I HOWARD STEINBERG and D. L.
HUNTER
Research Division, United States Borax & Chemical Corp., Los Angeles 5, Calif.
reparation and Rate of Hydrolysis of
Boric Acid Esters
,The possibility of preparing stable
esters b y consideration of the stereo-
chemical requirements in the hydrolysis
prompted the work reported which is
concerned with the synthesis of the
boric acid esters from 38 primary,
secondary, and tertiary alcohols, gly-
cols, and phenols and the determina-
tion of their rates of hydrolysis in
water and aqueous dioxane. Six new
esters of high hydrolytic stability are
included.
T H E literature contains numerous
references to the preparation of organic
esters of boric acid utilizing a wide
variety of alcohols, glycols, and phenols
( 7 7 , 73, 75, 77, 27, 25, 30, 34). Many
of the references include isolated and
qualitative statements as to the hydro-
lyric stability of the esters (75, 77, 25,
26, 34).
Scattergood and coworkers (30) have
formulated some generalizations as to
the rate of hydrolysis of some aliphatic
esters based on qualitative observa-
tions, and more recently isolated ex-
amples of quantitative data have ap-
peared (6, 70).
Preparation of Esters
The general procedure for the prep-
aration of the esters involved the reaction
of boric acid with the appropriate alco-
hol or phenol.
r O\
R B--0-R- 0-b R
'0
I I1
174 INDUSTRIAL AND ENGINEERING CHEMISTRY
HSBOB + 3ROH + (R0)jB + 3H20
The Lvater of the reaction bras removed
as (A) a binary azeotrope with excess
alcohol (2); (B) a binary azeotrope
with added toluene; or (C) a ternary
azeotrope with excess alcohol and ben-
zene (21). A packed column (12 X
3 j 4 inches) was employed to remove the
ternary azeotrope effectively. Excess
boron oxide (D) was also employed in
place of the boric acid, in which case
the water of the reaction is consumed
by the excess reagent (37).
B20j + 3ROH -+ (RO)zB + H8BO.j
Excess alcohol and added toluene or
benzene were then removed by distilla-
tion and the residual ester was purified
by distillation or recrystallization.
Wherever necessary, manipulations werc
performed in a dry box. Table I
records the preparative data.
Boron analyses were performed by
hydrolysis and titration of boric acid in
the presence of mannitol (35). Because
of prolonged periods of reflux necessary
for complete hydrolysis, the stable esters.
21, 23, 26-32, and 42, were analyzed
by fusion with sodium carbonate at
850" C., solution in water, and titration
of the boric acid. Triethanolamine bor-
ate, triisopropanolamine borate, and the
phenolic borates, 36-40, were also
analyzed by the fusion method to
avoid interference of the amine or
phenols in the final titration. In the
case of the two alkanolamine borates,
the samples were dissolved in concen-
trated hydrochloric acid for 72 hours
prior to the carbonate fusion.
The melting and boiling points of
15, 16, 19, 23, 26-31, and 42 are de-
termined by and vary with the stereo-
isomers present.
The structure of the trialkyl borates
is well documented. However, only
partial evidence exists on the structure
of the glycol biborates. Both tri-(hex-
ylene glycol) biborate (2-methyl-2,4-
pentanediol) and tri-(octylene glycol)
-
biborate (2,5 - dimethyl - 2,5 hexane-
diol) are capable of existence in two
forms (I and 11).
One indication that structure I is the
favored form is the failure to produce
a biborate from 2,5-dimethyl-3-hexyne-
2,5-diol. only polymeric material result-
ing. The acetylenic diol is incapable of
structure I because the linearity of the
triple bond prevents 7-membered ring
formation (38), but it could form the
14-membered rings of structure 11.
Further evidence indicates that 1,3-
diols lead to structure I, Trhereas 1,4-
diols give structure 11. Partial hy-
drolysis of the biborate from 2-methyl-
2,4-pentanediol led to the isolation of
111, whereas the corresponding 7-mem-
bered ring could not be demonstrated
to be present from the partial hydrolysis
of the biborate from 2,5-dimethyl-2,5-
hexanediol.
CHI CHa
C H s C/
H \/
I I\
0
'
0 CHI
B/
I
OH
I11
 6
e"0,
h
0
5 s
V
h

V
1 E
R
v) W I-
h m
4 4 'I
m m N N

7 7 N N
4 4 'I 'I
m m N N

.-3
e
i
3 s
3 i
s
v)

al
I

0
--
m
W

8
-- --a
m
W

0
m
W

V V V S

9 % 9 9
0, o_ o_
V 6 u" u"

m W a

-
0
h m
7
N
8 10
4
3
4
3
F
3
4
VI
L
aJ
c
Li w I
a
* v

2 w
c1 m
N m
PI h
v)

Y
.-v
L
0 0 0 0
m0 m0 2 x
0
m
%
0
. . . L o .
.-6
c
: : : 2 ;
u
L
m
m
3
0
a
aJ
h

-
w a
3
88 8

PI 4PIvPI4PI vF9 4F9 PI PI PIPIPIPIPIPIPI

h

0)
1
E
a
R
A
a

-
a
h

a
Y -
a R

5!
h
9
9
N

4 4 u;

