Desilylation and conversion of trimethylsilylmethyl epoxides into ketones under the influence of a bulky base

Article abstract of DOI:10.1002/hc.10036

Trimethylsilylmethyl epoxides were converted into ketones through a desilylation, epoxide ring-opening, and rearrangement reaction under the influence of a bulky base in the presence of 18-crown-6.

Full text of DOI:10.1002/hc.10036

Heteroatom Chemistry
Volume 13, Number 4, 2002
Desilylation and Conversion of
Trimethylsilylmethyl Epoxides into
Ketones under the Influence of a Bulky Base
Yuan Ma
Bioorganic Phosphorus Chemistry Laboratory, Department of Chemistry, School of Life Science,
Tsinghua University, Beijing 100084, People’s Republic of China
Received 20 July 2001; revised 9 October 2001
and aluminum dialkylamides have been investigated
ABSTRACT: Trimethylsilylmethyl epoxides were con-
widely in the reaction. Under these base-promoted
ring-opening conditions, epoxides yield generally al-
lylic alcohols; however, sometimes ketones are pro-
duced [1]. Trialkylsilylmethyl epoxides are important
kinds of functionalized epoxides. They, as synthetic
intermediates, have been widely used in the syn-
theses of bioactive compounds and natural prod-
verted into ketones through a desilylation, epoxide
ring-opening, and rearrangement reaction under the
influence of a bulky base in the presence of 18-crown-6.
C
2002 Wiley Periodicals, Inc. Heteroatom Chem 13:310–
315, 2002; Published online in Wiley Interscience (www.
interscience.wiley.com). DOI 10.1002/hc.10036
ucts [2,3]. Trialkylsilylmethyl epoxides can be con-
verted into diol monoesters in the presence of an
INTRODUCTION
organic acid [4,5], and converted into trialkylsilyl-
substituted allylic alcohols by the action of lithium
dialkylamide [6]. They also undergo a desilylation to
be converted into allylic alcohols through promotion
by tetraalkylammonium fluoride [2,7], a Lewis acid,
BF3 [8], or protonic acids, such as hydrochloric acid
[3] and trifluoroacetic acid [9]. Herein, I report a con-
version of trimethylsilylmethyl epoxides into ketones
under the influence of a bulky base in the presence
of 18-crown-6.
Epoxides are very important intermediates in syn-
thetic organic chemistry because of their facile
preparation, often with substantial stereochemical
control, and their high chemical reactivity, a fea-
ture attributable to the ring strain of these small-
ring heterocycles [1–3]. Epoxides are typically pre-
pared from olefins by oxidation with peracids or
dioxiranes. The preponderance of synthetic applica-
tions involves nucleophilic opening of the epoxide
ring, and an enormous range of nucleophilic species
has been used for this purpose. The conversion of
epoxides to their isomeric compounds under the in-
fluence of acidic reagents, including protonic acids
and Lewis acids, has also been utilized preparatively
[1–3]. Recently, much attention has been paid to non-
nucleophilic base-promoted ring-opening reactions
of epoxides. Organolithiums, lithium dialkylamides,
RESULTS AND DISCUSSION
Trimethylsilyl olefin 3a was prepared from cinnamyl
alcohol 1a through esterification with trifluoroacetic
anhydride and coupling with hexamethyldisilane
(TMS)2 under palladium(0)-catalysis by a procedure
described in the literature [10]. Allylic alcohols
1b,c were prepared from reactions of vinylmag-
nesium bromide and cyclohexanecarboxaldehyde
and heptanal, respectively. After esterification with
trifluoroacetic anhydride, their esters underwent a
Correspondence to: Yuan Ma; e-mail; yuan ma 99@yahoo.com.
Contract grant sponsor: Tsinghua University.
2002 Wiley Periodicals, Inc.
c
310

Desilylation and Conversion of Trimethylsilylmethyl Epoxides into Ketones 311
rearrangement and coupling with hexamethyldisi-
from 3-phenyl-2-propyn-1-ol according to a liter-
ature procedure [17]. Alcohol 1g was obtained
by reduction of ethyl cinnamate with lithium
aluminum deuteride [18]. Transformation of the
deuterio alcohols 1d–g into deuterio trimethylsilyl-
methyl phenyl epoxides 4d–g was carried out us-
ing the same method as for the alcohol 1a. The
deuterio trimethylsilylmethyl phenyl epoxides 4d–g
were also converted into the corresponding ketones,
deuterio 1-phenyl-1-propanones, respectively, in ex-
cellent yields in the same reaction conditions. The
results are summarized in Table 1.
