New route to 1,1-Difluoro-5-methylquasisilatrane

Article abstract of DOI:10.1134/S1070363211120115

A new route to 1,1-difluoro-5-methylquasisilatrane (N→Si) F ₂Si(OCH₂CH₂)₂NMe is elaborated: the reaction of chlorinated methyltrifluorosilanes F₃SiCH _3-nCln (n = 1-3) as well as trifluoro(3-chloropropyl) silane and trifluoro(propenyl)silane with N-methyl-bis(2-hydroxyethyl)amine. The reactivity of the silanes F₃SiCH_3-nCln increases with the number of chlorine atoms, that is, with the electronegativity of the CH_3-nCln group. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070363211120115

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 12, pp. 2490–2492. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.S. Soldatenko, E.A. Grebneva, N.F. Chernov, A.I. Albanov, O.M. Trofimova, M.G. Voronkov, 2011, published in Zhurnal
Obshchei Khimii, 2011, Vol. 81, No. 12, pp. 2043–2045.
New Route to 1,1-Difluoro-5-methylquasisilatrane
a
a
b
A. S. Soldatenko , E. A. Grebneva , N. F. Chernov ,
a
a
a
A. I. Albanov , O. M. Trofimova , and M. G. Voronkov
a
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia;
e-mail: omtrof@irioch.irk.ru
b
East-Siberian State Academy of Education, Irkutsk, Russia
Received April 12, 2011
Abstract—A new route to 1,1-difluoro-5-methylquasisilatrane (N→Si) F
the reaction of chlorinated methyltrifluorosilanes F (n = 1–3) as well as trifluoro(3-chloropropyl)
silane and trifluoro(propenyl)silane with N-methyl-bis(2-hydroxyethyl)amine. The reactivity of the silanes
2 2 2 2
Si(OCH CH ) NMe is elaborated:
SiCH3–nCl
3 n
F
3
SiCH3–nCl
n
increases with the number of chlorine atoms, that is, with the electronegativity of the CH3–nCl
n
group.
DOI: 10.1134/S1070363211120115
For a long time the reactions of splitting of theC–Si
bond have attracted the attention of organosilicon
chemists [1–3]. Our systematic studies in this field
have shown that the cleavage of the Ph–Si bond in the
phenyltrifluorosilane PhSiF3 and phenyl(methyl)
phenylmercury acetate PhHgC(O)OMe with the
formation of the С-chloromethyl derivatives of phenyl-
mercury [4, 5].
Cl
n
(H)n–3CSiF
(H)n–3CHgPh + MeC(O)OSiF
n = 1–3.
3
+ MeC(O)OHgPh
→
Cl
n
3
,
difluorosilane PhMeSiF by various nucleophiles are
2
of substantial synthetic interest [4–9]. In particular, it
was found that that the reaction of PhSiF with mono-,
Based on this observation and looking for new
synthetic routes to intracomplex compounds of hyper-
valent silicon we have elaborated an original method
of synthesis of 1,1-difluoro-5-methylquasisilatrane by
the reaction of the С-chlorinated trifluoro(methyl)-
3
bis-, and tris(2-hydroxyethyl)amines (HOCH CH ) NR
2
2 n
3–n
(n = 1–3) readily afforded 1,1,1-trifluorohyposilatranes
(
N→Si) F SiOCH CH NR (R = H , HMe, Me ) (А),
3
2
2
2
2
2
2
1
,1-di-fluoroquasisilatranes (N→Si) F Si(OCH CH ) NH
2 2 2 2
(
B), and 1-fluorosilatrane FSi(OCH CH ) N (C)
silanes Cl (H)3–nCSiF , where n = 1 (I), 2 (II), 3 (III),
n 3
2
2 3
[7–10].
with N-methylbis(2-hydroxyethyl)amine (IV).
Men
N
H
N
The reaction of trifluoro(chloromethyl)- (I) or tri-
fluoro(trichloromethyl)silane (III) with N-methyl-bis-
H2
−n
N
(2-hydroxyethyl)amine (IV) proceeds with the
F
O
O
cleavage of the C–Si and Si–F bonds, evolution of HF,
methyl chloride or chloroform, and the formation of
Si
F
O
O
Si
O
Si
F
O
F
F
F
1
,1-difluoro-5-methyl-quasisilatrane (N→Si) F2Si·
А
B
C
(
OCH CH ) NMe (V) in 77% (n = 1) or 93% (n = 3)
2
2 2
Nowadays, the compounds of hypervalent silicon
yield.
continue to attract the interest of many researchers due
to the unusual ability of the silicon atom to increase its
coordination number to five or six [11–15].
Cl
n
(H)3–nCSiF
I, III
3
+ (HOCH
2
2 2
CH ) NMe
IV
n 2 2 2 2
Cl (H)3–(n+1)C + F Si(OCH CH ) NMe, (1)
As early as in 1987, it was shown that the C–Si
bond in the С-chlorinated trifluoro(methyl)silanes
Cl (H) CSiF (n = 1–3) could be split by the action of
–
HF
V
n = 1, 3.
n
3–n
3
2
490

