Universal method for trimethylsilylation of acetylenic alcohols and glycols

Article abstract of DOI:10.1016/S0022-328X(97)00622-0

A highly convenient universal method for trimethylsilylation of acetylenic alcohols and glycols via treatment by hexamethyldisilazane in the presence of benzoic acid sulphimide as a catalyst has been developed. The rate of trimethylsilylation of acetylenic alcohols is reduced from primary to secondary and to tertiary alcohols accordingly, as well as with the decreasing of hydroxyl nucleophylicity. The toxicity of trimethylsilyl acetylenic ethers, except 2-trimethylsiloxy-3-butyne, is much lower than that of original compounds.

Full text of DOI:10.1016/S0022-328X(97)00622-0

Journal of Organometallic Chemistry 553 Ž1998. 129–133
Universal method for trimethylsilylation of acetylenic alcohols and
glycols
)
Maria Demina, Andrey Velikanov, Alevtina Medvedeva , Lyudmila Larina,
Mikhail Voronkov
Institute of Organic Chemistry, Siberian DiÕision, Russian Academy of Sciences, 1 FaÕorsky Street, Irkutsk 664033, Russian Federation
Received 14 May 1997
Abstract
A highly convenient universal method for trimethylsilylation of acetylenic alcohols and glycols via treatment by hexamethyldisilazane
in the presence of benzoic acid sulphimide as a catalyst has been developed. The rate of trimethylsilylation of acetylenic alcohols is
reduced from primary to secondary and to tertiary alcohols accordingly, as well as with the decreasing of hydroxyl nucleophylicity. The
toxicity of trimethylsilyl acetylenic ethers, except 2-trimethylsiloxy-3-butyne, is much lower than that of original compounds. q 1998
Elsevier Science S.A.
Keywords: Trimethylsilylation; Acetylenic alcohols; Acetylenic glycols
1
. Introduction
with methylphenylsilane, even in the presence of the
Speier’s catalyst in refluxing benzene, gives the corre-
Silylation of organic compounds is widely applied
sponding trimethylsilyl ether in minor yield 11%
Ž . w11x.
for the protection of hydroxyl group in organic synthe-
sis w1–3x. Trimethylsilyl ethers of some biologically
active compounds are used in pharmacology w4x. Thus,
Silyl ethers of primary, secondary and tertiary a- and
b-acetylenic alcohols were prepared by the reaction of
their trialkylstannyl ethers with Me3SiCl w12x.
anabolic drugs such as 17a-
Ž
trimethyl siloxy
.
androst-4-
1,1,1,3,3,3-Hexamethyldisilazane HMDS is widely
Ž .
en-3-one, patented as Silandron w5x and 17-O-trimethyl-
used as a silyl donor due to the possibility to carry out
the reaction in mild conditions with liberation of gaseous
ammonia. Trimethylsilylation of alcohols with HMDS
alone usually proceeds slowly and therefore the process
is activated by addition of acids, bases or salts of
ammonia w13,14x. The possibility to use the benzoic acid
silyl ether of 19-nortestosterone patented as Silabolin w6x
are more effective than original 17-hydroxy compounds.
This effect may be explained by a better penetration of
silicon ethers through lipid cell membranes. Silyl ethers
are easily hydrolyzed within the cells to form the initial
compounds. Trimethylsilylation of acetylenic alcohols
and glycols is far from being solved. So far, a universal
method for the preparation of trimethylsilyl ethers of
various acetylenic alcohols has not been developed.
Silylation of propargyl alcohol with trimethylchlorosi-
lane in the presence of base has been studied in more
detail w7–10x. To this point, the silylation of tertiary
sulphimide saccharin as a catalyst for the trimethylsi-
Ž .
lylation of saturated alcohols is described w14x.
2
. Results and discussion
acetylenic alcohols in ordinary ways was not successful,
and secondary acetylenic alcohols are difficultly sily-
lated. Thus, the interaction of 3-methyl-1-butyn-3-ol
Our aim is to work out a universal method for the
trimethylsilylation of acetylenic alcohols and glycols.