VOL. 49, NO. 2 FEBRUARY 1957 175

 h
h
hl
1 v,
Y v

W 3
h
09
ln W

b a
L:
* m
W

2
a
E
-
.dR
&

Lq
9
ON
@V

3 : : :
x

-3
a : : : .
.
N
N

a
b
*. ..
?
3

t-
3 . m
m . N
3 In
b m
N

M d
AX * E
Y

2
0
\
In
b
.-I

W N O b o * a
. .
3
3
? 3 N
4 4 s 0:
0 *
In O
a
N
m
m m e W
In
m
b
* N m
h
m
3-7
m l n 3

a W
0 a * ln - a a
h
a W b b e m

F9 F9 F 9 F 9 F9 RF9 w

a d d A d & i
N N m m m m m

176 INDUSTRIAL AND ENGINEERING CHEMISTRY

 Relative Rates of Hydrolysis
Table II. Rate of Hydrolysis of Boric Acid Esters in 60% Aqueous Dioxane at 2 1 C. 60% (Vol.) Aqueous Dioxane at 21
Initial Concn., C. The following procedure was devel-
Reactants, Mole/Liter Half-Life
oped for the measurement of the hydroly-
kl ,
Run (tlld, Bee-.' sis rates. A weighed sample of ester (0.4
No. Ester Ester Sec. x 104 to 1.2 mmoles) was dissolved in 15 ml. of
purified dioxane (9). A solution of 10
1 Trimethyl borate 0.0238 0.0117' ml. of dioxane, 3 drops of phenolphtha-
2 Triethyl borate 0.0216 0.0106 lein, 15 ml. of a 9.09 weight % solution
3 Tri-n-propyl borate 0.0246 0.0123
of mannitol in water, and one half of the
4 Triisopropyl borate 0.0231 0.0116
5 Tri-( 1,3-dichloro-2-propyl) borate 0.0284 0.0142
amount of 0.2457 or 0.1130N sodium
6 Tri-n-butyl borate 0.0238 0.0117 hydroxide (approximately 2 ml.) neces-
7 Triisobutyl borate 0.0252 0.0128 sary for neutralization of the boric acid
8 Tri-(P,i3,@-trichloro-terL-butyl)borate 0.0088 0.0044
Too fast to >6930 resulting from complete hydrolysis were
measure
9 Tri-(hexylene glycol) biborate 0.0123 0.0121 added a t zero time. The resulting solu-
10 Triphenyl borate 0.0235 0.0118 tion was swirled to effect homogeneity
I1 Tri-o-chlorophenyl borate 0.0168 0.0084 and the time for fade of the indicator was
12 Tri-o-cresyl borate 0.0247 0.0121 recorded as the half life (Table 11).
13 Tri-(o-phenylphenyl) borate 0.0075 0.0038 A blank determination with 1 mmole
14 Tri-(0-cyclohexylphenyl) borate 0.0142 0.0071,
15 Tri-n-amyl borate 0,0238 1.0 6930
of boric acid and 0.5 meq. of sodium
16 Tri-(octylene glycol) biborate 0.0107 1.5 4620 hydroxide under the above conditions
17 Tri-n-hexyl borate 0.0238 2.9 2390 was too fast to measure. Compensation
18 Tri-sec-butyl borate 0.0230 3.5 1980 for the phenols liberated in runs 10 to
19 Tri-( 1-ethynylcyclohexyl) borate 0.0130 13.7 506 12 with additional base still led to half
20 Tri-n-octyl borate 0.0238 16.0 433 lives which were too fast to measure.
21 Trioleyl borate 0.0078 16.7 415 91% (Vol.) Aqueous Dioxane at 21'
22 Tri-n-dodecyl borate 0.0128 21.3 326 and 55' C. The limited solubility of
23 Tristearyl borate 0.0086 21.7 319 several of the esters in 6OY0 dioxane
24 Tri-2-octyl borate 0.0110 136 51.0
25 0.0128
necessitated their hydrolyses in more con-
Tri-(2-ethylhexyl) borate 213 32.6
26 Tri-(methylisobutylcarbinyl) borate 0.0156 242 28.6
centrated dioxane. I n addition three
27 Tri-tert-butyl borate 0.0235 428" 16.2 other solid esters required an elevated
28 Tri-3-pentyl borate 0.0228 1220 5.68 temperature for homogeneity.
29 Tri-3-heptyl borate 0.0124 1416 4.90 Weighed samples of the esters (0.4
30 Tri-(2,6,8-trimethyl-4-nonyl)borate 0.0046 1.27 x 104 0.546 to 0.8 mmole) were dissolved in 70 ml,
(3.53 hr., of dioxane containing 5 ml. of water and
550 C.) enough 0.1130N sodium hydroxide (ap-
a Half life a t 5 5 O C. was 44.4 seconds @I = 156 X lo4 sec.-1). proximately 2 ml.) to neutralize ong

