Peculiarities of the reaction of alkali metal bis(trimethylsilyl)amides with halobenzenes

Article abstract of DOI:10.1007/s11172-015-1122-0

Lithium and sodium bis(trimethylsilyl)amides react with fluoro-, bromo-, and chlorobenzenes in THF or toluene to give a mixture of N,N-bis(trimethylsilyl)aniline and N,2-bis(trimethylsilyl)aniline. The latter compound is resulted from 1,3-shift of the trimethylsilyl group from nitrogen to ortho-carbon atom of the benzene ring. Effects of the solvent, halogen, and alkali metal nature as well as the reaction conditions on the ratio of isomers were examined. Reaction of iodobenzene with sodium bis(trimethylsilyl)amide in THF produces N,N-bis(trimethylsilyl)aniline and 2-iodo-N,N-bis(trimethylsilyl)aniline, while in toluene a mixture of three products, two indicated above and N,N-bis(trimethylsilyl)benzylamine, was obtained.

Full text of DOI:10.1007/s11172-015-1122-0

Russian Chemical Bulletin, International Edition, Vol. 64, No. 9, pp. 2090—2094, September, 2015
2090
Peculiarities of the reaction of alkali metal bis(trimethylsilyl)amides
with halobenzenes*
A. V. Lis, I. P. Tsyrendorzhieva, A. I. Albanov, B. A. Gostevskii, and V. I. Rakhlin
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Eꢀmail: vir@irioch.irk.ru
Lithium and sodium bis(trimethylsilyl)amides react with fluoroꢀ, bromoꢀ, and chlorobenzꢀ
enes in THF or toluene to give a mixture of N,Nꢀbis(trimethylsilyl)aniline and N,2ꢀbisꢀ
(trimethylsilyl)aniline. The latter compound is resulted from 1,3ꢀshift of the trimethylsilyl
group from nitrogen to orthoꢀcarbon atom of the benzene ring. Effects of the solvent, halogen,
and alkali metal nature as well as the reaction conditions on the ratio of isomers were examined.
Reaction of iodobenzene with sodium bis(trimethylsilyl)amide in THF produces N,Nꢀbisꢀ
(trimethylsilyl)aniline and 2ꢀiodoꢀN,Nꢀbis(trimethylsilyl)aniline, while in toluene a mixture of
three products, two indicated above and N,Nꢀbis(trimethylsilyl)benzylamine, was obtained.
Key words: dehydrobenzene, alkali metal bis(trimethylsilyl)amides, halobenzenes, trimethylꢀ
silyl group shift.
In recent years, the interest in aryne chemistry shows
present work, we studied the effect of the nature of the
halogen atom in halobenzenes (PhHal) on structure and
compositions of the products arising from their reactions
with lithium and sodium bis(trimethylsilyl)amides.
It has been noted earlier8 that the halogen nature
does not affect the yield and ratio of the products in the
reactions of arynes generated by treatment of aryl halides
with strong bases. Moreover, the extensive structural and
mechanistic studies of transformations of 2ꢀhalo derivaꢀ
tives of aryllithium into the corresponding arynes9 show
substantial effects of the nature of both solvent and