We have studied the reaction of primary, secondary and
tertiary acetylenic alcohols 1a–e and glycols 3, 5 with
HMDS and benzoic acid sulphimide as a catalyst.
)
Corresponding author.
0
022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

1
30
M. Demina et al.rJournal of Organometallic Chemistry 553 (1998) 129–133
The reasons for the preparative trimethylsilylation of
acetylenic alcohol involve: stoichiometric ratio of
reactants; with no solvent, if the alcohols 1a–f, react
because these reagents act as their own polar solvents.
Crystalline 2-butyne-1,4-diol and 5-methyl-3-non-
yne-1,5-diol were dissolved in suitable solvents:
dimethylsulphoxide
1 mol% of saccharin;
reaction mixture is 708C, mainly for the removal of
ammonia and driving the reaction to the right. The
silylation of 5 at both functional groups was carried out
in refluxing chloroform.
1-Pentyn-4-ol
Ž
1f
.
reacts analogously to the Scheme
Ž
a
.
1.
Ž
b
.
HMDS
HC[CCH CHŽOH.Me
™
HC[CCH CHŽOSiMe .Me
2 3
saccharin
2
1
f
2f
3
Ž .
2
Ž .
5
Ž .
Ž
DMSO. Ž
3
.
and trichloromethane
.
d temperature of the
The reactivity of compounds was controlled by GLC.
The yields of trimethylsilyl ethers 2a–f are 93–99%.
The structure of synthesized ethers 2a–f was proved by
Ž
5
.
;
Ž
c
.
Ž
1
13
29
H, C, Si NMR spectroscopic data
Spectra film : n C[C 2086–2100, 2165 cm
; n Si–O–C 1037–1086 cm
The yield of trimethylsilyl ethers 2a–f considerably
depends on the structure of initial acetylenic alcohol
Table 3 . Thus, 2-methyl-3-butyn-2-ol 1c shows no
reaction with HMDS alone at room temperature, whereas
2-propyn-1-ol 1a gives trimethylsilyl ether 2a in 94%
yield for 10 h at the same temperature. The use of
Table 1 and IR
Ž .
y1
Ž
.
Ž
.
Ž
2d,
y1
e
.
Ž
.
Table 2 .
Ž .
HMDS
1
2
1
2
RC[CCR R OH
™
RC[CCR R OSiMe
1
Ž .
3
1
saccharin
2
Ž
.
Ž
.
1
2
1
2
1
2
1
RsR sR sH a ; RsR sH, R sMe b ; R sR
Ž . Ž .
1 2
sMe
Ž
c
.
; RsMe Si, R sR sH
Ž
d
.
; RsEt Ge, R
Ž
.
3
3
2
sR sH e
Ž .
Table 1
1
13
29
H, C, Si NMR data of the synthesized trimethylsilyl ethers 2a–f, 4, 6, 7
1
a
13
a
29
a
Compound
H NMR d Žppm.
C NMR d Žppm.
Si NMR d Žppm.
2
2
a
4.28 Žd, Js2.5 Hz, 2H, –CH .
82.26ŽHC[C.
73.16ŽHC[C.
50.85ŽCH2 .
21.6
2
2
0
.39 Žt, Js2.5 Hz, 1H, HC[.
.17 Žs, 9H, SiŽCH . .
3
3
y0.33 ŽSiŽCH . .
3
3
b
4.51 Žqd, Js6.6 Hz and 2.2 Hz, 1H, CH.
86.23ŽHC[C.
71.66ŽHC[C.
58.40ŽCH.
19.1
2
1
0
.38 Žd, Js2.2 Hz, 1H, HC[.
.44 Žd, Js6.6 Hz, 3H, CH .
3
.17 Žs, 9H, SiŽCH . .
25.36ŽCH3.
3
3
0
.13ŽSiŽCH . .
3 3
2
2
c
2.40 Žs, 1H, HC[.
13.5
1
0
.49 Žs, 6H, CH3.