Table 111. Rate of Hydrolysis of Boric Acid Esters in 91% Aqueous Dioxane at 21 O and 55' C.
Initial Concn.,
Reactants, Mmole/Liter Half Life
Run Sodium Time, Hydrolyzed, (tl/d?
No. Ester Ester hydroxide Sec. X 10-8 % Hours
Temperature, 55" C.
31 Tri-tert-amyl borate 10.7 5.35 0.148 51.3 2.38 4860
(min.)
32 Tri-(2-phenylcyclohexyl) borate" 5.63 2.82 3.48 72.2 0.522 368
33 Tri-(diisobutylcarbinyl) borate 5.97 2.97 28.2 83.2 3.03 63.3
34 Tri-(2,6,8-trimethyl-4-nonyl)borate 5.32 2.66 29.4 78.4 3.70 52.2
35 Tri-(2-cyclohexylcyclohexyl) boratea 5.48 2.75 27.6 66.5 4.86 39.7
36 Tri-(dicyclohexylcarbinyl) borate 4.70 2.36 29.7 27.4 17.8 10.8
37 Tri-(2-phenylcyclohexyl) borate" 5.33 .. 5.88 72.8 0.867 222
38 Tri-(diisobutylcarbinyl) borate 5.22 .. 76.2 39.4 29.4 6.57
39 Tri-(2,6,8-trimethyl-4-nonyl)borate 5.14 .. 75.6 25.7 49.2 3.92
40 Tri-(2-cyclohexylcyclohexyl) borateD 6.56 .. 76.5 17.9 74.5 2.59
41 Tri-(dicyclohexylcarbinyl) borate 5.38 .. 75.9 8.2 170 1.13

Temperature, 21° C.
42 Tri-tert-amyl borate 6.36 3.18 1.80 56.9 0.411 468
43 Tri-trans-(2-phenylcyclohexyl) borate 5.04 2.53 71.3 80.9 8.32 23.2.
44 Tri-(2-phenylcyclohexyl) borate" 4.90 2.47 73.0 76.3 9.72 19.8
45 Tri-cis-(2-phenylcyclohexyl) borate 5.60 2.79 72.7 69.6 11.7 16.4
46 Tri-(2,6,8-trimethyl-4-nonyl) borate 4.71 2.35 243 74.8 33.9 5.67
47 Tri-tert-amyl borate 10.0 8.22 74.6 1.15 167
..
. I

48 Tri-trans-(2-phenylcyclohexyl) borate 5.24 71.1 60.8 14.6 13.2

49 Tri-(2-phenylcyclohexyl)boratea 5.00 .. 72.7 55.6 17.2 11.2
50 Tri-cis-(2-phenylcyclohexyl) borate 5.67 .. 71.5 48.8 20.4 9.37
51 Tri-(2,6,8-trimethyl-4-nonyl)borate 6.05 .. 243 24.3 167 1.15

0 Cis-trans mixture.

VOL. 49, NO. 2 FEBRUARY 1957 177-

half of the boric acid resulting from com- necessary to neutralize the boric acid
plete hydrolysis of the ester, I n half resulting from complete hydrolysis was Table V. Hydrolysis of
the runs the base was eliminated, and added to a weighed sample of ester. The Triisopropanolamine Borate in
7 ml. of water was used. mixtures were agitated, and the time for Water at 25" C.
The solutions were maintained a t 21 " fade of the indicator was recorded as Concn. of, Hydro-
or 5 5 " C. for various periods, cooled to the half time. Compensation for the Time, Ester (a - x ) , lyzed,
room temperature, and diluted with 300 liberated phenols (runs 53, 54, and 59) Hr. Mole/Liter 7%
ml. of water. Mannitol and phenol- with additional base did not materially 0 0.0954 0
phthalein were added, and the boric change the half times. 0.37 0.0948 0.62
acid was titrated with 0.1 130N sodium The esters with half times greater than 3.55 0.0925 2.96
5.83 0.0916 3.94
hydroxide. I n one case (run 36) the 2 days were back-titrated with 0.0240N 23.3 0.0904 5.17
unconsumed base was back-titrated with hydrochloric acid within the first day. 94.7 0.0897 5.89
0.0240N hydrochloric acid. The per The half times were then calculated, 120 0.0896 6.02
cent hydrolysis allows calculation of the assuming first-order kinetics. Table IV 172 0.0894 6.28
264 0.0891 6.53
half life and first-order rate constant summarizes the heterogeneous hydrolysis 458 0.0582 7.48
(Table 111). data. 571 0.0877 7.99
Water at 21' C. (Heterogeneous). Tri-(hexylene glycol) biborate may
I n order more closely to approximate have undergone only partial hydrolysis
actual conditions of possible applications to structure 111. Such a material was
of the boric acid esters, the esters were isolated in 897, yield from a neutral was performed at 35' C. to prevent
subjected to hydrolysis by agitation in hydrolysis in the absence of mannitol; solidification of dodecyl alcohol and
water. A solution of 50 ml. of water, 5 melting point 74.4-75.2' C. Analysis. erratic results. The half time at 21 O C.
grams of mannitol, 4 drops of phenol- Calcd. for CeH1303B: B, 7.52%. was calculated from the value at 35" C.
phthalein, and one half the amount of Found: B, 7.447,. ( 3 64 minutes) assuming a rate doubling
0.2457 or 0.1 130Ar sodium hydroxide The hydrolysis of the dodecyl borate for every 10 temperature increase.
Alkanolamine Borates in Water at
25 " C. The nitrogen-containing water-
soluble ester. triisopropanolamine borate,
Table IV. Relative Rates of Hydrolysis of Boric Acid Esters in Water ot 21 C. was subjected to hydrolysis by dilution
Reactants of a 1.8986-gram sample to 100 ml. in a
Sodium volumetric flask. Ten-milliliter aliquots
Run Ester, hydroxide, Relative mere periodically removed and titrated
No. Ester mmoles meq. Half Time Rate with O.0235OA1-hydrochloric acid. The
52 Trimethyl borate 2.27 1.13 1 Too fast to data are given in Table 1'.