Based on the results and literature, the mech-
anism for the conversion is suggested as follows
(Scheme 2). After the epoxides 4 were attacked on
their silicon atoms by a base N(TMS)2, they undergo
a ␤-elimination to give allyloxide anions A, which can
form allylic alcohols 5 after treatment with water.
The allyloxide anions A could lose their ␣-hydrogens
and undergo a double bond rearrangement to give
rise to dianions B because the ␣-hydrogens of the al-
lyloxide anions A are more acidic because of their
location in the allylic position (in both allylic and
benzylic positions for 4a,d–g). After treatment with
water, the dianions B can form enols C, which tau-
tomerize into ketones 6. The process, in which an
allylic alcohol can be converted into a ketone, was
confirmed by Crandall and his colleagues [13].
Although a trialkylsilylmethyl epoxide can un-
dergo a ␤-elimination to produce a trialkylsilyl al-
lylic alcohol through ␤-abstraction by potassium di-
alkylamide [6], no trimethylsilyl allylic alcohol was
found in my cases. It also supports the suggested
mechanism that ␤,␤-dideuterio epoxide 4g gener-
ates 3,3-dideuterio-1-phenyl-1-propanone (6g). In
the absence of 18-crown-6, both allylic alcohol 5a
and ketone 6a were obtained from 4a in the reaction.
Epoxide 4a and its deuterio derivatives 4d–g yielded
ketones 6a,d–g as the sole products in the pres-
ence of 18-crown-6. It is rationalized that 18-crown-6
lane (TMS)2 under palladium(0)-catalysis to produce
trimethylsilyl olefins 3b,c [10]. The trimethylsi-
lyl olefins 3 were converted into trimethylsilyl-
methyl epoxides 4 in high yields by oxidation
with di(chloromethyl)dioxirane, generated in situ
from 1,3-dichloroacetone and Oxone (potassium per-
oxomonosulfate) [11]. When trimethylsilylmethyl
phenyl epoxide 4a was treated with a bulky base,
potassium tert-butoxide, not only was a desilylated
allylic alcohol (5a) obtained, but also desilylated
1-phenyl-1-propanone (6a). The yield of 6a was in-
creased slightly when a more bulky base potas-
sium bis(trimethylsilyl)amide KN(TMS)2 was used
instead of potassium tert-butoxide. Only 6a was ob-
tained in almost quantitative yield when an equimo-
lar amount of 18-crown-6 was added with the base.
However, two alkyl-substituted trimethylsilylmethyl
epoxides (4b,c) yielded a mixture of allylic alcohols
5b,c and ketones 6b,c, respectively, in the same re-
action conditions (Scheme 1).
In earlier papers [12–15] on the reactions
of epoxides with strongly basic, nonnucleophilic
reagents, two major competing reaction pathways
were suggested, the relative efficiencies of which de-
pend on the specific molecule in question. In sys-
tems where a favorable cis, coplanar, transition-state
geometry can be readily attained, ␤-elimination to
give allylic alcohols is preferred. When such is not
the case, the products are thought to evolve from ␣-
elimination at an epoxide ring carbon and carbenoid
insertion into a neighboring carbon–hydrogen bond
to form multiple ring compounds, or carbenoid rear-
rangement into ketones. In the latter case, one of the
hydrogen atoms in an epoxide ring carbon is more
acidic and/or a stronger base is used.
In order to understand this conversion, four
deuterio-substituted trimethylsilylmethyl epoxides
4d–g were also prepared (Table 1). Deuterio-
substituted cinnamyl alcohols 1d–f were prepared
SCHEME 1 Desilylation and conversion of trimethylsilylmethyl epoxides into ketones under the influence of a bulky base.