.19 Žs, 9H, SiŽCH . .
3 3
d
4.20 Žs, 2H, CH2 .
.17 Žs, 18H, SiŽCH . ..
103.57ŽSiC[C.
89.78ŽSiC[C.
21.4ŽSi–O.
y18.1ŽSi–C[.
0
3
3
y0.15 ŽŽCH . SiC[.
3
3
y0.35 ŽOSiŽCH . .
3
3
2
2
e
f
4.31 Žs, 2H, CH2 .
21.1
19.1
0
.81–1.16 Žm, 15H, C H .
2 5
0
.18 Žs, 9H, SiŽCH . .
3
3
3.96 Žs, Js6.2 Hz, 1H, CH.
81.68ŽHC[C.
69.91 ŽHC[C.
67.37ŽCH.
2
1
1
0
.28 Ždd, Js6.2 and 2.6 Hz, 2H, CH .
2
.99 Žt, Js2.6 Hz, 1H, HC[.
.25 Žd, Js6.2 Hz, 3H, CH .
29.39 ŽCH2 .
23.22ŽCH3.
3
.13 Žs, 9H, SiŽCH . .
3
3
0
.13ŽSiŽCH . .
3 3
4b
6
21.0
18.3
4.31 Žs, 4H, CH2 .
0
.16 Žs, 18H, SiŽCH . .
3 3
4.32 Žbrs, 1H, OH.
3
2
0
.68 Žt, Js7 Hz, 2H, CH O.
2
.42 Žt, Js7 Hz, 2H, CH .
2
.93–1.44 Žm, 12H, CH , n C H .
3
4
9
7
3.68 Žt, Js6.8 Hz, 2H, CH O.
18.7
2
3
2
0
0
.27 Žbrs, 1H, OH.
.42 Žt, Js6.8 Hz, 2H, CH .
2
.93–1.44 Žm, 12H, CH , n C H .
3
4
9
.14 Žs, 18H, SiŽCH . .
3
3
a
In CDCl3.
In DMSO-d6.
b

M. Demina et al.rJournal of Organometallic Chemistry 553 (1998) 129–133
131
Table 2
Data for the trimethylsiyl ethers 2a–f and 7
2
0
IR Žcmy1
n ŽC[C.
Compound
B.p. Ž8Crmm Hg.
n
.
Elemental analyses found Žcalc.. Ž%.
D
n ŽSi–O–C.
C
H
Si ŽGe.
2a
2b
2c
2d
2e
2f
7
59 Ž50.
109
116
65.5 Ž11.
74 Ž8.
59 Ž33.
81 Ž1.
1.4080
1.4044
1.4075
1.4291
1.4573
1.4118
1.4588
2086
2093
2100
2164
2165
2106
2229
1057
1086
1036
1079
1086
1064
1057
56.08 Ž56.18.
59.46 Ž59.46.
61.09 Ž61.48.
54.18 Ž53.92.
50.64 Ž50.07.
62.52 Ž62.74.
61.66 Ž61.13.
9.04 Ž9.04.
21.76 Ž21.85.
19.19 Ž19.74.
18.54 Ž17.97.
27.60 Ž28.02.
9.15 Ž9.76.
17.62 Ž17.96.
17.62 Ž17.90.
10.64 Ž9.94.
10.66 Ž10.32.
10.33 Ž10.07.
9.87 Ž9.76.
10.31 Ž10.30.
10.07 Ž10.81.
saccharin in 1 mol% permits the reaction to be signifi-
cantly promoted. The trimethylsilylation of propargyl
analog 1d reacts with HMDS four times more slowly.
This difference is determined by higher nucleophilicity
alcohol
Ž
1a
.
at 708C was completed for 0.5 h in 99%
of 3-triethylgermyl-2-propyn-1-ol
with the silicon analog 1d w15x. 3-Trimethylsiloxy-2-
propyne 2a was used in the synthesis of organometal-
1e in comparison
Ž .
yield of 2a. Tertiary alcohol 1c gives 93% of 2c for 2.5
h under the same conditions. The reaction time was
Ž
.
reduced to 2 h at 708C in the latter case
. The silylation of 3-butyn-2-ol 1b proceeds for 2 h
at 708C yield 91%
Ž
93% yield of
lic acetylenic alcohols 1 d–f in high yields 85–87%
w16x whereas these compounds were prepared from
2
c
.