53
54
Tri-o-chlorophenyl borate
Triphenyl borate
1.02
1.08
0.510
0.540
,/ measure

6.0 sec.
>1.91 X
>1.91 X
3.18 X
lo7
lo7
lo6
The sensitivity of triethanolamine
borate to acid (6) precludes the possi-
55 Tri-n-amyl borate 0.735 0.368 7.7 sec. 2.48 X 106
bility of following the hydrolysis in
56 Triethyl borate 1.41 0.699 7.8 sec. 2.45 X 106 neutral solution by titration of the
57 Tri-n-hexyl borate 0.558 0.278 11.8 sec. 1.62 X 106 amine ; however, reproducible values
58 Tri-( 1,3-dichloro-2-propyl) borate 0.987 0.493 12.0 sec. 1.59 X 106 may be obtained by back-titration of
59 Tri-o-cresyl borate 0.660 0.330 13.5 sec. 1.42 X 106
60 Tri-n-butyl borate 0.800 0.399 18.3 sec. 1.04 X 106
unconsumed hydrochloric acid. Con-
61 Tri-n-octyl borate 0.456 0.227 21.7 sec. 8.80 x 106 sequently a 0.7207-gram (4.59-mmole)
62 Tri-n-propyl borate 1.29 0.646 38.8 sec. 4.92 X 106 sample of triethanolamine and 19.4
63 Tri-(2-ethylhexyl) borate 0.538 0.270 70.0 sec. 2.73 X 106 ml. of 0.2367,V hydrochloric acid (4.59
64 Triisobutyl borate 0.932 0.468 82.5 sec. 2.32 x 105
65 Tri-(hexylene glycol) biborate 0.588 0.581 106 sec. 1.80 x 106
meq.) were rapidly mixed and diluted
66 Trioleyl borate 0.463 0.232 3.80 min. 8.37 x 104 to 50 mi. Five-milliliter aliquots werr
67 Tri-(octylene glycol) biborate 0.529 0.530 8.59 min. 3.70 x 104 removed and rapidly titrated with
68 Tri-n-dodecyl borate 0.323 0.162 9.60 min. 3.31 X 104 0.024955 sodium hydroxide. Table
69 Triisopropyl borate 1.06 0.530 9.68 min. 3.28 x 104
70 Tri-( 1-ethynylcyclohexyl) borate 0.787 0.392 10.4 min. 3.06 x 104 VI summarizes the data.
71 Tri-2-octyl borate 0.719 0.360 16.1 min. 1.98 x 104
72 Tri-see-butyl borate 1.11 0.555 53.7 min. 5920 Discussion
73 Tristearyl borate 0.868 0.435 58.0 min. 5490
74 Tri-(methylisobutylcarbinyl) Scope a n d Limitations. 4 point
borate 0.703 0.353 71.7 min. 4430 which the present work does not explore
75 TIi-tert-amyl borate 0.992 0.497 2.58 hr. 2050
is the nature of the actual species neutral-
76 Tri-tert-butyl borate 0.911 0.455 2.81 hr. 1890
77 Tri-3-heptyl borate 1.22 0.610 4.64 hr. 1140 ized by the sodium hydroxide. I t has
78 Tri-(P,P,P-trichloro-terf- been assumed to be the boric acid-man-
butyl) borate 0.633 0.317 47.0 hr. 113 nitol complex which would result from
79 Tri-(2,6,8-trimethyl-4-nonyl)
borate 0.813 0.407 3.33 days 66.3
(16.6y0, 21.03 hr.)
80 Tri-3-pentyl borate 1.78 0.890 6.36 days 34.8
(1.52%, 3.38 hr.) Table VI. Acid-Catalyzed Hydrolysis
81 Tri-( 2-cyclohexylcyclohexyl) 0.877 0.437 15.3 days 14.4
boratea (3.88y0, 21.02 hr.) of Triethanolamine Borate in Water at
82 Tri-(dicyclohexylcarbinyl) borate 0.770 0.384 18.6 days 11.9 25" C.
(3.2570, 21.35 hr.) Concn. of
83 Tri-(2-phenylcyclohexyl) boratea 0.900 0.448 42.0 days 5.27
(1.44y0, 21.1 hr.) Time, Ester (a - z), Hydrolyzed,
84 Tri-(diisopropylcarbinyl) borate 1.34 0.675 68.5 days 3.23 See. Mole/Liter %
(0.895%, 21.37 hr.) 0 0.0918 0
85 Tri-(diisobutylcarbinyl) borate 1.09 0.546 221 days 1 152 0.0360 60.8
(0.27570, 21.2 hr.) 322 0.0184 80.0
467 0.00698 92.4
Q Cis-trans mixture. 617 0.00395 95.7

