846

EKN~ST GKUNWALDD S. WINSTEIN AN

Vol.

io

the time of reilloval of the first tube a f t u attainment of temperature. The infinite titer of bromide ion agreed well with the expected as indicated by the equivaleni weights of the CYbromopropionic acid samples. The infinite titer of base was usually unreliable by a few per cent., probably due to reaction of the glass. Soft glass tubes were used in the experiments with methanolic solutions, and Pyrex tubes were employed for the aqueous runs. In the ruiis with high bast concentration, the reaction was followed chiefly by titration for bromide ion. With the low base concentrations, titration was carried out for both base and bromide ion except where bromide ion was added in large amounts initially. When added sodium perchlorate the rate constants based on the two titrations agreed closely (Table 11). With added sodium nitrate, the rate constants from bromide titration were steady but those based on base titration were lower and drifted downward. In run 21 with 0.5 M added sodium nitrate, the base consumed during a run averaged 98.8 * 0.7% of the bromide ion produced, while the analogous figure was 96.6 f 1.5% for run 19 with Madded sodium nitrate.

The variation of k1 with change in solvent and ionic strength is discussed in terms of a rate-determining ionization either to the zwitterion I1 (specific rate kc), or the a-lactone I (specific rate kb). An unambiguous decision regarding the reaction mechanism is not possible from the salt and solvent effects alone.

I1

Summary The hydrolysis and methanolysis of sodium abromopropionate in the presence of sodium hydroxide or methoxide was investigated in solutions of varying ionic strength a t 64.04. A kinetic analysis reveals that both the bimolecular and unimolecular specific reaction rate constants, kz and kl, respectively, increase with ionic strength.
[CONTRIBUTION FROM

However, the sign of these effectsand related evidence, particularly the high reactivity of a-bromopropionate ion compared to isopropyl bromide and the contrast with a-bromoisobutyrate ion, are consistent with the rate-determining ionization symbolized by ka. The ratio of rate constants for reaction of the intermediate in the solvolysis of a-bromopropionate ion with bromide ion and solvent, kBr/ks, derived from measurements in solutions containing high bromide ion concentrations, is 2.0 in methanol and 0.76 in water.
Los ANGELES CALIPORNIA RECEIVEDU N E 11, 1947 24, J

THE

CHEWISTRY DEPARTMENT THE UNIVERSITY O F CALIFORNIA, L O S ANGELES] OF

The Correlation of Solvolysis Rates

BY ERNEST GRUNWALD S. WINSTEIN AND
rates with the aid of such a set of Y values and a simple functional relationship between k1 and Y. Also, the theoretical implications of the method are discussed. In addition to the solvolysis mechanism A there occurs solvolysis in neutral and acidic solvents by ki a process or processes (B,rate constant k,) or RX+R+fX(1) depends on the so-called ionizing power of the which the nucleophilic character as well as the solvent, and it is possible from such rates to ar- ionizing power of the solvent is important. The range solvents in a relative order. For example best understood concerted process is the so-called substitution of the unimolecular types proceeds bimolecular substitution in which a solvent moleslightly more rapidly in acetic acid than in abso- cule plays a role such as that of a pyridine molelute ethan01.~The rate is increased by addition of cule in the Menshutkin reaction. One of the imwater to alcohol or partly aqueous acetone or diox- portant problems for the proper understanding of ane.S2 Further, substitution is about as rapid in such subjects as reactivity, stereochemistry of displacements and rearrangementsIb is that of formic acid as in 50% aqueous ethanoLS sorting out the fractions of solvolysis proceeding The question arises whether it is possible to assign to each solvent a definite number Y which by mechanisms A and B. The scheme for correlating solvolysis rates alis a quantitative measure of its ionizing power in determining K1. In this article is reported a lows one to make deductions regarding the rate scheme for correlating unimolecular solvolysis by process A and therefore the fraction of solvolysis by mechanism A. This application of the (1) (a) Hughes, Trans. Far. Soc., 87, 611 (1941); (b) Dostrovsky, method is being actively pursued and the proceHughes and Ingold, Chcm. Soc., 173 (1946). dure is illustrated in tne present article for isopro(2) Hammett, Physical Organic Chemistry, McGraw-Hill Book Co., New York, N. Y.,1940, pp. 166 8. pyl p-bromobemenesulfonate. (3) Winstein, Grunwald, Buckles and Hanson, THIS JOURNAL, 70, A Quantitative Measure of Ionizing Power. 816 (19481. The Y Fqctioa.-The specific solvolysis rates K (4) Winstein, Hanson, and Grunwald, ibid.. TO, 812 (1948). for a number of halides which, t h e accumulation (6) Dootrovsty and Hughes, J . Chcm. Soc., 166, 171 (1946). One of the important mechanisms (A) for solvolysis1.2 of alkyl halides involves more than ene stage and is at present best formulated as involving a rate-determining ionization (equation 1) to a cationic intermediate. The rate constant k~
J.