Ž
.
Ž
.
.
bis bromomagnesium derivatives of 1a in 40–54%
Ž .
yield w17,18x:
So we observed the high sensitivity of trimethylsily-
lation to the steric environment of acetylenic alcohols.
The ease of silylation of a-acetylenic alcohols de-
creases in order: primary)secondary)tertiary. The
remoteness of the triple bond from the reactive centre
improves the reactivity of the latter towards HMDS,
that should be ascribed to the increase of hydroxyl
nucleophilicity. As seen from Table 3, the b-acetylenic
1. EtMgBr
HC[CCH OSiMe
™
. R SiCl or R GeBr
3 3
R MSiC[CCH OH
3 2
2
3
2
2
a
1
3
. H 3O
3
Ž .
MsSi, RsMe 1d; MsGe, RsEt 1e; MsSi, RsEt
1g.
alcohol 4-pentyn-2-ol
a-analog of 1b 1 h, 98% and 2 h, 91%, respectively
This difference in reactivity of acetylenic alcohols
according to the structure is determined by steric and
Ž
1f
.
is silylated twice as fast as
The advantage of the method w16x is a good solubility
Ž
.
.
of 3-bromomagnesium-1-trimethylsiloxy 2-propyne in
Et O unlike to with low-soluble 1,3-bis bromo
Ž
2
Ž
.
magnesium derivative of 1a.
.
electronic influence of substituent at the carbon atom
containing hydroxyl group.
The influence of catalyst concentration on the effi-
ciency of alcohols silylation was illustrated with 2-
3
ols,
-Trimethylsilyl- and 3-triethylgermyl-2-propyn-1-
1d,e show a considerably different reactivity to-
wards HMDS in the presence of saccharin. The ease of
silylation of 1e and propargyl alcohol 1a
methyl-3-butyn-2-ol
saccharin from 1 to 5 mol% at 708C allows to accelerate
the reaction approximately 3.5 times yield of 2c 90–
98% . However, less hindered alcohols as primary 1a,
1c . The increase in the amount of
Ž .
Ž
.
Ž
Ž
RsEt Ge
.
Ž
.
.
3
is practically identical. At the same time, the silicon
d, e and secondary 1b, f are readily silylated by the
addition of 1 mol% of saccharin for 0.5–2 h in 91–95%
yield of TMS ethers 2a–f.
Table 3
Reaction conditions and yields of trimethylsilyl ethers 2a–f, 4, 6, 7
It is known that N,O-bis
trimethylsilyl sulphamate
Ž .
Compound Amount of catalyst Reaction Temperature Yield
Me SiNHSO SiMe is a very efficient silyl donor w19x.
3
3
3
Žmol %.
time Žh. Ž8C.
Ž%.
Nevertheless, our attempt to use it for the trimethylsily-
lation of 1b has not been successful because of
oligomerization of the reaction mixture. Probably, alco-
hol 1b will undergo an acid-catalyzed acetylene-allenic
rearrangement to an unstable, easily polymerized prod-
2
a
y
1
1
y
1
2
3
5
1
1
1
1
y
1
10.0
0.5
2.0
10.0
2.5
2.0
25
70
70
25
70
70
70
70
70
70
70
70
25
70
94
99
91
y
93
98
97
90
98
99
98
90
90
92
2
2
b
c
uct 20 . The trimethylsilylation of 2-butyn-1,4-diol 3
Ž .
w
x
1.5
0.75
in an appropriate solvent DMSO in the presence of 1
mol% of saccharin is completed for 5 h. The yield of
Ž
.
2
2
2
4
6
7
d
e
f
2.0
0.5
1.0
5.0
6.0
6.0
1
,4-bis
Ž
trimethylsiloxy
.