178 INDUSTRIAL AND ENGINEERING CHEMISTRY

complete hydrolysis of the ester. How- there is a tendency toward direct pro-
ever, the possibility of more than portionality of the half life and ( a - b). Table VII. Relative Rates of Hydrolysis
momentary existence of partially hydro- As initial ester and base concentrations of Boric Acid Esters in Aqueous Dioxane
lyzed species, (R0)zBOH and ROB- in the ratio of 2 to 1 are increased, t1/2 Relative
(OH)2, cannot be ruled out, since 1- increases. Although these problems Ester Rate
menthoxyboric acid, CloHISOB(0H) 2, have not been resolved, a comparison Trimethyl borate
has been isolated by partial hydrolysis of hydrolysis rates was made on the basis Triethyl borate
of 1-menthyl metaborate trimer (24). of the pseudo-unimolecular reaction Tri-n-propyl borate
Such species would be expected to be Triisopropyl borate
rate constants, kl, calculated by use Tri-( 1,3-dichloro-2-propyl)
capable of at least partial titration in the of the integrated form of the expression borate
presence of mannitol, as has been per- for a first-order reaction Tri-n-butyl borate
formed with the similar boronic (79, 33) Triisobutyl borate
and borinic acids (20). The partially 2.303 Tri-(P,P,&trichloro-tert- >5.87 X IO6
hydrolyzed species (111) can be quanti-
ki = - log
t
2-
(a - x)
butyl) borate
Tri-(hexylene glycol)
tatively titrated in the presence of man- biborate
nitol. where a is the initial concentration of Triphenyl borate
The effects of the changing ionic Tri-o-chlorophenyl borate
the ester and ( a - 2) is the concentration Tri-o-cresyl borate
and basic strength of the medium due to of the ester remaining at time t. Such Tri-(o-phenylphenyl) borate
the reaction of the sodium hydroxide first-order rate constants appear in Tables Tri-(o-cyclohexylphenyl)
with the boric acid produced have also I1 and 111. I n support of this arbitrary borate I
Tri-n-amyl borate 5.87 x 105
been neglected. procedure are the identical relative Tri-(octyiene glycol) biborate 3.92 X lo5
The hydrolysis of esters of inorganic orders of the esters for the hydrolyses Tri-n-hexyl borate 2.02 x 105
acids in general is accelerated by alkali, in both basic and neutral solution Tri-sec-butyl borate 1.68 x 105
but the effect is not very marked (23). (Table 111). Tri-( 1-ethynylcyclohexyl)
borate 4.29 x 104
The basic catalysis of the boric acid Comparison of Rates. The rates at Tri-n-o ctyl borate 3.67 x 104
ester hydrolyses is made evident by 21 " C . in 60% dioxane (Table 11) and at Trioleyl borate 3 . 5 3 x 104
comparison of the rates of groups 1 and 55 " C. in 91% dioxane (Table 111) were Tri-n-dodecyl borate 2.77 x 104
2 and groups 3 and 4 of Table 111. In adjusted to a common basis as follows. Tristearyl borate 2.71 x 104
Tri-2-octyl borate 4.33 x 103
the presence of base, the average rate Comparison of the half lives of tri-(2,6,8- Tri-(a-ethylhexyl) borate 2.77 x 103
a t 55" C. increased by a factor of 9.9 trimethyl-4-nonyl) borate at 55 " C. in Tri-(methylisobutylcarbinyl)
and a t 21" C. by a factor of 2.6. The 60% dioxane (run 30) and 91% dioxane borate 2430
hydrolyses in 6070 dioxane are further (run 34) shows the hydrolysis to proceed Tri-tert-butyl borate 1370
Tri-3-pentyl borate 483
complicated by the presence of the man- 1.05 times faster in the 60y0 dioxane. Tri-tert-amyl borate 449
nitol. Any basic catalysis present ini- Comparison of the half lives for tri- Tri-3-heptyl borate 415
tially is diminished as the hydrolysis tert-butyl borate in 60y0dioxane at 21 " Tri-trans-(2-phenyl-
proceeds because of neutralization of and 55" C. (run 27) shows the reaction cyclohexyl) borate 40.0a
the base by the acidic boric acid-man- Tri-(2-phenylcyclohexyl)
to proceed 9.63 times faster at the ele- borateb 34.1
nitol complex. This effect is made vated temperature. Therefore, to com- Tri-cis-(2-phenylcyclohexyl)
evident when the mannitol is added to pare the rates a t 21 " C. in 60% dioxane borate 28.2'
the system a t some point after zero time. to the base rate of tri-(dicyclohexyl- Tri-(diisobutylcarbinyl)
borate 5.86
The half life of 2-ethylhexyl borate was carbinyl) borate at 55" C. in 91% di- Tri-(2,6,8-trimethyl-4-nonyl)
diminished from 213 to 115 seconds oxane (run 36), the rates at 21" C. in borate 4.83
when the mannitol was added after 50 6OY0dioxane are multiplied by 1/ 1.05 X Tri-(2-cyclohexylcyclohexyl)
borate 3.67
seconds and further diminished to 107 9.63 = 9.17. Table VI1 records the
seconds when the mannitol was added Tri-(dicyclohexylcarbinyl)
relative rates. borate 1
after 100 seconds. Hydrolyses in Aqueous Dioxane. 5 Rate constant increased by factor of 18.6
The exact function of the base in the The relative rates of the aliphatic and ali- to compensate for temperature differential
hydrolysis is not elucidated. If the cyclic esters are in the order predicted (runs 32 and 44, Table 111).
sole function of the hydroxyl ion were by the steric requirements in the nucleo- * Cis-trans mixture.
to compete with water in an attack upon philic attack of water (or hydroxyl ion)
the boron atom of the ester, an over-all on the central boron atom.
acceleration of rate would result as OR OR
shown above. However, an inverse
H RO H
relationship of half life and concentra-
\
'0: + \
$-OR +
\ .0- A+
'-
I
- -B -
P-