the leaving halogen atom on regioselectivity of these reꢀ
actions.
We found that the reactions of bromoꢀ (4), chloroꢀ (5),
and fluorobenzenes (6) with sodium and lithium bis(triꢀ
methylsilyl)amides (1 and 7, respectively) in all cases afꢀ
ford a mixture of compounds 2 and 3 (GC and NMR
data). The ratio of products 2 and 3 is predetermined by
the structure of the started reagents and the reaction conꢀ
ditions but it is not affected by the degree of conversion.
The data given in Table 1 show that the isomeric ratio
is virtually independent on reaction temperature and is
determined by the solvent polarity and the nature of the
halogen atom in halobenzene PhHal 4—6. At 100 C, the
content of the rearrangement product formed in THF is
decreased in the following order 4 > 5 > 6, while in less
polar toluene, the order is reversed.
fast increase due to unique reactivity of arynes and their
promising applications in organic synthesis.1—3 To date,
a number of methods for the aryne generation are known,4
which have both advantages and certain limitations. Thereꢀ
fore, the aryne generation is intensively studied.
Earlier, we have found5 that bromobenzene reacts with
sodium bis(trimethylsilyl)amide (1) to give a mixture of
N,Nꢀbis(trimethylsilyl)aniline (2) and N,2ꢀbis(trimethylꢀ
silyl)aniline (3), which resulted from the trimethylsilyl
group 1,3ꢀshift from the nitrogen atom to the orthoꢀcarbon
of the benzene ring. The reaction proceeds via dehydroꢀ
benzene intermediate. Subsequent nucleophilic addition
of hexamethyldisilazane to dehydrobenzene could be acꢀ
companied by the trimethylsilyl group migration. Interꢀ
mediate formation of dehydrobenzene is confirmed by the
obtaining N,Nꢀdiethylaniline in the reaction carried out
in triethylamine.6
Reaction of halobenzenes with alkali metal bis(triꢀ
methylsilyl)amides is of interest in two aspects. First, this
reaction is a new route for the aryne generation. Second,
since the 1,3ꢀshift of trimethylsilyl group from nitrogen to
carbon is rather scarcely studied (we found the only examꢀ
ple7 described by Yoshida et al.), it is of interest to reveal
the effects of different factors on rearrangement accompaꢀ
nying the reaction of aryl halides with alkali metal silylꢀ
amides. These findings will allow rational synthesis of varꢀ
ious types of aromatic siliconꢀnitrogen compounds. In the
Examining the effect of the molar reagent ratio on the
composition of the products formed in the reaction of 1
with halobenzenes 4—6 revealed that content of product 2
decreases upon an increase in the amount of halobenzene
* Dedicated to Academician of the Russian Academy of Sciences
N. S. Zefirov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2090—2094, September, 2015.
1066ꢀ5285/15/6409ꢀ2090 © 2015 Springer Science+Business Media, Inc.