-2-butyne 4 is 90%.
Ž .
HMDS
HOCH C [ CCH OH ™
2
2
3 saccharin
Me SiOCH C [ CCH OSiMe
3
4
Ž .
3
2
2
4

1
32
M. Demina et al.rJournal of Organometallic Chemistry 553 (1998) 129–133
Table 4
The toxicity of acetylenic alcohols and their trimethylsilyl ethers
No.
Compound
DL50 mgrkg
No.
Compound
DL50 mgrkg
1
1
1
1
1
a
b
c
f
HC[CCH OH
100
200
200
350
150
2a
2b
2c
2f
HC[CCH OSiMe
650
1000
175
400
500
2
2
3
HC[CCHŽOH.Me
HC[CCŽOH.Me2
HC[CCHŽOSiMe .Me
3
HC[CCŽOSiMe .Me
3
2
HC[CCH CHŽOH.Me
HC[CCH CHŽOSiMe .Me
2
2
3
d
Me SiC[CCH OH
2e
Et GeC[CCH OSiMe
3
3
2
3
2
A necessary condition for the preparation of 4 in
the internal standard tetramethylsilane. Samples were
analized in CDCl3 or DMSO-d6 solution. IR spectra
high yield is to remove ammonia from the reaction
mixture by distillation with benzene. Otherwise the
yield of 4 does not exeed 70% even if the reaction time
is increased. The reactivity of 4 towards HMDS is much
were recorded on an IR-75 Spectrometer liquid film .
Ž .
GLC analysis was carried out on a Chromatograph
LKhM-80 with 3 m columns packed with PMS on
lower than that of 2-propyn-1-ol
nucleophilicity of the latter.
Ž
1a
.
due to higher
Chromaton. The alcohols 3-butyn-2-ol
3-butyn-2-ol 1c , 4-pentyn-2-ol 1f were prepared by
1b , 2-methyl-
Ž .
Ž
.
Ž .
The high sensitivity of silylation to steric factors was
used for the selective protection of primary hydroxyl
reaction of sodium acetylide with the corresponding
carbonyl compounds or propylene oxide in liquid am-
group in 5-methyl-3-nonyn-1,5-diol
silylation of 5 by HMDS alone in dichloromethane at
Ž
5
.
w21x. Thus, the
monia by a method described in w21,22x. N,O-bis
methylsilyl sulphamate was prepared by a method de-
scribed in w19x. The solvents
CHCl , DMSO were
Ž
tri-
.
1
1
0–258C was realized with regioselective formation of
Ž
.
3
-trimethylsiloxy-5-methyl-3-nonyn-5-ol in 87%
Ž
6
.
dried and distilled, HMDS was carefully fractionated to
98.5% purity.
yield fixed by GLC. With a raising of temperature from
08C to ambient reaction is accelerated more than
twice. The trimethylsilylation of both hydroxyl groups
in 5 leads to 1,5-bis trimethylsiloxy -5-methyl-3-nonyne
. Žreaction 6
. The latter was obtained in 92% yield in
1
5
Ž .
3
.1. General procedure for the trimethylsilylation of
Ž
.
acetylenic alcohols 1a–f
Ž
7
.
the presence of 1 mol% of saccharin under reflux in
CHCl3 for 6 h. The structure of monotrimethylsilyl
Saccharin
solution of alcohol 1a–f
mmol of HMDS at room temperature. The temperature
Ž
0.36 g, 1 mol%
.
was added to a stirred
Ž
200 mmol
.
and 16.3 g 100
Ž
ether
Ž
6
.
was proved by its transformation in 7, and by
Table 2
.
IR spectra
Ž
.
.
of the reaction mixture exothermally arose to 408C.
Then the mixture was heated to 708C to the completion
of the reaction
control . Trimethylsilyl ethers 2a–f were isolated by
distillation in vacuo.
Ž
cessation of ammonia evolution, GLC
.
Ž
Ž
5
.
.