Feb., 1945

THECORRELATION OF SOLVOLYSIS RATES

TABLE I

847

S~LVOLYSIS OF SOME RATES HALIDES AND Y VALUES FOR SOLVENTS

k(sec.-1) Y Ref. Absolute EtOH 25.97 9.70 x 10-8 Table I1 -1.974 90% EtOH, NH,O = 0 2 2 .6 1.73 x 10-8 6 -0.727 23.06 9.24 x 10- 6 80% EtOH, N H ~ = 0.448 O 0.000 70% BtOH, NH*O= 0.582 4.07 x 10-5 6 0.644 60% EtOH, NH*O= 0.684 1.27 x 10-4 6 1.139 22.92 3.67 X lo-' 6 1.604 50% EtOH, NH,O = 0.765 2.151 1.29 X lo-* 6 40% EtOH. NH,O= 0.829 22.6 1.94 X 10-6 6 80% (CHaIiCO 2.57 X 10-2 7 3.449 5% (CHJKO, NH~O 0.987 = 22.8 1.81x 10-4 8, llb 48.61wt. % H 2 0 in dioxane 1.292 H20-MeOH, NH,O= 0.000 2:5.0 8.20 x 10-7 8,Table I1 -1.052 Hz0-MeOH, NE,O = 0.070 - 0.722. 1.75 X 10-6 8 H20-MeOH, = 0.175 4.33 x 10-0 8 -0.329 7.14 X lo-' Hz0-MeOH, = 0.230 8 -0.112 H20-MeOH, NH*O 0.282 = 1.13 X 10-6 8 0.088 2.12 x 10-6 8 H20-MeOH, NE,O = 0.346 0.361 HpO-MeOH, NR%O 0.432 = 5.28 X lo-' 0.757 8 HaO-MeOH, NH,O = 0.497 1.023 9.75 x 10-5 8 3.56 H2Oe o' 3.3 x l HCOOH~ 22.9" 1.1 x lo-' 9a 2.08 26.43 2.13 x 10-7 Table I1 -1.633 AcOH, 0.025 M KOAc AcOII-AcsO, N A ~ O = 0.042 H 26.4" 4.77 x 10-9 Table I1 -3.287 0.017M KOAc 23.0" 5.69 X 10-6 1OC EtOH 90% EtOH 7.14 X 10-6 1Oa 22.8 3.63 x 10-4 10a 80% EtOH 22.5" 5.22 x l o' 10d 76.5% EtOI-T, NH,O = 0.501 21.7 60% EtOH 3.76 x 10-3 1Oa 2.10 x 10-0 10b - 2.402" 22.7 95% (CHa)zCO, N H ~ = 0.178 O 1.27 X 10-6 1Oe -1.549" 20.8 90% (CHJzCO, NHZO 0.313 = 20.8" 1.10 x 10-4 loa 0.527' 80% (CHa)zCO, NHZO 0.506 = 70% (CHa)zCO, NHZO 0.637 = 0.205' 5.15 x 10-4 1Oe 23.5" 8.8 X 10-9 lla CH&!HCICH==CHg 25.0 EtOH 50% Et013 1.14 X 10-1 1 la 23.5" 8.1 X lo-' llb HzO (CH3)sCCHIBr 95.0 70% EtOH 1.54x 10-7 5 29.0 5 50% EtOH x 9 . 2 ~ 10-7 1.53 x 10-0 5 HCOOH (CsHs)nCHC1 25.0 EtOH 0 5.30 X 10-5 1 f 90% EtOH 4.90 x 10-4 12b 80% EtOH 1.72 x lo-' 12b 19.6 4.60 X 10-6 10e -3.377d 90% (CH312CO 21.0 7.24 x 10-5 1Oe - 1.797d 80% ( C H W O 3.20 x 10-4 10e -0.945d 70% (C?&)zCO WsCHClCHt 50.0 EtOH 21.9" 5.85 x 10-7 13 21.4 80% EtOH 1.64 x 10-4 12" MeOH ' 2.' 17 7.06 X 10W 13 21.8" 1.44 x 10-6 13 80% (CHJzCO 21.5" 4.19 X 10-6 13 60% (CHdzCO AcOH, 0.2 M KOAc 3.9 x 10-6 14 Rate constants have been reported" a t 1 . ' ranging from 2.0 X 10-4 to 3.9 X 10-4 50 0 Value used by the authors. sec.-l. An average value was used. Rate measurements in formic acid are complicated by decomposition of the solventgb,e into carbon monoxide and water. e From t-butyl bromide. d From benzhydryl chloride. e Obtained by extrapolation from the plot of log kBuC* vs. NH,Ousing the datao.' in aqueous acetone. Compound C. Solvent
Tpp..

E', kcal.

(CH3)sCCI

25.0

(8) Hughes, J . Chcm. Soc., 255 (1935). JOURNAL, MI, 658 (1946). (7) Swain and R m ,THIS (8) Olson and Halford, ibid., 69, 2644 (1937). (9) (a) Bateman and Hughes, J . Chrm. Soc., 935 (1940); (b) Bateman and Hughes, ibid., 940 (1040): (c) Weissberger and

Proskauer. "Organic Solvents," Clarendon Press, Oxford, 1935, p. 145. (10) (a) Bateman, Cooper, Hughes and Ingold, J . Chcm. Sot.. 925 (1940); (b) Cooper and Hughes, ibid., 1183 (1987): (c) Hughes, Ingold, Masterman and McNulty, ibid., 899 (1940); (d) Petrenko-

S48

ERNEST GRUNWALD S. WINSTEIN AND

TABLE XI

Vol. 70

FIRST-ORDUR SovvoLysis RATE CONSTANTS 70.0". FOR I-BUTYL AT CHLORIDE PINACOLYL AND AND

ISOPROPYL p -

BROYOBENZENESULFON ATES
Compound Solvent

gz
40.3 42.3 12.04 19.25 19.60' 18.43' 52.16 37.25 52.16* 37. 25b 19.21 37.40 33.46 19.40 24.71 22.61 34.29 27.60 16.55 12.37 7.16 19.82 12.06 5.87 9.94 12.84 30.65 36.72 21.81 28.33

(ROAc)

ivM

k, s e c - 1

(CHi)sCCl

AcOH-97.5% ACZO NA,OH =0.042 ACOH-O.l% A s 0

EtOH

MeOH

19.07 15.67 24.63 24.54 24.89 24.91 60.2 35.0 60.2 35.0 58.5 58.5 19.91 8.99

(CHs)rCCH(OS02 Cd-IJWCH3

80% EtOH" AcOH-97.5% Ac2O N A ~ O H0.042 = AcOH-80.3% Ac2O N A ~ O = 0.294 H ACOH-O.l% Ac~O
EtOH

...
..