312 Ma
TABLE 1 Desilylation and Conversion of Trimethylsilylmethyl Epoxides into Ketones
Trimethylsilymethyl
Yield of 5
Yield of 6
Entry
Epoxide 4
Base
(%)
(%)
a
tBuOK
KN(TMS)2
23
68
98
KN(TMS)2
18-Crown-6
b
KN(TMS)2
18-Crown-6
c
d
KN(TMS)2
18-Crown-6
KN(TMS)2
18-Crown-6
e
f
KN(TMS)2
18-Crown-6
KN(TMS)2
18-Crown-6
g
KN(TMS)2
18-Crown-6
SCHEME 2 Suggested mechanism for desilylation and conversion of trimethylsilylmethyl epoxides into ketones under the
influence of a bulky base.

Desilylation and Conversion of Trimethylsilylmethyl Epoxides into Ketones 313
prefers to coordinate with a potassium cation so as to
5.11 g (24.3 mmol) of trifluoroacetic anhydride were
added in the indicated order. The mixture was stirred
for 15 h. A brown oil was obtained after removal
of solvent. The oil could be used without further
purification.
increase the basicity of KN(TMS)2. The stronger base
N(TMS)2 can abstract the ␣-hydrogen of the allylox-
ide anion A completely when epoxide 4a is treated
by KN(TMS)2 in the presence of 18-crown-6 because
the ␣-hydrogen located in both the allylic and the
benzylic position is more acidic. Then, allyloxide A
could convert into a dianion B completely. Thus, only
1-phenyl-1-propanone 6a is obtained from the epox-
ide 4a. For intermediates A of the epoxides 4b,c,
their ␣-hydrogens located in the allylic position are
not acidic enough for the base N(TMS)2 to abstract
their ␣-hydrogens of the allyloxide anions A and con-
vert them into dianions B completely. Thus, both al-
lylic alcohols 5b,c and ketones 6b,c are obtained.
The proposed structures for all unknown com-
pounds are based on 1H NMR, 13C NMR, mass spec-
tral, and elemental analyses.
In conclusion, aromatic-substituted trimethylsi-
lylmethyl epoxides were converted into ketones
through a desilylation, epoxide ring-opening, and re-
arrangement reaction under the influence of a bulky
base and in the presence of 18-crown-6. However,
aliphatic-substituted trimethylsilylmethyl epoxides
gave both allylic alcohols and ketones in the same
conditions.
A 150-ml flask was charged with Pd(DBA)2
(255 mg, 0.45 mmol) and 83 ml of THF under N2.
The palladium complex was dissolved with stirring
to afford a deep purple solution. Then the ester 2 pre-
pared as described previously (15 mmol) and hexam-
ethyldisilane (TMS)2 (4.38 g, 30 mmol) were added
in the indicated order. The reaction mixture turned
pale yellow, and the reaction was carried out at RT
for 12 h. After the reaction, the reaction mixture was
diluted with Et2O (300 ml), washed with saturated
NaHCO3 (300 ml), and dried over Na2SO4. After col-
umn separation, a colorless oil was obtained.
3-Trimethylsilyl-1-phenyl-1-propene (3a): Color-
less oil. Yield 73% [22].
1-Cyclohexyl-3-trimethylsilyl-1-propene (3b):
Colorless oil. Yield 62% [10].
1-Trimethylsilyl-2-nonene (3c): Colorless oil.
Yield 56% [22].
1-Deuterio-3-trimethylsilyl-1-phenyl-1-propene
(3d): Colorless oil. Yield 70%. IR (KBr): 3079.4,
3059.0, 2954.4, 2896.1, 1629.4, 1494.5, 1248.2,
1
1
1145.6, 1020.4, 846.6, 769.7, 693.2 cm . H NMR
: 7.38–7.21 (5H, m, ArH), 6.30 (1H, tt, J = 8.4,
2.4 Hz, CH ), 1.72 (2H, d, J = 8.4 Hz, CH2), 0.11
(9H, s, SiMe3). MS m/z: 191 (M+), 176, 73. HRMS
Anal. Calcd. for C12H17DSi: 191.1239. Found:
191.1236.
EXPERIMENTAL
Melting points were obtained on a Yanaco melt-
ing point apparatus and are uncorrected. Elemental
analyses were carried out on an Elementar Vario
1
EL elemental analyzer. The H NMR spectra were
1,2-Dideuterio-3-trimethylsilyl-1-phenyl-1-pro-
pene (3e): Colorless oil. Yield 73%. IR (KBr): 3078.8,
3058.7, 3022.7, 2954.5, 2896.3, 1610.2, 1494.6,
recorded on a Varian Inova 300 or Brucker AM400
spectrometer with TMS as an internal standard in
CDCl3. The IR spectra were taken on a Brucker Vec-
tor 22 FT-IR spectrophotometer in KBr. Mass spec-
tra were obtained on a VG ZAB-HS mass spectrom-
eter. TLC separations were performed on silica gel
G plates with petroleum ether (30–60 C)/ethyl ac-
etate (10:1), and the plates were visualized with UV
light.