Alkali metal silazanides and halobenzenes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015 2091
Table 1. Effects of the solvent nature, halogen, and reaction
temperature on the ratio of products 2 and 3 formed in the
reaction of (Me3Si)2NNa (1) with halobenzenes 4—6a
more polar THF the effect of additives of (Me3Si)2NH 8 is
less pronounced. Reaction of sodium bis(trimethylsilyl)ꢀ
amide 1 with bromobenzene 4 in hexamethyldisilazane 8
affords a mixture of products 2 and 3 in a 4 : 1 ratio in 45%
total yield.
PhHal
Ratio 2 : 3 (yield (%))
Reaction of halobenzenes 4—6 with lithium bis(triꢀ
methylsilyl)amide (Me3Si)2NLi (7) also produces a mixꢀ
ture of products 2 and 3, however their ratio is noticeably
different from one obtained in the reactions involving comꢀ
pound 1 (Table 4).
Toluene, 100 C Toluene, 130 C THF, 100 C
4
5
6
3.69 : 1 (56)
2.72 : 1 (46)
11.7 : 1 (49)
3.33 : 1 (53)
14.1 : 1 (48)
11.5 : 1 (53)
0.74 : 1 (58)
1.15 : 1 (76)
1150 : 1 (45)b
a Reaction time is 3 h.
b Reaction time is 48 h.
A comparison of the data given in Tables 1 and 4 reꢀ
vealed that the content of the rearrangement product 3
formed in the reactions of halobenzenes with lithium amide
7 in THF increases in the order 4 < 5 < 6, while in the
similar reactions involving (Me3Si)NNa 1 a ratio of prodꢀ
ucts 2 : 3 changes in the reversed order.
Table 2. Effect of the reagent ratio on the ratio of products 2
and 3 formed in the reaction of (Me3Si)2NNa (1) with haloꢀ
benzenes 4 and 5*
Hartwig and coꢀworkers have studied Pdꢀcatalyzed reꢀ
gioselective synthesis of arylamines via the reaction of aryl
chlorides and aryl bromides with lithium bis(trimethylꢀ
silyl)amide (7).10 For instance, they have examined cataꢀ
lystꢀfree reactions of some aryl bromides with lithium
amide 7 in toluene: migration of the trimethylsilyl group
to the aromatic ring did not occur, but the yields of arylꢀ
amines were relatively low. These data are in agreement
with the results obtained by us (see Table 4) since the
trimethylsilyl group shift is observed only in the reactions
of compounds 7 and 6.
Ratio
PhHal : 1
Ratio 2 : 3 (yield (%))
Toluene, 130 C THF, 100 C
4
5
4
1 : 2
1 : 1
2 : 1
12.1 : 1 (66)
3.9 : 1 (60)
2.6 : 1 (67)
7.3 : 1 (63)
4.2 : 1 (57)
2.8 : 1 (60)
8.9 : 1 (54)
0.85 : 1 (61)
0.65 : 1 (65)
* Reaction time is 3 h.
Thus, several factors enable formation of rearrangeꢀ
ment product 3. The content of product 3 is higher when
using sodium bis(trimethylsilyl)amide 1 but not its lithiꢀ
um analog 7 and decreases in the following order of
halobenzenes 4 > 5 > 6. An increase in both the solꢀ
vent polarity and mole fraction of halobenzenes relative
to the corresponding amide also favors formation of
product 3.
We obtained unexpected results by studying the reacꢀ
tion of iodobenzene (9) with sodium bis(trimethylsilyl)ꢀ
amide 1 in THF. The reaction produces a mixture of two
products: compound 2 and 2ꢀiodoꢀN,Nꢀbis(trimethylꢀ
silyl)aniline (10) (Scheme 1) with a ratio 2 : 10 = 1 : 6 in
57% total yield.
relative to sodium bis(trimethylsilyl)amide 1 (Table 2).
Similar antibate dependence was also observed by varying
both solvents and halogen atom in halobenzene. A deꢀ
crease in the amount of halobenzenes 4—6 in the reaction
mixture always results in a significant increase in the conꢀ
tent of product 2 (see Table 2).
Table 3 summarizes the effects of the addition of hexaꢀ
methyldisilazane 8 in twoꢀfold excess relative to the
reagents.
From Table 3, it is clearly seen that addition of hexaꢀ
methyldisilazane 8 to the reaction mixture leads to
a noticeable increase in the content of product 2, when the
reaction is carried out in toluene (cf. Table 1). However, in
Table 3. Effects of additives of hexamethyldisilazane 8
on the ratio of products 2 and 3 formed in the reaction
of (Me3Si)2NNa (1) with halobenzenes 4—6a,b
Table 4. Effects of the solvent and halogen nature
on the ratio of products 2 and 3 formed in the
reaction of lithium bis(trimethylsilyl)amide (7)
with halobenzenes 4—6a
PhHal
Ratio 2 : 3 (yield (%))
PhHal
Ratio 2 : 3 (yield (%))
Toluene, 130 C
THF, 100 C
Toluene, 130 C
THF, 100 C
4
5
6
15.8 : 1 (69)
10.5 : 1 (67)
15.4 : 1 (51)
0.56 : 1 (66)c
1.8 : 1 (73)c
140 : 1 (48)c
4
5
6
1 : 0 (45)b
1 : 0 (16)b
2.1 : 1 (85)b
4.65 : 1 (25)
3.77 : 1 (21)
3 : 1 (44)
a Reagent ratio is 8 : 1 : PhHal = 2 : 1 : 1.
b Reaction time is 3 h.
c Reaction time is 48 h.
a Reaction time is 16 h.
b Reaction time is 24 h.