(1.625 * 0.048) x 10-8 (7.12 * 0.12) X lo-; (7.45 * 0.10) x 10-5 (8.78 * 0.17) X lo-' (8.91 * 0.20) x 10-7 (3.19 * 0.03) X 10-6 (3.12 * 0.03) X (3.82 f 0.07) X 10-7 (3.69 * 0.07) X lo-' (2.07 * 0.07) X lo-' (2.10 * 0.03) x 10-4 1.51 X (11.49 * 0.15) X 11.66 X 10-6 (7.89 * 0.11) x 10-5 (2.734 * 0.026) X lo-' (2.742 * 0.033) X lo-' (2.811 * 0.022) X 10-9 (7.02 * 0.10) X (7.01 * 0.13) X (7.09 * 0.09) x (3.19 * 0.06) X lo-' (3.15 * 0.05) X lo-' (3.29 f 0.05) X lo-' (1.369 0.018) X lo-$ (1.386 * 0.017) X lo-' 1.30 X lo-' 1.50 X 1.46 X lo-* (8.45 * 0.11) X
f

(1.620

* 0.048)

X (0-6

...

24.87

...

...
...

MeOH

... ...

80% EtOH
(CH&CHOSOI C&Br AcOH-97.5% Act0 NAoaa = 0.042 A c O H - ~ O . ~Ac~O % NA.OH = 0.294 AcOH-O.l% Act0

... ... ...

...

22. 2gd 10. 25d

...

EtOH MeOH

80% EtOH

R,

Data at 34.85'; E* = 2 . 3 kcal./mole. 64 = 3.61 X lO-'~ec.-~hP1.

(6.98 * 0.08) X lo-' 42.66 ... (6.90 * 0.05) x 10-5 26.72 (7.41 == 0.07) X 24.10 25.03 (2.64 * 0.04) X lo-' 23.16 ... 23.31 (7.34 0.08) x 10-4 ..* (7.28 * 0.16) X lo-' 18.15 1.73 X lo-' ... 11.35 1.67 X lo-' 11.93 f Data a t 34.43O; E +i = 25.97 kcal./mole. c From data o Hughes.'

...

... ...

of evidence indicates, react by the unimoleculartype mechanism A, are summarized in Table I together with the values of the corresponding Arrhenius activation energies, E *,wherever available. The solvolysis rates for any one compound have been corrected to one temperature with the
Kritschenko, Ba., 61, 862 (1928): (e) Bateman, Church, Hughes, Ingold and Taher, J . Chem. Soc.,979 (1940); (0Hughes, Ingoid 8nd Taher. ibid., 949 (1940). (11s (a) Young and Andrens, THISJOURNAL. 66,421 (1944); (h) Winstein and Grunwald, ibid., 10, 828 (1948). (12) (a) Ward, J . Chcm. Soc., 446 (1927); (b) Ward, ibid., 2186
(1927).

(IS)'Hughes, Ingoldand Scott, ibid., 1201 (1937).

(11) Bt.iaarnrsd Hmnamatt, TBXU JORRNAL, 6 9 , Z S W (191)7),

aid of available values of E * or else on the basis of reasonable estitnates of E *. The values of E * for any one compound are fairly insensitive to solvent change and all values of E * hover near 22 kcal (Table I). It is therefore possible to estimate E A with sufficient accuracy since the corrections made are small. Even an error of 2.0 kcal. in E * would cause an error of no more than 0.079 in log k for a 20' correction. Supplementing the data in Table I are the solvolysis rates k we have measured for t-butyl &loride and a-methylneopentyl p-bromobenzenesulfonate, (CHI)aCCH(OSOIC&J3r)CHa, in a num-

Feb., 1945

TIIE CORRELATIONSOLVOLYSIS OF RATES

S49

hcr of solvents. These mcasrirements are suminnrized in Table I I. Inspection reveals a simple quantitative relationship among the various solvolysis rate constants. Thus, when the values of log k for any one compound in a number of solvents are plotted against log k of some other compound in the same solvents a straight line is obtained. This linear relationship is illustrated for a number of compounds in Fig. 1.

- 2 - 1

+ log kBUC'.

values of Y it is clear from the near constancy of E& in various solvents that any other reference temperature would give an almost identical set of Y values. The linear relationships illustrated in Fig. 1 combined with the defining equation 2 for Y lead to equation 3 for the variation of solvolysis rate constant k with solvent for these compounds. In log k = nzY + log K O (3) this equation, m and log KO are parameters, although physically KO is the solvolysis rate constant in "80%" ethanol. Equation 3 is the basis of the quantitative scheme for correlating solvolysis rates. In Table I are summarized values of Y for an extensive series of solvents. Y values for all solvents except the acetone-water mixtures were calculated from the available data for t-butyl chloride a t 25.0' (Tables I, 11). In order to obtain Y values in the latter solvent mixtures the parameters m and log KO were evaluated for t-butyl bromide and benzhydryl chloride from data a t 25.0' in ethanol-water mixtures, and Y was calculated for various acetone-water mixtures with the aid of equation 3, using the available values of log k for these compounds. Two different sets of Y are obtained in this way, of which one (from t-butyl bromide) is used for aliphatic compounds while the other (from benzhydryl chloride) is used with a-phenylethyl chloride. Acetone-water mixtures were the only solvents where it was found necessary to use two different sets of Y in order to correlate all rates of unimolecular-type solvolysis scrutinized by the authors to date. The functional relationship between Y and the composition of mixed solvents is apparently not