NEW ROUTE TO 1,1-DIFLUORO-5-METHYLQUASISILATRANE
2491
(2)
Cl
2
HCSiF
II
3
+ (HOCH
2
CH
IV
2
)
2
NMe
F
2
Si(OCH
2
CH
2
)
2
NMe + Cl
2
2 2 2
CH(F)Si(OCH CH ) NMe.
–
2 2
HF, –Cl CH
V
VI
The reaction of trifluoro(dichloromethyl)silane (II)
with N-methylbis(2-hydroxyethyl)amine (IV) results in
breaking not only the C–Si but also the Si–F bond with
the formation of 1,1-difluoro-5-methylquasisilatrane
increases with the number of chlorine atoms (n),
that is, with the electronegativity of the C(H) Cl
3
–n
n
group, where n = 1, 2, 3 (σ* = 1.05, 1.94, 2.65 respect-
tively).
(
N→Si) F Si(OCH CH ) NMe (V) (60%) and 1-
2 2 2 2
In the reaction of trifluoro(3-chloropropyl)silane
VII) with N-methylbis(2-hydroxyethyl)amine (IV)
both the C–Si and Si–F bonds are split with the
formation of 1,1-difluoro-5-methylquasisilatrane (V)
(48%) and propyl chloride.
fluoro-1-dichloromethyl-5-methylquasisilatrane (N→Si)
Cl CH(F)Si(OCH CH ) NMe (VI) (22%).
(
2
2
2 2
The reactivity of the С-chlorinated trifluoro(methyl)-
silanes Cl (H) CSiF (I–III) in reactions (1) and (2)
n
3–n
3
Cl(CH
2
)
3
SiF
VII
3
+ (HOCH
2
CH
2
)
IV
2
NMe → F
2
Si(OCH
2
CH
2
)
V
2
NMe + PrCl + HF.
(3)
In the series Cl(СH ) SiF the electronegativity of
carbon (J 4.4–4.6 Hz), but only with one, apparently,
2
m
3
the Cl(CH ) group decreases with the number of the me-
the equatorial, fluorine atom.
2
m
thylene groups (m) [σ* = 1.05 (m = 1), σ* = 0.13 (m = 3)],
but reaction (3) still occurs (3). Yet trifluoro(chloropro-
pyl)silane Cl(СH ) SiF does not react with mercury
The presence of narrow signals and long-range
1
13
19
29
coupling constants in the Н, С, F, Si NMR
spectra of compounds V and VI is determined by the
stereochemical direction of the bonds and is indicative
of the existence of stereodynamically rigid molecules
of the studied quasisilatranes in solution.
2
3
3
salts [4, 5].
The reaction of N-methylbis(2-hydroxyethyl)amine
IV) with trifluoro(propenyl)silane VIII proceeds in a
(
similar way.
EXPERIMENTAL
F
3
SiCH=CHMe + (HOCH
2
CH
IV
NMe + MeCH=CH
2
)
2
NMe
1
13
19
29
VIII
Н, С, F, and Si NMR spectra were registered
on a Bruker DРХ-400 spectrometer (400.13, 100.61,
76.50, 79.5 MHz, respectively) in CDCl and DMSO-
→
F
2
Si(OCH
2
CH
2
)
2
2
+ HF.
(4)
V
3
3
d6, internal reference TMS.
The structure of compounds V and VI was proved
by Н, C, F, Si NMR spectroscopy
С-Chlorinated derivatives of trifluoro(methyl)silane
F SiCCl H (n = 1–3), trifluoro(3-chloropropyl)silane
1
13
19 29
3
n
3–n
F Si(CH ) Cl, and trifluoro(propenyl)silane F SiCH=CHMe
1
3
2 3
3
In the Н NMR spectrum of quasisilatrane VI the
were synthesized by the Swarts reaction of SbF with
3
protons of the ОСН and NСН groups are non-
2
2
the corresponding С-chlorinated derivatives of tri-
chloro(methyl)silane, trichloro(3-chloropropyl)silane,
or trichloro(propenyl)silane.
2
equivalent and resonate as AB-quartets ( J 11.1 and
HH
1
2.1 Hz, respectively), with each component split into
3
a triplet with J 6.1 Hz. In the upfield part of the
НН
АВ-multiplet of each group of protons a long-range
1,1-Difluoro-5-methylquasisilatrane (V). а. Reac-
tion (1), n = 1. To the solution of 1.87 g of ClCH SiF
3
interaction with the fluorine atom is observed
2
4
5
(
JF–Si–N(O)–C–H ~ J
= = 2.4 Hz).
in 10 ml of anhydrous benzene (5°С) 1.43 g of freshly
distilled N-methylbis(2-hydroxyethyl)amine was added
dropwise. The reaction mixture was stirred with a
magnetic stirrer at room temperature for 20–30 min,
the formed precipitate was filtered off and sublimed in
a vacuum. Yield 1.96 g (77%), mp 160–161°С. Found,
%: C 33.15; H 6.30; F 20.56; N 7.28. C F H NO Si.
F–Si–O(N)–C–C–H
13
In the С NMR spectrum of quasisilatrane VI only
the NMe and CHCl carbon atoms are split by the
2
coupling with the fluorine atom, whereas the signals of
the carbon atoms of the atrane rings remain singlets.
1
3
In the С NMR spectrum of quasisilatrane V the
spin–spin coupling is observed also for the ОСН2
5
2
11
2
Calculated, %: C 32.76; H 6.05; F 20.74; N 7.64.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