Deuterio-substituted cinnamyl alcohols 1d–g
were prepared according to literature procedures
[17–19]. 1-En-3-ols 1b,c were obtained by reaction
of cyclohexanecarboxaldehyde and heptanal, respec-
tively, with vinylmagnesium bromide. Their spec-
tral data are in good agreement with literature data
[20,21].
1
1
1248.2, 1149.3, 844.0, 721.2, 692.5 cm . H NMR
: 7.35–7.18 (5H, m, ArH), 1.69 (2H, s, CH2), 0.08
(9H, s, SiMe3). MS m/z: 192 (M+), 177, 73. HRMS
Anal. Calcd. for C12H16D2Si: 192.1301. Found:
192.1307.
2-Deuterio-3-trimethylsilyl-1-phenyl-1-propene
(3f): Colorless oil. Yield 71%. IR (KBr): 3079.8,
3059.9, 3024.1, 2954.5, 2896.4, 1626.5, 1598.7,
1
1
1495.6, 1248.1, 1149.9, 860.8, 718.2, 693.5 cm . H
NMR : 7.34–7.08 (5H, m, ArH), 6.25 (1H, s, CH ),
1.68 (2H, s, CH2), 0.07 (9H, s, SiMe3). MS m/z: 191
(M+), 176, 73. Anal. Calcd. for C12H17DSi: C, 75.32;
H + D, 10.01. Found: C, 75.33; H + D, 9.89.
3,3-Dideuterio-3-trimethylsilyl-1-phenyl-1-pro-
pene (3g): Colorless oil. Yield 68%. IR (KBr): 3023.2,
2954.2, 2897.4, 1639.4, 1495.2, 1247.3, 996.6, 843.3,
Preparation of Trimethylsilyl Olefins 3
1
691.7 cm . 1H NMR : 7.34–7.08 (5H, m, ArH), 6.26
General Procedure. To a solution of allyl alco-
hol 1 (20.6 mmol) in 19 ml of dichloromethane with
stirring at 0 C, 2.87 g of Et3N, 0.25 g of DMAP, and
(2H, s, CH CH), 0.07 (9H, s, SiMe3). MS m/z: 192
(M+), 177, 73. HRMS Anal. Calcd. for C12H16D2Si:
192.1301. Found: 192.1297.

314 Ma
1
2892.4, 1249.8, 1020.1, 860.3, 746.9, 697.0 cm .
Preparation of Trimethylsilylmethyl Epoxides 4
1H NMR : 7.35–7.24 (5H, m, ArH), 2.97 (1H, dd,
J = 5.4, 8.4 Hz, CH), 1.28 (1H, dd, J = 5.4, 13.8 Hz,
H in CH2), 0.81 (1H, dd, J = 8.4, 13.8 Hz, H in CH2),
0.098 (9H, s, SiMe3). 13C NMR : 137.9 (ArC), 128.3
(ArC), 127.7 (ArC), 125.2 (ArC), 61.34 (CHO), 59.59
(t, J = 25.7 Hz, CDO), 21.32 (CH2), 1.08 (SiMe3).
MS m/z: 207 (M+). Anal. Calcd. for C12H17DOSi:
C, 69.51; H + D, 9.23. Found: C, 69.39; H + D,
8.96.
General Procedure. To an acetonitrile (14 ml)
solution of allylsilane 3 (1 mmol) was added an
aqueous Na2EDTA solution (9 ml, 4 10 M), fol-
4
lowed by addition of 15 mg of Bu4NHSO4. The
resulting mixture was cooled to 0–1 C and 1,3-
dichloroacetone (292 mg, 2.3 mmol) was added. To
this solution was added in portions a mixture of
sodium bicarbonate (1.43 g, 21 mmol) and Oxone
(4.3 g, 7 mmol) over a period of 1.5 h. After the re-
action was complete, the product was extracted with
hexane (3 30 ml), and dried over Na2SO4. After re-
moval of the solvent under reduced pressure, the
residue was purified by flash chromatography to give
the pure epoxide.