Fig. 1.-Plots of log k os. log kBuC': I, t-butyl bromide 25.0'; 1 , a-methylallyl chloride, 25.0'; 111, a-methyl1 neopentyl p-bromobenzenesulfonate, 70.0 IV and V, neopentyl bromide, 95.0,and n-butyl bromide, 59.4 ', both v s . t-butyl chloride, 26.0"; solvents: 0, HzO; 0 , EtOH-H20; 0, MeOH-HtO; V, ACOH-AC~O; A, acetone-HiO; 63, HCOOH.
O;

The linear plots illustrated in Fig. 1 indicate that log Put* (EuCl = t-butyl chloride) satisfies the requirements for a useful quantitative measure of ionizing power of a given solvent. However, log kBuC1varies with temperature and is usually a negative entity of an inconvenient order of magnitude. It is convenient to define Y by equation 2, where kBuCl and k,Buc' are the rate constmts of'
Y = log
P"C'

- log k0B"C'

(2)

t-butyl chloride a t 25.0' in the given solvent and in "80%" ethanol, respectively. By virtue of this definition, U is zero in ' i 8 0 ~ 0 "ethanol, a solvent often employed and of intermediate reactivity, and Y varies from ca. +4 to -3 for the most common solvolyzing media. Although 25.0'' is chosen as the reference temperature for computing

0
"20.

0.5

Fig. 2.--Plot

of Y us. mo1e:fraction of water (Nn@) for:

X, Ha0-MeOH; 11, HIO-EtOH.

850

ERNEST GRUNWALD S. WINSTEIN AND

Vol. 70

simple. Plots oi Y vs. weight % or volume % of water in aqueous ethanol and methanol have considerable curvature. The plot of Y os. iriole is fraction of water, N H , ~ , more nearlylinear for these systems as illustrated in Fig. 2. The latter observation is useful for purposes of interpolation. The parameters ttz and log k, in equation 3 have been evaluated for a number of compounds by the method of least squares, using the values of k and Y in Tables I and 11. The results are summarized in Table I11 together with the probable error of the fit,lS r . The fit is satisfactory, particularly since the values of k often vary by 3 to 6 powers of ten, the mean value of r for the whole table being less than 0.05. The probable errors in m are of the order of 0.05 or less.
TABLE I11
CORRELATION OF SOLVOLYSIS RATES VARIOUS SOLVENTS IN
NO.

all activity coefficients to the gas phase so that equation 5 reduces to 6. Jn this equation H A and H Z are the Henrys law constants16 of reactant
ki
K=

(HA/K?)

(6)

and transition-state. Coniparisoii of equations (j arid 3 lends t u T which implies a liiienr rtl:itionship, 8, hetwecii
fI2 log ( I - . . A / H ~ ) log (HB,;) and
I~ = log -- A mY
ko + log (7)

for any two com-

pounds A and B solvolyzirig by the unimoleculartype mechanism in a series of solvents. This deduction calls to mind the ob~ervation~ there that exists an even simpler linear relationship, shown in equation 9, between log ( f ~ / f ~ a + ) for any two

Compound

Tyw

c.

711

logko

1 &Butyl chloride 2 t-Butyl bromide

:J

5
6 7 S

In the case of solvolysis by mechanism A the change AZ ---t AZ is from the dissolved halide or ester to the partly ionized and strongly solvated transition-state molecule. Equation 3 and thus b is successful for variations in the ionizing group to Equation 4 gives the variation of m with teinpcr- include chloride, bromide and bromobenzenesulature T . This is slight since for most solvents the fonate. Also, the change XZ --+ AZ is not restricted entirely to the A-Z bond. For example, dni E* - E: 2.303 Y - = resonance will diffuse any positive charge of the dT HP carbon transition state to the difference between the activation energy E * and alphaand paraatom in the an alpha phenyl group. positions of the activation energy EO in 80% ethanol is ortho in aliphatic cases the positive charge will be Even small for unimolecular-type solvolysis (Tables spread. Now evidently equations 3 and 8 hold for T TT\ I, Ll). considerable variation in the R part of the solTheoretical Interpretation. The Activity volyzing molecule K X but further work is necesPostulate.-Application of the Bronsted theory sary to clearly outline the scope and limitations to the variation o f k1 with solvent for unimolecular- in this respect. The nccd for two sets of Y values m for aqueous acetone mixtures is one of the liniitations which has already appeared. Solvolysis of &Butyl Chloride.-The solvolysis type solvolysis leads to equation 5 where K is the specific rate in the standard state of unit activity rate of t-butyl chloride in a range of mixed and f A and are the activity coefficients of reac- aqueous solvents has previously been correlated tant and transition-state. In the case of dilute by Olson and HalfordBwith the aid of the fugacsolutionsl6 of non-electrolytes it is useful to refer ity rate equation 11 where pw and pa are vapor

50.0 1.195 -3.808 ,072 59.4 0.392 - 5.972 ,026 75.1 0.331 -5.419 .034 The value of k for HOAc, 0.2 M KOAc (Table I ) , was not included smce no value of Y is available at such high acetate concentration. From the above data k = 1.74 x 10-6sec.- at 0.025 M KOAc (Y = -1.633) in reasonable agreement with the value in Table I.

Neopentyl bromide a-Methylneopentyl p-bromoberizenesulfonate a-Methylallyl chloride Benzhydryl chloride a-Phenylethyl chloride n-Rutyl broinide

25.0 1.000 25.0 0.917 95.0 .712

-5.031 -3.476 7.248

...
0.026 ,059

conjugate acid-base systems B and B in a series

of solvents.

70.0 25.0 25.0

.706 .894 .757

-2.837 -6.314 - 2.779

.096 .052 .004

The success of equation 3 for correlating solvolysis rates of the unimolecular type may be due to the validity of a general relationship regarding ratios of activity coefficients. For systems undergoing similar changes of the type AZ 3 AZ, BZ + BZ, etc., the postulated general relationship may be expressed by equation 10, p and fl being parameters.

fz

(15) Margeiiau and1 Murphy, Mathematics of Physics and Chemistry, D. Van Xoslrand Co.,Inc., New York, N. Y., 1943, p 502. *&(I@ Lewis and Randall, Thermodynamics, McGraw-Hill Book Co., Inc., New York, N. Y.. 1923, Chapter XX.