2
492
SOLDATENKO et al.
b. Reaction (1), n = 3. To the solution of 0.23 g of
e. Reaction (4). Gaseous F SiCH=CHMe was
3
N-methylbis(2-hydroxyethyl)amine in 7 ml of anhyd-
rous benzene (5°С) 0.47 g of Cl CSiF was added
dropwise. The reaction mixture was stirred with a
magnetic stirrer at room temperature for 5–10 min, the
formed precipitate was filtered off and sublimed in a
vacuum. Yield 0.39 g (93%), mp 160–161°С. Found,
passed through the solution of 1.14 g of N-methylbis-
(2-hydroxyethyl)amine in 10 ml of anhydrous hexane
(–20°С) for 20 min. The reaction mixture was stirred
at room temperature for 20 min, the formed precipitate
was filtered off and sublimed in a vacuum. Yield 1.77 g
(87%), mp 160–161°С. Found, %: C 32.43; H 6.32; F
20.46; N 7.45. C F H NO Si. Calculated, %: C 32.76;
3
3
%
: C 32.56; H 5.87; F 21.06; N 7.79. C F H NO Si.
5 2 11 2
5
2
11
2
Calculated, %: C 32.76; H 6.05; F 20.74; N 7.64.
H 6.05; F 20.74; N 7.64.
c. Reaction (2), n = 2. To the solution of 0.49 g of
N-methylbis(2-hydroxyethyl)amine in 7 ml of anhyd-
rous benzene (5°С) 0.82 g of Cl CHSiF was added
dropwise. The reaction mixture was stirred with a
magnetic stirrer at room temperature for 10–20 min,
the formed precipitate was filtered off and sublimed in
a vacuum. Yield 0.53 g (60%), mp 160–161°С. Found,
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3
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2
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5
6
3
2
.97 d. t (2Н, NCH , J 12, J 6.0 Hz), 3.91, 3.97 d.t
2
1
3
(
(
2Н, OCH ). C NMR spectrum, δ , ppm: 43.28
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FC
2
С
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3
3
FC
2
2
19
4
.6 Hz). F NMR spectrum, δ , ppm: –149.50 d (F ,
F eq
2
1
2
JFF 29.4, J 197.2 Hz), –143.21 d (F , J 29.4,
SiF
ax
FF
7
8
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1
29
JSiF 129.7 Hz). Si NMR spectrum: δ –113.6 ppm.
Si
Crystallization of the reaction mixture from
chloroform gave compound VI. Yield 0.19 g (22%),
mp 280°C (decomp.). Found, %: C 28.67; H 4.61; Cl
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2
%
8.90; F 7.86; N 5.57. C Cl FH NO Si. Calculated,
6 2 12 2
1
: C 29.04; H 4.87; Cl 28.57; F 7.60; N 5.60. Н NMR
4
spectrum (CDCl ), δ, ppm: 2.60 d (3Н, NCH , J
3
3
2
3
1
.5 Hz), 2.78, 2.96 d. t. d (2Н, NCH , J 12.1, J 6.1,
2
4
4
(5)
2
J 2.3 Hz), 3.92, 3.99 d. t. d (2Н, OCH , J 11.1,
2
(5)
3
13
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C
2
HF
3
NMR spectrum, δ , ppm: 43.36 (NCH , J 6.1 Hz),
С
3
FC
5
4.02 (NCH ), 58.02 (OCH ), 63.64 d (СН, CHCl ,
2 2 2
2
19
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JCF 67.7 Hz). F NMR spectrum: δ –143.15 ppm
F
1
29
(
F , J 279.2 Hz). Si NMR spectrum: δ –99.2 ppm.
ax SiF Si
d. Reaction (3). To the solution of 0.61 g of N-
methylbis(2-hydroxyethyl)amine in 8 ml of anhydrous
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benzene (5°С) 0.97 g of Cl(CH ) SiF was added drop-
2
3
3
wise. The reaction mixture was stirred with a magnetic
stirrer at room temperature for 25–35 min, the formed
precipitate was filtered off and sublimed in a vacuum.
Yield 0.53 g (48%), mp 160–161°С. Found, %: C
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5
2
11
2
Calculated, %: C 32.76; H 6.05; F 20.74; N 7.64. The
evolved Me(CH ) Cl was identified chromatographically.
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2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011