. J. S. Dewar and R. J. Sampson, J . Chem. SOC.,2789 (1956);
2946 (1957). (3) L. S. Bartell, J. Am. Chem. SOC.,83, 3567 (1961). (4) R. A. Scott and H. A. Scheraga, J . Chem. Phys., 42,2209 (1965). For the H tt C interaction the function given by J. B. Hendrickson, J. Am. Chem. SOC.,83,4537 (1961), was used.
Communications to the Editor
464 Table I. Rate Constants and Isotope Effects for 1-111 at 25.00' Compd
Solventa
Mechanism
Ia Ib IC IC Id IIa IIb IIb' IIC IIC IId IId' IIIa IIIC IIId
A A A
Lim Lim Unknown Unknown Unknown Lim Lirn Lim Unknown Lim Lim Lim Nucl Nucl Nucl
B B C C C C D D D E E E
k X 106, sec-1
46.15 i 0.59 45.44 f 0.34 5.44 f 0.12 17.99 f 0.18 18.09 f 0.24 0.3126 f 0.0045 0.3086 i~0.0028 0.2366 f 0.0004 0.0099 f 0.0005 4.49 i 0.11 4.51 i 0.04 3.32 f 0.02
1.029 f 0.015
Table II. Calculated kIajkIb from Nonbonded Potential Functions, V(r)
deg
deg
,----V(r)*AAE,', cal/mole
0 15 30 45 60 75 90
0 7.5 14 18 20 20 0
- 870 -710 - 460 - 250 -116 -90 -81
kIa/kIbl 25" 4.31 3.32 2.17 1.52 1.21 1.16 1.15
-V(rYAAE,' cal/mole
- 530
kIalkIbr 25" 2.43 2.03 1.48 1.18 1.07 1.03 1.03
-420 -230
- 100 -40 - 20 - 38
a AAE = AEH - AED. From ref 3. AAE calculated as outlined in ref 3. c From ref 4. AAE = 0.135/mz[V" 1/zlt2 VIv]. In both b and c the values used (angstroms) were: /m = 0.09, It = 0.16 for H C1 and H 0 interactions; I, = 0.10, It = 0.14 for H cf C interactions.
-
+
-
+5.9 f 8 . 2
1.013 f 0.024 1 . 3 2 1 c f 0.021
-7.7 i 14 -165 f 9
1.00 f 0.05 1 . 3 5 c f 0.05
0 f 29 -178 f 23