= i

( k , 9,

+ k.

P ~ ~ ~ B U C I

(11)

pressures of water and alcohol, respectively. This eqbation, which empirically fits the rates but not
(17) Ref. 2, Chapter IX.

Feb., 1948

THECORRELATIONSOLVOLYSIS OF RATES

851

the products, l 8 is based on assumed bimolecular reactions between halide and water or alcohol but it is set up according to an activity rate formulation, the respective terms not being divided by the activity coefficients of the corresponding transition states. Actually higher order'* fugacity rate equations lit the rates at least as well as equation 11. Scrutiniziiig the data with our present approach, seeking generalizations regarding activity coefficients involved, we find that log k is a linear function OF log H B u C l for the range of solvents treated by Olson and Halford. Equation 12 fits
log W C ' = 1.232 log H B ~ - ~ c 9.811 (12)

holds the variation in kBuCl is due largely to changes in I I B ~ c ~On the other hand, in the . poorer ionizing media the variation in KBuC1 is due largely to changes in H&cI.
I

I " " " '

the data a t 25.0' for all partly aqueous solvents (including also water and methanol) (Tables I, I+ 11, IV, ref. 8) with a probable error of 0.06. Thus, only two parameters are necessary. - 3 - 2 -1 0 1 2 3 The linear relation expressed in equation 12 5 log kBuCI* indicates, according to equation 6, that a linear Fig. 3.-Plots of log HBuC' and (log HiBuC1 log K ) relation exists between log H&CI log H B ~in I against log kBuC1,25.0': 0, Hz0-EtOH; 0, Hz0-MeOH; and C the solvent range involved. This linear relation 8 , H20-dioxane; V, AcOH-AclO; A , HaO-acetone; takes the form shown in equation 13. 0, Hz0.

Solvolysis of Isopropyl pBromobenzenesulfonate.-For the simple secondary alkyl compound, isopropyl p-bromobenzenesulfonate, HENRY'SLAW CONSTANTS FOR t - B U m CHLORIDE AT without essentially prohibitive steric hindrance 25.0' to nucleophilic attack on carbon such as evilo-' RBuCI, Solvent mm. dently obtains in the case of pinacolyl p-bromoHOH 5 x 108 benzenesulfonate, the nucleophilic character of EtOH 1.09 *0.09 the solvent is very important. The first-order HOAc, 0.025 M KOAc 1.23 t0.05 solvolysis rate constants k for isopropyl p-bromo0.786 * 0.020 HOAC AQO, NA~OH = 0.042 benzenesulfonate are summarized in Table I1 and inspection reveals the contrast with the other While there are indications that linear log-log re- compounds treated successfully by equation 3. lationships between the activity coefficients of For example, the rate constant in ethanol is much non-electrolytes are fairly general, l9 the linear log- greater than in acetic acid although the Y value log relation expressed by equations 12 and 13 for for acetic acid is the higher. This contrast is due t-butyl chloride and its solvolysis transition state to the fact that ionizing power and nucleophilic breaks down when one proceeds to the more character of solvents do not go hand in hand. Inpoorly ionizing solvents such as absolute alcohol stead of the rates in all solvents being manageable or acetic acid-acetic anhydride combinations. together i t is now necessary to differentiate beThe plot in Fig. 3 of log kBuC1vs. bgHBuC1 a t 25.0' tween basic solvents and others. illustrates the linear relation for one range of Quite a satisfactory understanding of the solsolvents and the large departure for the slower volysis rates of isopropyl p-brompbenzenesulfonsolvents mentioned. Even with the departure ate may be reached on the assumption that solvolfrom linearity the curve is smooth. However, a ysis proceeds by both mechanism types A and smooth curve is not necessarily to be expected and. B, B being slight or negligible in the acidic type this feature may be fortuitous. solvents such as acetic acid or its mixtures with Further insight into the above-described situa- acetic anhydride and serious in the inore basic tion is derived by reference again to equation 6. solvents. As shown in equation 14, (log H13,cl-log KBuC') is a In the acetic acid-acetic anhydride solvents the log H&CI log h = log 1 1 ~ - ~ 1 kB"C1 (14) ~ log plot of log k for isopropyl p-bromobeiizenesulfonmeasure of log H&CI, this quantity is plotted ate against log K' for pinacolyl p-bromobenzeiieand against log kBuC1in Fig. 3. It can be seen that in sulfonate gives the least squares line shown in 36. The the partly aqueous solvents where equation 12 equation 15, theprobableerrorl6beingO.1
TABLE IV

log H&CI = -0.232 log H B ~ C IConstant

(13)

(18) (a) Bartlett, TEISJOURNAL, 61, 1630 (1939); (b) Winstein, ibid., 81, 1635 (1939); (c) Bateman, Hughes, and Ingold, ibid., 60, 3080 (1938); (d) Bateman, Hughes and Ingold, J . Ckcm. Soc., 881 (1938). (19) Grunwald, Dissertation, University of California at Los Angeles, Calif., 1947, sections 6, 17.

log k = 1.204 log k'

+ 0.031

(13)

straight line fit is not as satisfactory here as in the other cases, possibly because the acetolysis is not cleanly of the unimolecular type (k = kl). It is not out of the question that acetic acid can func-