-:OR + HO-B
/
f ROH
tion would also be a necessary conse-
quence. This follows from the inte-
grated expression for the second-order
H
/
RO
/
H
/
OR
I
4
etc.
Hz.OO
'R

reaction rate constant, kl. The greater the bulk of the alcohol the Rz = butyl). In every case, the esters
slower the rate of hydrolysis. Thus in derived from secondary alcohols hy-

2.303 b(a - x )
k) = ___ b ) log
t(a - -
a(b X )
where a, 6 , and x are the initial concen-
tration of ester, initial concentration of
base, and concentration of ester con-
sumed, respectively. At 50% reaction
or at the half life, x = I / Z U
The half life is inversely proportional
to the difference in initial concentrations
of ester and base (a - 6). I n actuality
- -
the normal alkyl borates: methyl-
ethyl propyl butyl > amyl > hexyl
> octyl > dodecyl > stearyl. Branching
of the alkyl chain produces a further
decrease in rate: n-octyl > 2-ethylhexyl.
In the esters derived from straight-
chain secondary alcohols, (RlRzCHO)sB,
the bigger the R1 and Rz groups the
slower the rate of hydrolysis: isopropyl
(RI = R2 = methyl) > sec-butyl (R1 =
methyl, R 2 = ethyl) > 2-octyl (R1 =
methyl, R 2 = hexyl) > 3-pentyl (R, =
R Q = ethyl) > 3-heptyl (R1 = ethyl,
drolyze more slowly than their primary
counterparts.
The tertiary alcohols in turn give rise
to more stable esters than do the sec-
ondary alcohols: sec-butyl > tert-butyl,
3-pentyl > tert-amyl. In the tertiary
series itself, I-ethynylcyclohexyl with two
groups tied back in a ring hydrolyzes
more rapidly than tert-butyl, which in
turn hydrolyzes more rapidly than the
more bulky tert-amyl.
The glycol biborates follow the second-
ary-tertiary trend. Hexylene glycol

VOL. 49, NO. 2 0 FEBRUARY 1957 179

 biborate with one secondary and one
tertiary oxygen-bearing carbon hydro-
lyzes more rapidly than octylene glycol
biborate which possesses two tertiary
linkages. I n addition, hexylene glycol
biborate with its six carbon atoms tied
back in a ring and away from the boron
atom is more susceptible to hydrolysis
than the analogous open-chain methyl
isobutyl carbinyl borate.
Cis-2-phenylcyclohexyl borate hydro-
lyzes more slowly than the trans isomer.
These results are in accord with Vavon
and coworkers (36), who found that
cis-2-cyclohexylcyclohexyl succinate sa-
ponified more slowly than the trans
succinate.
T h e primary requisite for stability in
the present group of aliphatic and ali-

t
cyclic esters appears to be the shielding of
the boron atom with bulky groups below -1.06
and above the plane of the BO3 grouping.
Cyclohexylcyclohexyl groups serve this I I I I I I I
purpose, as do isobutyl or larger groups. 0 100 200 300 400 500 600
T h e symmetry of the dicyclohexylcar- t, hr.
binyl group compared to the 2-cyclo-
hexylcyclohexyl grouping allows for Figure 1. Hydrolysis of triisopropanolamine borate
equal distribution of the bulk below and
above the BO3 plane and, indeed, the
ester derived from the former is more Heterogeneous Hydrolyses in Water. -2.303 gives the first-order reaction
stable than the 2-cyclohexylcyclohexyl The divergence of solubilities, viscosities, rate constant for triisopropanolamine
borate. I n turn, the 2-cyclohexylcyclo- state of aggregation, and wetting proper- borate, 4.67 X 10-5 hr,-I, which is
hexyl group affords more protection ties of the various borates precludes the equivalent to a half-life of 618 days.
than the less bulky 2-phenylcyclohexyl validity of generalizations; however, Extrapolation to zero time indicates
group and is therefore more stable. some trends appear to be operative. 5.4% of a more rapidly hydrolyzed im-
Electronic and polar effects can sub- T h e rates of hydrolysis of the butyl purity.
stantially effect the hydrolysis rates. borates are as would be predicted on The first-order reaction rate constant
Tri - - - -
(p,P,p trichloro tert butyl) purely steric grounds: n-butyl > iso- for the acidic hydrolysis of triethanol-
borate might be expected to hydrolyze butyl > sec-butyl > tert-butyl, and once amine borateobtained from a plot (Figure
more slowly than its unsubstituted count- again the most stable members contain 2) of the data of Table V I is 5.32 X
erpart, tri-tert-butyl borate, because of the flanking cyclohexyl or isobutyl set.-'. The half-life in the presence
the added bulk of nine chlorine atoms. groups. of one equivalent of hydrochloric acid
However, the inductive effect of the Alkanolamine Borates. A plot (Fig- is thus 130 seconds as compared to the
halogen atoms serves to increase the ure 1) of the log of the total ester con- half life of 181 seconds (with 0.5 equiva-
electrophilic reactivity of the boron atom centration us. time (Tabel V) reveals a lent of acid present) as found by Brown
sufficiently and produce an over-all ac- straight line after 50 hours. Multiplica- and Fletcher (6).
celeration of rate. Analogous reasoning tion of the slope (-2.03 X 10-5) by The cryoscopic molecular weight data
could be applied to the triisopropyl
borate and tri-(1,3-dichloro-2-propyl)
couple. Both, unfortunately, hydro-
lyze too rapidly to be measured by the
present method.
The aromatic borates (phenyl, o-
chlorophenyl, and cresyl) also hydrolyze
too rapidly to be measured. This is
not unexpected in view of the lowered
electron density on the boron atom due
to the withdrawal of electrons by the
aromatic nucleus (7).