3
.2. 1,4-bis(trimethylsiloxy)-2-butyne (4)
6
To a stirred solution of 2-butyne-1,4-diol
Ž
Ž
3
. Ž8.6 g,
0.36 g, 1
were added and
the reaction mixture was heated at 708C for 5 h. Ben-
zene 6 ml was added to remove ammonia from the
mixture and azeotrope ammonia–benzene was distilled
every 2 h. The yield of 4 90% was determined by
1
00 mmol
mol%
.
in 20 ml of DMSO, saccharin
16.3 g, 100 mmol
.
and HMDS
Ž
.
As seen from Table 4, trimethylsilyl ethers 2a, b, f
are less toxic than the starting alcohols 1a, b, f. The
Ž
.
toxicity of 1-trimethylsiloxy-2-propyne
methylsiloxy-3-butyne 2b are five and six times lower
than those for alcohols 1a, b. In the cases of 2-trimeth-
ylsiloxy-2-methyl-3-butyne 2c , 2-trimethylsiloxy-4-
pentyne 2f and corresponding alcohols 1c, 1f the
toxicity is similar.
2a and 2-tri-
Ž .
Ž
.
Ž
.
GLC. Pure compound 4 was not isolated because of
close boiling points of 4 and DMSO.
Ž
.
Ž
.
3
.3. 1-Trimethylsiloxy-5-methyl-3-nonyn-5-ol (6)
To the solution of 5
CHCl3 was added HMDS
reaction mixture was stirred at room temperature for 6.5
h, then concentrated to give 6 control by GLC , IR
film : n SiO–C 1080, n C[C 2240, n OH 3370
Ž
1.7 g, 10.0 mmol
.
in 5 ml of
3
. Experimental details
Ž
0.8 g, 5.0 mmol
.
. The
1
13
29
H, C, Si NMR spectra were recorded using
1
3
29
JEOL-FX-90Q spectrometer
1
Ž
C, 22.49 MHz; Si,
Ž
.
7.75 MHz . Chemical shifts were measured relative to
.
Ž
.
Ž
.
Ž
.
Ž
.

M. Demina et al.rJournal of Organometallic Chemistry 553 (1998) 129–133
133
cmy1. The attempt to distil 6 in vacuo leads to a
mixture of 6 and 7.
w2x A.E. Pierce, Silylation of Organic Compounds, Pierce Chemi-
cal, Rockford, IL, 1968.
w3x M.M. Demina, A.A. Velikanov, A.S. Medvedeva, O.I. Mar-
gorskaya, M.G. Voronkov, Pat. SSSR 1833392 Ž1991.. Bull.
Izobret. No. 29 Ž1993. 146.
3
.3.1. 5-Methyl-1,5-bis(trimethylsiloxy)-3-nonyne (7)
To the solution of crude 6 2.4 g, 10.0 mmol in 5 ml
CHCl , saccharin 0.018 g, 1 mol% and HMDS 0.8 g,
were added. The mixture was heated at
reflux for 6 h. The solvent was evaporated and the
residue was distilled in vacuo to give 7 2.88 g, 92%
Ž
.
w4x M.G. Voronkov, J.I. Zelchan, E. Lukevitz, Silizium und Leben,
Ž
.
Ž
Academie-Verlag, Berlin, 1975.
3
.0 mmol
.
w5x S. Pavlenko, Organosilicon Chemistry, Berlin, New York, 1986,
5
p. 133.
w6x A.A. Shishkina, G.I. Ivanenko, N.A. Zarubina, O.N. Volzhina,
Ž
.
.
V.G. Angarskaya, K.K. Pivnitsky, Khimiko-Farm. Zh. 20 Ž1986.
2
32.
3
.4. 3-Triethylgermyl-2-propyn-1-ol (1e)
w7x E.O. Tsetlyna, S.F. Pavlov, I.M. Korotaeva, Jzv. Akad. Nauk
SSSR, Ser. Khim. Ž1974. 2856.