852

ERNEST GRUNWALD S. WINSTEIN AND

Vol. io

Mataials.-The t-butyl chloride was Eastman Kodak eo. White Label grade, b. p. 51.2 (752 mm.), n Z 6 D 1.3520. a-Methylneopentyl alcohol, b. p. 120.0-120.3 (754 mm.), was prepared by Miss Anita Stiran from t-butyl magnesium chloride* and acetaldehyde. a-Methylneopentyl ~-hroniobenzenesulfonatc I and isopropyl p-bromohenzenesulforiate I1 were preparctl ill CQ. 50T0 yield in 0.05mole batches from the correspo!itliiig alcohols and p-bromobenzenesulfonyl chloride in pyridine by conventional methods.z4 I crystallized upon pouring the pyridine reaction mixture into ice-cold 6 N hydrochloric acid and was recrystallized several times from petroleum ether (b. p. 60-80); m. p. 53.2-53.5; equivalent weight from quantitative solvolysis: calcd., 321-2; found, 323.2 (in acetic acid), 320.1 (in 80% ethanol). TABLE V Anal. Calcd. for ClaH170sSBr: C, 44.86; H, 5.34. Found: C, 44.99; H, 5.49. SOLVOLYSIS OF ISOPROPYL ~-BROMOBENZENESULPONATE AT I1 separated as an oil upon pouring the pyridine 70.0 IN NUCLEOPHILIC : SOLVENTS reaction mixture into 6 N hydrochloric acid. The oil was 10kl Calcd. Calcd. Calcd. 104kl sec. IO+. IOOR~/B Sol vel1 t f separated with the aid of GU. 40 ml. o carbon tetrachloride and the solution was dried over anhydrous potassium 0.108 2.53 4.1 EtOH 2.64 carbonate. After evaporation of the solvent a t room 6.68 6.63 9.3 MeOH 7.31 temperature the viscous residue was induced to crystal3.86 13.1 22.7 80% EtOH 17.0 lize. The solid was purified by reprecipitat? under petroleum ether (b. p. 00-80); m. p. 32.334.1 . EquivIt is interesting that k , in the small range of alent weight from quantitative solvolysis : calcd. 279.2; comparably nucleophilic alcoholic solvents is fit found 282.1 (in acetic acid), 278.3 (in methanol). Analby a linear equation of the same type as 3, equa- ysis for carbon and hydrogen was unsuccessful because decomposed rapidly tion 16 fitting the data in Table V with a probable I1 Solvents.-Synthetic on heating. containing less than methanol, 0.030/, of water by the miscibility temperature with 1 1 6, = 0.360 Y - 2.857 0: (16) cyclohexane,*6was used. error of 0.046. In these solvents the rate of solEthanol was dried by the ethyl formate methodz6 and volysis by mechanism B seems to depend on the contained less than 0.02% of water by Robertsons same properties of the solvent which control the paraffin oil test.16 80% ethanol by adding 317.5 g. of rate of the A type, the slope m, however, being conduct-ivity water was preparedethanol. to 1000 g. of quite small. Acetic acid containing 0.0142 M (0.1%) acetic anIt is an especially satisfactory feature of the hydride by Kilpis anthranilic acid analysis* was preassumed way of accounting for the solvolysis rates pared as described in a previous a r t i ~ l e . ~ To Reagent Grade of isopropyl p-bromobenzenesulfonate that the acetic 379.0 g. of Baker and Adamson 51.20 * 0.06 by anhydride, equivalent weight slope in equation 16 is so small andso nearlyequal hydrolysis and titration with standard aqueous base to to the one which is derivable for n-butyl bromide. the phenolphthalein endpoint (mole fraction of acetic 0.042), was added 80.6 of acetic acid There is reason to believe that the latter halide acidwt. of acetic anhydride g. give a solvent containing to of equiva0.1 solvolyzes exclusively by mechanism B in alco- lent weight 52.63 * 0.06 (mole fraction of acetic acid holic solvents, and Bird, Hughes and IngoldZ0 have 0.294). In order to prepare solvents containing potassium acetate supplied rates of solvolysis in various aqueous ethanol and methanol solvents.21 Using their the Baker and Adamson Reagent Grade salt was dried in a tared glass-stoppered at data a plot of log k against log kBuCl is linear as il- to constant wweightdissolved in the desired weightflasksol110 in u u c and of lustrated in Fig. l and equation 3 fits the data well vent. as summarized in Table 111. The values of m in Kinetic Measurements.-Rates were meas-

tion in solvolysis by mechanism B. While the addition of O.O%h< potassium acetate to glacial acetic acid gives no serious change in first-order rate constant the addition of 0.01M potassium acetate to the solvent rich in acetic anhydride produces a predominantly bimolecular reaction. However, the slope of the line represented by equation 15 is reasonable for solvolysis largely by inechanisin A. The value of 1.204 combined with an m value of O.iOG for piriacolyl p-bromobenzenesulfonate (Table 111) corresponds to 0.550 for m in the case of the isopropyl ester. Assuming k = kl in the acidic solvents, equation 15 allows one to estimate kl in the nucleophilic alcoholic solvents;. These estimates are listed in Table V along with k, (4. z., k - kl) an$ the percentage of solvoXysis by mechanism A, 100 k l / k .

fact, values of nz are also auite simi1aP for other prinlary halides apparent]+ solvolyzing by mechanism B. Experimental and Kinetic Part

aqueous methanol a t 59.1 and aqueous ethanol a t 75.1 are 0.392 and 0.331, respectively. In

(20) Bird, Hughes and Ingold, J . Chem. SOC., 255 (1943). (21) In the case of n-butyl bromide, the fugacity rate equation 11 has been found b y Bird, Hughes and Iagold*o t o fit both rates and products. I t must bir noted that R may be expressed as the ratio of the vapor pressure of halide to either its mole fraction or its molarity. Olson and Halfordha,ve used mole fraction as is also done in the present article, and Bird, Hughes and Ingoldlo have used molarity However, because of differences in molar volumes of various mixed solvents, if the use o l molarity furnishes a fit for the product compositions, the m e of mole fraction cannot furnish such a fit. A recalculation of the data of Bird, Hughes and Ingold, using mole fraction in evaluating H . sbovs that equation 11 will fit the rates hut not the products.