bO

Even the highly hindered aromatic

I
0 IO0
I
2 00
I
300
I I
400
I
500
I
600
borates (0-phenylphenyl and o-cyclo-
t, sec.
hexylphenyl) hydrolyze a t a rate too
fast to measure. Figure 2. Hydrolysis of triethanolamine borate

1 80 INDUSTRIAL AND ENGINEERING CHEMISTRY

of Hein and Burkhardt (74) for tri-
ethanolamine borate in neutral solution
can be interpreted into a n approximate
rate of hydrolysis. They found the
freezing point depression of a water s o h -
tion (0.107,M) at 20’ C. to increase
with time and level after 271 min-
utes. Assuming 99 to 99.99% hydroly-
sis a t that time, the half life would
range from 40.8 to 20.4 minutes.
A comparison of the rates of hydrolysis
of triethanolamine borate and triiso-
propanolamine borate with their closest
open-chain analogs, triethyl borate and
triisopropyl borate, shows the nitrogen-
containing “cage” structures (IV) to
be far the more stable.
CHR CHR CHR
IV. R = H, CHI
Brown and Fletcher (6) noted that
triethanolamine borate could exist either
in the cage structure IV or the tetra-
hedral structure V resulting from a
transannular interaction of the “lone
pair’’ of electrons on the nitrogen atom
with the open sextet of the boron atom.
V. R = H,CHa
From the inertness of the nitrogen atom
toward methyl iodide and toward meth-
anesulfonic acid in nitrobenzene, these
authors concluded that a transannular
bond must be present.
Neglecting the solvent effects of water
and GOO/, aqueous dioxane in the
present work, triethanolamine borate
hydrolyzes a t <1/130 the rate of triethyl
borate and triisopropanolamine borate
reacts a t <1/5.35 X 107 the rate of its
open chain counterpart, triisopropyl
borate. However, the accessibility of
the boron atom in the cage structure
(IV) to attack by water would indicate
a rate of hydrolysis a t least comparable
in order of magnitude to those of the
open-chain analogs. T h a t this situation
does not hold provides independent
support for the existence of a transan-
nular bond in molecules of this kind.
I n addition, intramolecular coordination
of amino nitrogen to boron has been sug-
gested in P-aminoethyl diphenylborinate
(20).
Comparison of the half lives of 130
seconds a t 25’ C. for triethanolamine
borate and 618 days a t 25’ C. for tri-
isopropanolamine borate indicates the
latter to hydrolyze 4.11 X l o 5 times
slower than the triethanolamine borate.
This deceleration of rate in proceeding
from a primary to secondary alcohol far
surpasses any decreases observed in the
open-chain esters: n-octyl > 2-octyl
by a factor of 8.5, n-amyl > 3-pentyl
by a reactor of 1220, and n-hexyl >
3 heptyl by a factor of 487.
It is hoped a more detailed study of
the kinetics of the hydrolysis of tri-
isopropanolamine borate and its ap-
parent equilibration with its hydrolysis
products may be presented later.
Summary
Thirty-eight boric acid esters from a
variety of alcohols, glycols, and phenols
have been synthesized, characterized,
and subjected to hydrolysis in water,
GO and 91% aqueous dioxane a t 21 ’and
55’ C. Six new esters of high hydrolytic
stability are included. T h e relative
rates of the aliphatic and alicyclic mem-
bers are in the order predicted by the
steric requirements in the nucleophilic
attack of water (or hydroxyl ion) on
the central boron atom. T h e rapid
rate of hydrolysis of the highly hindered
aromatic and chlorine substituted ali-
phatic esters indicates a shift from steric
to electronic controlling factors for
these members.