2,3-Dideuterio-2-trimethylsilylmethyl-3-phenyl-
oxirane (4e): Colorless oil. Yield 97%. IR (KBr):
2955.3, 2930.5, 2858.8, 1719.3, 1271.5, 1248.7,
1
1
1110.2, 865.0, 838.7, 709.8, 668.1 cm . H NMR :
7.35–7.24 (5H, m, ArH), 1.28 (1H, d, J = 13.8 Hz,
H in CH2), 0.80 (1H, d, J = 13.8 Hz, H in CH2),
0.09 (9H, s, SiMe3). 13C NMR : 137.9 (ArC), 128.8
(ArC), 127.8 (ArC), 125.4 (ArC), 60.98 (t, J = 27.17
Hz, CDO), 59.54 (t, J = 25.66 Hz, CDO), 21.2 (CH2),
1.04 (SiMe3). MS m/z: 208 (M+). Anal. Calcd. for
C12H16D2OSi: C, 69.17; H + D, 9.67. Found: C, 68.99;
H + D, 9.49.
2-Trimethylsilylmethyl-3-phenyl-oxirane (4a):
Colorless oil. Yield 97%. IR (KBr): 2954.7, 2892.2,
1
1245.1, 1020.5, 860.9, 747.4, 697.3 cm . 1H NMR :
7.37–7.24 (5H, m, ArH), 3.54 (1H, d, J = 1.8 Hz, CH),
2.97 (1H, ddd, J = 1.8, 5.1, 8.4 Hz, CH), 1.28 (1H,
dd, J = 5.1, 14.4 Hz, H in CH2), 0.81 (1H, dd, J = 8.4,
14.4 Hz, H in CH2), 0.09 (9H, s, SiMe3). 13C NMR :
137.9 (ArC), 128.3 (ArC), 127.8 (ArC), 125.2 (ArC),
61.5 (CHO), 60.0 (CHO), 21.4 (CH2), 1.1 (SiMe3).
MS m/z: 206 (M+). Anal. Calcd. for C12H18OSi: C,
69.84; H, 8.79. Found: C, 70.07; H, 8.72.
2-Deuterio-2-trimethylsilylmethyl-3-phenyl-oxi-
rane (4f): Colorless oil. Yield 93%. IR (KBr): 2954.2,
2893.1, 1495.9, 1457.0, 1276.5, 1249.9, 863.8, 841.3,
1
743.8, 697.1 cm . 1H NMR : 7.35–7.25 (5H, m,
ArH), 3.55 (1H, s, CH), 1.28 (1H, d, J = 14.4 Hz, H
in CH2), 0.81 (1H, d, J = 14.4 Hz, H in CH2), 0.10
(9H, s, SiMe3). 13C NMR : 137.9 (ArC), 128.2 (ArC),
127.6 (ArC), 125.1 (ArC), 60.89 (t, J = 24.91 Hz,
CDO), 59.80 (CHO), 21.09 (CH2), 1.13 (SiMe3). MS
m/z: 207 (M+). Anal. Calcd. for C12H17DOSi: C, 69.51;
H + D, 9.23. Found: C, 69.77; H + D, 9.36.
2-Cyclohexyl-3-trimethylsilylmethyl-oxirane
(4b): Colorless oil. Yield 94%. IR (KBr): 2926.2,
1
1
2852.8, 1450.1, 1249.1, 859.8 cm . H NMR : 2.79
(1H, ddd, J = 2.1, 5.1, 8.8 Hz, CH), 2.41 (1H, dd,
J = 2.1, 6.6 Hz, CH), 1.86 (1H, m, CH), 1.76–1.65
(4H, m, 2CH2), 1.25–1.05 (6H, m, 3CH2), 1.16 (1H,
dd, J = 4.5, 10.8 Hz, H in CH2), 0.58 (1H, dd, J = 8.8,
10.8 Hz, H in CH2), 0.09 (9H, s, SiMe3). 13C NMR :
64.7 (CHO), 55.82 (CHO), 40.58 (CH), 29.91 (CH2),
29.29 (CH2), 26.41 (CH2), 25.85 (CH2), 25.67 (CH2),
21.22 (CH2), 1.04 (SiMe3). MS m/z: 212 (M+). Anal.