To a Grignard reagent Mg 24.0 g, 1.0 mol; EtBr
Ž
w8x V.F. Mironov, N.G. Maximova, Izv. Akad. Nauk SSSR, Otd.
Khim. Nauk Ž1960. 2059.
1
09.0 g, 1.0 mol; 300 ml of Et20 of 2a 128.3 g, 1.0
in 100 ml Et O was added on an ice bath cooling.
.
Ž
w9x P. Brison, M. Liford, Ger. Offen, 1,1954,961, C.A. 73 Ž1970.
mol
The reaction mixture was stirred at room temperature
for 3 h and Et GeBr 237.0 g, 1.0 mol in 150 ml of
.
2
1
4978u.
w10x K.A. Andrianov, I.A. Shikhiev, J.F. Nasirov, E.M. Movsum-
Ž
.
3
zade, M.I. Shikhieva, R.Yu. Gasanova, Dokl. Akad. Nauk SSSR
215 Ž1974. 1117.
Et O was added. The mixture was stirred for 3 h,
2
w11x L.G. Kulieva, R.M. Mustafaeva, S.I. Sadykhzade, Zh. Vses.
neutralized with aqueous NaHCO solution, extracted
3
Khim. Obshchestva 29 Ž1984. 231.
with Et O and dried over Na SO . The solvent was
2
2
4
w12x M.F. Shostakovsky, R.G. Mirskov, V.M. Vlasov, Sh.I.
Tarpishchev, Zh. Obshch. Khim. 37 Ž1967. 1738.
w13x M.D. Mizhiritsky, Yu.A. Yuzhelevsky, Usp. Khim. 56 Ž1987.
evaporated and the residue was distilled in vacuo to
2
0
give 1e
.4841. IR
w21x: B.p. 1128Cr9 mm Hg, n 1.4822. 3-Trimethyl-
Ž
194.0 g, 85%
.
. B.p. 90–928Cr3 mm Hg, n
D
y1
1
Ž
film : n C[C
.
Ž
.
2185, n
Ž
OH
.
3380 cm
.
609.
2
0
w14x C.A. Bruynes, T.K. Jurriens, J. Org. Chem. 47 Ž1982. 3966.
D
w15x A.N. Egorochkin, O.I. Margorskaya, S.E. Skobeleva, A.S.
silyl-2-propyn-1-ol
ol 1g were prepared similarly in 86 and 87% yield,
1d and 3-triethylsilyl-2-propyn-1-
Ž .
Medvedeva, A.I. Borisova, N.S. Vyazankin, Izv. Akad. Nauk
SSSR, Ser. Khim. Ž1986. 1789.
Ž
.
respectively.
w16x A.S. Medvedeva, O.I. Margorskaya, M.G. Voronkov, Inventor’s
Certificate SSSR, 1705297 Ž1989.. Bull. Izobret. No. 2 Ž1992.
1
02.
w17x I.A. Shikhiev, I.A. Aslanov, B.G. Yusupov, Zh. Obshch. Khim.
1 Ž1961. 3647.
Acknowledgements
3
w18x M.F. Shostakovsky, N.V. Komarov, O.G. Yarosh, Izv. Akad.
This work was supported by the Russian Foundation
of Basic Research, grant 95-03-09302a.
Nauk SSSR, Ser. Khim., Ž1966. 101.
w19x B.E. Cooper, I. Westall, J. Organomet. Chem. 118 Ž1976. 135.
w20x M.V. Mavrov, V.F. Kucherov, Usp. Khim. 36 Ž1967. 553.
w21x M.F. Shostakovsky, V.M. Vlasov, A.S. Lozhenitsyna, A.A.
Gavrilovskaya, Izv. Akad. Nauk SSSR, Ser. Khim. Ž1965. 709.
w22x M.F. Shostakovsky, V.M. Vlasov, A.S. Medvedeva, G.G.
References
w1x R. Tacke, H. Linon, Bioorganosilicon chemistry, S. Patai, Z.
Rappoport ŽEds.., Chap. 18, Wiley, New York, 1989.
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