Acknowledgment
T h e authors wish to thank the United
States Borax and Chemical Corp. for
permission to publish this work. They
would also like to acknowledge the value
of discussions with S. Winstein, E. W.
Fajans, and A. L. McCloskey and
the assistance of L. L. Petterson and G. N.
Thomas in the determination of some
of the physical constants.
Literature Cited
(1 ) Ahmad, T., Haider, S. Z., Khundkar,
M. H., J.Appl. Chem. 4,543 (1954).
(2) Bannister, W. J. (to Commercial
Solvents Corp.), U. S. Patents
1,668,797 (May 8, 1928).
(3) Beran, F., Prey, V., Bohm, H., Mitt.
Chem. Forsch.-lnst. Wbtsch. Osterr. 6,
54-6 (1952).
(4) Berti, G., J . Am. Chem. SOC.76, 1213
(1954).
(5) Blatt, A. H., “Organic Syntheses,”
Collective Vol. 11, p. 106, Wiley,
New York. 1948.
Brown, H. C:, Fletcher, E. A., J. Am.
Chem. Soc. 73, 2808 (1951).
Colclough, T., Gerrard, W., Lappert,
M. F., J. Chem. SOC.1955, p. 907.
Cook, H. G., Ilett, J. D.. Saunders,
B. C., Stacey, G: J., Ibih., 1950, p:
3125.
(9) Fieser, L. F., “Experiments in Organic
Chemistry, 2nd ed., p. 369,
Heath, New York, 1941.
.(IO) George, P. D., Ladd, J. R., J . Am.
Chem. Soc. 77, 1900 (1955).
(11) Gerrard, W., Lappert, M. F., Chem-
istry & Industry, 1952,p. 33.
(12) Graves, G. D., Werntz, J. H. (to E. I.
du Pont de Nemours & Co.), U. S.
Patent 2,053,474 (Sept. 8, 1936).
(13) Haider, S. Z.,Khundkar, M. H.,
Siddiqullah, Md., J . A@l. Chem. 4,
93 (1954).
(14) Hein, F., Burkhardt, R., 2. anorg.
Chem. 26%. 159 (195.2).
(15) Hiickel, W.,’Neun‘hoeffer, O., Gercke,
A., Frank, E., Ann. 477, 99 (1929).
(16) Jones, J. I., Lindsey, A. S.,J . Chem,
SOC.1950, p. 1836.
(17) Jones, W. J., Thomas, L. H., Pritch-
ard, E. H., Bowden, S. T., Ibid.,
1946, p. 824.
(18) Kahovec, L., Ber. 43, 109 (1939).
(19) Kuivila, H. G., Keough, A. H.,
Soboczenski, E. J., J . Org. Chem. 19,
780 (1954).
(20) Letsinger, R. L., Skoog, I., J . Am.
Chem. SOC.77, 2491 (1955).
(21) Lippincott, S. B. (to Standard Oil
Development Co.), U. S. Patent
2,642,453 (June 6, 1953).
(22) Mauersberger, E. A., Ibid., 2,036,593
(April 7, 1936).
(23) Noller, C. R., “Chemistry of Organic
Compounds,” p. 95, W. B. Saun-
ders, Philadelphia, 1951.
(24) O’Connor, G. L., Nace, H. R., J . Am.
Chem. SOC.77, 1578 (1955).
(25) Prescott, R. F., Dosser, R. C., Sculati,
J. J. (to Dow Chemical Co.), U. S.
Patent 2.260.336 (Oct. 28. 1941).
(26) Zbid., 2,260;337’and2,260,338.
(27) Ibid., 2.260.339.
(28) Zbid.; 2;300;006(Oct. 27, 1942).
(29) Price, C. C., Karabinos, J. V., J. Am.
Chem. SOC.62, 1159 (1940).
(30) Scattergood, A., Miller, W. H., Gam-
mon, J., Zbid., 67, 2150 (1945).
(31) Schlesinger, H. I., Brown, H. C . ,
Mayfield, D. L., Gilbreath, J. R.,
Ibid., 75, 213 (1953).
(32) Shriner, R. L., Fuson, R. C., “Identi-
fication of Organic Compounds,”
3rd ed., p. 163, Wiley, New York
- _ .-.
1948
(33) Snyder, H. R., Kuck, J. A., Johnson,
J. R., J. Am. Chcm. SOC.60, 105
(1938).
\ - - - - I .
(34) Thomas, L., J. Chem. SOC. 1946,p. 820.
(35) Van Liempt, J. A. M., Rec. trav. chim.
39. 358 (1920).
(36) Vavdn, G,’, Anziani, Herynk, Bull.
SOG. chim. 99, 1138 (1926).
. . Webster. S . H.. Dennis. L. M.. J.Am.
(37)
Chem. SOC.55, 3233 (1933). ’
(38) Wheland, G. W., “Advanced Organic
Chemistry,” 2nd ed., p. 376, Wiley,
New York, 1949.
(39) Wuyts, H., Duquesne, A., Bull. soc.
chim. Belg. 48, 77 (1939).
RECEIVED
for review January 23, 1956
ACCEPTED June 1, 1956
Division of Organic Chemistry, 128th
Meeting, ACS, Minneapolis, Minn., Sep-
tember 1955.
VOL. 49, NO. 2 FEBRUARY 1957 181