Calcd. for C12H24OSi: C, 67.86; H, 11.39. Found: C,
67.61; H, 11.27.
2-Trimethylsilyldideuteriomethyl-3-phenyl-oxi-
rane (4g): Colorless oil. Yield 96%. IR (KBr): 3033.2,
2954.5, 2897.4, 1496.0, 1457.9, 1249.7, 1009.0, 929.2,
1
1
752.6, 731.1, 697.4 cm . H NMR : 7.35–7.24 (5H,
m, ArH), 3.54 (1H, d, J = 2.1 Hz, CH), 2.96 (1H,
d, J = 2.1 Hz, CH), 0.096 (9H, s, SiMe3). 13C NMR
: 138.00 (ArC), 128.1 (ArC), 127.8 (ArC), 125.2
(ArC), 61.34 (CHO), 59.91 (CHO), 20.56 (quintet,
J = 18.1 Hz, CD2), 1.09 (SiMe3). MS m/z: 208 (M+).
Anal. Calcd. for C12H16D2OSi: C, 69.17; H + D, 9.67.
Found: C, 69.04; H + D, 9.41.
2-Hexyl-3-trimethylsilylmethyl-oxirane
(4c):
Colorless oil. Yield 89%. IR (KBr): 2956.6, 2929.1,
1
2857.9, 1458.3, 1249.7, 1185.4, 860.0, 841.3 cm . 1H
NMR : 2.72 (1H, ddd, J = 2.1, 5.7, 8.1 Hz, CH), 2.60
(1H, ddd, J = 2.1, 5.7, 5.4 Hz, CH), 1.52–1.25 (10H,
m, 5CH2), 1.12 (1H, dd, J = 5.7, 14.4 Hz, H in CH2),
0.88 (3H, t, J = 7.0 Hz, Me), 0.61 (1H, dd, J = 9.1,
14.4 Hz, H in CH2), 0.08 (9H, s, SiMe3). 13C NMR
: 60.3 (CHO), 57.0 (CHO), 32.5 (CH2), 31.8 (CH2),
29.3 (CH2), 26.1 (CH2), 22.7 (CH2), 20.9 (CH2), 14.2
(CH3), 1.10 (SiMe3). MS m/z: 214 (M+). Anal. Calcd.
for C12H26OSi: C, 67.22; H, 12.22. Found: C, 67.41;
H, 12.27.
Desilylation and Conversion of
Trimethylsilylmethyl Epoxides 4 into Ketones
General Procedure. To a solution of a suitable
base (0.3 mmol) or a base and 18-crown-6 (79.2 mg,
0.3 mmol) in 2.5 ml of THF at 78 C under a nitrogen
atmosphere, 0.25 mmol of epoxide 4 was added. The
resulting mixture was stirred for 4–6 h at 78 C and
warmed to RT. The mixture was treated with water,
3-Deuterio-2-trimethylsilylmethyl-3-phenyl-oxi-
rane (4d): Colorless oil. Yield 93 %. IR (KBr): 2954.1,

Desilylation and Conversion of Trimethylsilylmethyl Epoxides into Ketones 315
[6] Dubac, J.; Laporterie, A.; Manuel, G.; Iloughmane, H.;
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extracted with 3 10 ml of ethyl acetate, washed
with water and dried over sodium sulfate. After re-
moval of the solvent, the residue was purified on a
silica gel column to give a colorless oil.
3,3-Dideuterio-1-phenyl-1-propanone (6g): Col-
orless oil. Yield 93%. IR (KBr): 3062.6, 2940.1,
1689.8, 1598.3, 1449.7, 1333.2, 1268.3, 1185.4, 950.0,
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1
1
745.6, 720.7, 691.2 cm . H NMR : 7.40–7.20 (5H,
m, ArH), 2.99 (2H, m CH2), 1.22 (1H, m, CHD2).
13C NMR : 206.6 (CO), 136.7 (ArC), 132.6 (ArC),
128.3 (ArC), 127.7 (ArC), 31.5 (CH2), 8.0 (quintet,
JCD = 19.0 Hz, CHD2). MS m/z: 136 (M+). Anal. Calcd.
for C9H8D2O (136.08): C, 79.37; H + D, 8.88. Found:
C, 79.41; H + D, 8.77.
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