ured by the usual sealed ampoule technique. Titrations were made on 5-ml. aliquots from 5nil. microburets. For the measurements in ethanol, methanol and S O ~ o ethanol, titration
(22) Winstein and Grunwald. unpublished work. (23) Puntambeker and Zoellner, Organic Syntheses, Vol. 23, John Wiley and Sons, Inc., New York, N. Y., 1943, p. 510. (24) Winstein, Grunwald and Ingraham, THISJOURNAL,70, 821 (1948). (25) Jones and Amstell, J . Ckcm. SOC.,1321 (1930). (25) Robertson, Laboratory Practice of Organic Chemiatry, Macmillan Co., New York, N. Y., 1943, pp. 178, 295. 9 (27) Kilpi, Suomcn Kcmisfilchfi, 18B. 1 (1940); C. A . , 86, 2446
(1041).

Feb., 1948

THE CORRELATIONSOLVOLYSIS OF RATES

t-BuC1

853

K = (t-BuCl)/(t-BuOAc)(HCl). Measurement of Henry's Gaw Constants.sium acetate. Using the data obtained during the Approximate Henry's law constants were delatter part of the run where the potassium ace- termined as follows: A 500-rnl. standardtate has been neutralized, k1 was calculated from taper round-bottom flask equipped with a graduthe slope (obtained by the method of least squares) ated dropping funnel and an outlet tube leading of the linear plot of log (RX) vs. time, t. The de- by way of a T-joint to a manometer and an oil rivative, -d In (RX)/dt, was then obtained a t pump was placed in a thermostat and evacuated various concentrations of potassium acetate from until the pressure was below 2 mm. A known a large-scale plot of In (RX) vs. t with the aid of a volume of standard solution of t-butyl chloride in tangent meter. Substitution in equation 17 gave the appropriate solvent was introduced carefully satisfactorily constant values for kz. The average from the dropping funnel and the increase in presvalue of k2 for this and a duplicate run was (3.61 * sure read. Room temperature was maintained above that of the thermostat to avoid condensa0.07) X see.-' M.-l tion of the vapors. A typical set of experimental TABLE I V data is given in Table VIII. In computing the ACETOLYSIS I s o p R o p n #-BROMOBENZENESULFONATE fraction of t-butyl chloride, allowance was OF' mole (RX) IN 4 2 MOLE% ACETIC . ACIDIN ACETIC ANHYDRIDE made for the materials in the known vapor space.
-d In (RX)/dd =
kl

for acid was camed out with 0.05 N sodium hydroxide using brom thymol blue as indicator. Titrations in glacial acetic acid and mixtures of acetic acid and acetic anhydride were performed as described previouslyaJ4 except that 0.05 N p toluenesulfonic acid was substituted for perchloric acid in the solvents containing large amounts of acetic anhydride. Reactions were usually followed to ca. 75% completion. Reaction mixtures were prepared gravimetrically except for the rateruns involving t-butyl chloride where initial concentrations were obtained from the "infinite" titer of acid and/or from Volhard titration for chloride ion. In order to avoid errors due to the volatility of t-butyl chloride, the vapor space above the reaction solutions in the ampoules was kept quite small. The observed kinetics were fist-order within the experimental error of 1-2% in k over the range of concentrations investigated except for the solvolysis of isopropyl p-bromobenzenesulfonate (RX) in 4.2 mole yoacetic acid in acetic anhydride in the presence of potassium acetate. A representative set of experimental data is shown in Table VI. These data were fitted satisfactorily by equation 17 which assumes a simultaneous first-order solvolysis and second-order reaction with potas-

rium mixture according to equation 18. The rate

+ HOAC = t-BuOAc + HC1

(18)

of establishment of equilibrium is considerably faster than the rate of solvolysis in the presence of potassium acetate. For example, a t 40.0' cu. 977' of the equilibrium concentration of hydrogen chloride is produced from a solution of t-butyl chloride within 28 hours whereas the solvolysis in the presence of potassium acetate is only ca. 207' complete within the same period. The pertinent equilibrium data are summarized in Table VII. The data were obtained by the sealed-ampoule technique described for the kinetic runs. The equilibrium titre of hydrogen chloride was constant within experimental rrrnr over a period of several days.
TABLE VI1 EQUILIBRIUMTHE SYSTEM &BUTYL IN CHLORIDE, &BUTYL ACETATE, HYDROGEN CHLORIDE
Initial I-BuCI IOSM

T,'C.

at equilibrium

WCI)

1' 0M

Ka

81.8 158.3 81.8 158.3

a

60.2 60.2 40.0 40.0

6.02 * 0.2 8.12 * .2 4.15 f .2 5.65 * .1

2.1 x 103 2.3 X lo3 4.5 X lo3 4.8 x 1 3 0

+ Rl(K0Ac)

(17)

AT 7 . ' 00

0.0 11.6 20.7 30.95 54.1 70.5 103.1 -120.1 143.1

36.72 26.89 22.74 19.20 15.68 14.25 12.05 11.02 9.62

22.28 12.45 8.30 4.76 1.24

..
5.84 4.47

TABLE VI11 HENRY'S LAWCONSTANT OF I-BUTYL CHLORIDE IN ACETIC ACID CONTAINING 0.025 M POTASSIUM ACETATE, 25.0'
NBUCI

p, mm.0

10-*H , mm.

..

... ... ...

...

1.94

.. .. ..
..

1.13 1.22 1.26 1.29 p = pressure increase due to the solution.

0.0000 .0338 .0359 .0293 .0137

16.0 53.6 59.1 52.3 33.5

*.

Equilibrium in the System t-Butyl Chloride, t-Butyl Acetate, Hydrogen Chloride.-In analogy with the report of Steigman and HammettI4 for a-phenylethyl chloride, t-butyl chloride solvolyzes in initially neutral acetic acid to give an equilib-

The Henry's law constant of t-butyl chloride in water was estimated from the vapor pressure and a rough determination of the solubility of the halide in water (cu. 3 X M). Summary For compounds which appear to solvolyze by a

854

ERNST BERLINER N D A

FRANCES

J. BONDHUS

VOl.

'To

rate determining ionization, plots of the logarithm of the first-order rate constant k in various solvents (either from the literature or here reported) against log k for t-butyl chloride are linear. A set of values of the so-called ionizing power, Y,defined by the equation

for the relationship among the pertinent activity f2, coefficients( f ~ , etc.) for any two compounds A and B. It is postulated that linear logarithmic relationships among ratios of activity coefficients of this type may be quite general. The solvolysis of t-butyl chloride is discussed in terms of the Bronsted equation. It is shown Y = log kBQCl - log k p l that, to a good approximation, log f&c1 varies (kBUcl and koBu'21 being solvolysisrate-constants for aqueous solt-butyl chloride a t 25.0' in the given solvent and linearly with logfBUa in the partlyvariation in k vents and that in these solvents the in SOY0 ethanol) has been set up for a number of is due largely to changes infBuC1. On the other solvents includmg water, methanol, ethanol, aque- hand, in the more poorly ionizing solvents changes ous alcohols, formic acid and acetic acid. The in k are attributable mainly to changes in f&~. solvolysis rate constants (varying sonietimes by The reported method of correlating unimolecusix orders of magnitude) are fitted by the equation lar type solvolysis rates is useful in elucidating the log k = mY + log K O nature of the solvolysis of materials the rates of with a mean probable error of less than 0.05 in the which depend markedly on the nucleophilic charcases of t-butyl bromide, neopentyl bromide, a- acter of the solvent. For isopropyl p-bromomethylneopentyl 9-bromobenzenesulfonate, a- benzenesulfonate the rates of solvolysis in acetic methylallyl chloride, a-phenylethyl chloride and acid and acetic acid-acetic anhydride mixtures furnish estimates of unimolecular solvolysis rates benzhydryl chloride. The observed linear relationships, interpreted in ethanol, methanol and aqueous ethanol. The on the basis of the Bronsted equation, lead to the actual solvolysis rates are considerably larger in the latter solvents, the fractions of unimolecular equation solvolysis being low. log -- = mA log& .fA constant Los ANCELES CALIFORNIA 24, RECEIVED AUGUST 15, 1947 f h mB

[CONTRIBUTION FROM THE

MARION EDWARDS PARK LABORATORY BRYN MAWR OF COLLEGE]

Hyperconjugation. 1 . The Competitive Bromination of Benzene and 1 t-Butylbenzene

B ERNST Y BERLINER N D FRANCES BONDHUS A J. When benzene and t-butylbenzene in an equimolecular mixture in 92% acetic acid are allowed to compete for an insufficient amount of bromine, the corresponding brominated hydrocarbons are formed in proportions which show that the ratio of the rates of bromination a t 25' is about 115: 1 in favor of t-butylbenzene. At 45' the ratio is about 72 :1. 'Therefore the bromination of benzene requires a higher energy of activation than the bromination of t-butylbenzene.' Since under the same conditions toluene is brominated about four times faster than f-butylbenzene,2*a rate the of bromination of toluene appears to be about 465 times faster than that of benzene. Values for the individual rates of chlorination of toluene
(1) The bromination of difierent aromatic compounds is probably another case in which the differences in rate are primarily due t o dit. ferences in the E term of the Arrhenius equation (Scheffer and Blanks-, Rcc. Iros. chim., 46, 522 (1928); Bradfield and Jones, J . Chcm. SOC., 1006 (1928)); i:e.,the relationship (log ki/ka)n = T:/TI (log ki/ka)Ta should. hold. In the competitive bromination of toluene and I-butylbensene the calculated ratio a t 45" is 3.70 (found, 3.80); in the present bromination the agreement is less satisfactory (calculated ratio n l 4.5': 86.7. found: 71.8). This may be due to irregularities on account o the greater difference in rate. f (2) Berliner and Rondhus, T i m JOURNAL,68, 2355 (104G). (3) De 111 Mnrr :itmI I<ol>ertsnn,J . Chc,~r. o r . , ?7!) (1943). S

and benzene iix the ratio a t about 345,a,4 whereas in nitration with acetyl nitrate toluene reacts twenty-three times faster than benzene.6 The difference in the rates of bromination of toluene and t-butylbenzene was explained by nobond resonance of the Baker-Nathan type,2B8*6 which involves carbon-hydrogen bonds, but the much greater difference between t-butylbenzene and benzene clearly cannot be accounted for by such resonance, since no a-hydrogen atoms are available for conjugation.' On the other hand, it would be hard to see how the inductive effect, which, on the basis of the Baker-Nathan theory, should be operative in the absence of hydrogen atoms, could alone account for the great activation and strong ortho-$Jura directive influence of the t-butyl group, particularly since inductive effects of alkyl groups are conceded to operate through a rather feeble relay mechanism. The definitions that make the Baker-Nathan type of resonance
(4) This ratio is for 80% acetic acid; the ratio of the rate of chlorination o I-butylbenzene and benzene is 110. f ( 5 ) Ingold, Lapworth, Rothstein and Ward, J . Chcm. Soc., 1959
( I 931). ( 0 ) Baker nnd Nathan, i b i d . , 1840 (1!)3.5).

(7) Baker, i h i d . , 1150 (1939).