2092
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015
Lis et al.
Scheme 1
Scheme 2
(1)
(2)
Massꢀspectrometry confirms the formation of comꢀ
pound 10 exhibiting a peak for the molecular ion [M]+
with m/z 363 and an intense peak for the fragment ion
1
[M – Me – I]+ with m/z 221. H NMR spectrum conꢀ
tains additional singlet signal of the trimethylsilyl group
at  0.12. 13C NMR spectrum exhibits characteristic sigꢀ
nal at  95.39 attributed to the C atom bonded to the
iodine atom.
The reaction mechanism is shown on Scheme 2.
Similar mechanism involving simultaneous reactions
proceeding via dehydrobenzene 11 and the corresponding
iodineꢀate complex (hypervalent iodine complex) was sugꢀ
gested by Durst and coꢀworkers11 upon studying the reacꢀ
tion of iodobenzene 9 with lithium tetramethylpiperidine
in THF at –40 C leading to a mixture of Nꢀ(2ꢀiodopheꢀ
nyl)ꢀ2,2,6,6ꢀtetramethylpiperidine and Nꢀphenylꢀ2,2,6,6ꢀ
tetramethylpiperidine.
(3)
Iodobenzene 9 reacts with (Me3Si)2NNa 1 in hexaꢀ
methyldisilazane 8 at 130 C to give a mixture of three
products 2, 3, and 10 in a ratio of 10 : 3.4 : 1 in 54% total
yield. Formation of compound 3 and a dramatic decrease
in the content of compound 10 can be due to the poor
solubility of (Me3Si)2NNa (1) in hexamethyldisilazane 8.
This leads to a significant decrease in concentration of
intermediate dehydrobenzene 11 thus enabling the triꢀ
methylsilyl group 1,3ꢀshift from nitrogen to C(2) atom of
the benzene ring in zwitterion 12 (Scheme 3).
(4)
Simultaneously, low concentration of (Me3Si)2NNa 1
results in a decrease in the rate of the reaction of zwitterꢀ
ion 12 following the B pathway (see Scheme 2, reaction
(3)) to give a C(2)ꢀmetallated intermediate 15. This, in
turn, decreases the possibility of the iodineꢀate complex to
form and, consequently, formation of compound 10 is
less probable.
(5)
(6
Reaction of iodobenzene 9 with (Me3Si)2NNa 1 in
toluene proceeds unexpectedly affording three products,
2, 10, and N,Nꢀbis(trimethylsilyl)benzylamine (19), in the
ratio of 5.9 : 1 : 1 in 60% total yield (Scheme 4). This reꢀ
action also produces benzene (18), which is confirmed by
GC using an internal standard.
Formation of amine 19 is evidenced by the presence in
mass spectrum of a molecular ion peak with m/z 251 [M]+
and a fragment ion peak with m/z 162 [M – Bn]+; 1H NMR
spectrum contains the singlet signal of the Me3Si group at
 0.08. 1H and 13C NMR spectra reveal the signals of the
methylene group at  4.09 and 48.46, respectively.
A plausible mechanism of formation of product 19 is
shown on Scheme 5. Iodineꢀate complex 16 decomposes
eliminating phenyl sodium (17) (see Scheme 2, reacꢀ
tion (5)), which metallates toluene (20) to give benzyl

Alkali metal silazanides and halobenzenes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015 2093
Scheme 3
Experimental
NMR spectra were recorded on a Bruker DPXꢀ400 instruꢀ
ment (working frequencies are 400.13 MHz (1H), 100.58 MHz
(
13C), and 79.46 MHz (29Si)) in CDCl3 using Me4Si as an interꢀ
nal standard.
Mass spectrometry (EI, 70 eV) was performed with a Shiꢀ
madzu GCMSꢀQP2010 Ultra instrument (column HPꢀ1MS,
30000×0.25 mm) equipped with a quadruple mass filter, an ion
source temperature of 250 C, working mass range of 35—500 Da.
The compositions of the reaction mixtures were analyzed by
GC performed on a Tsvetꢀ500 gas chromatograph equipped with
a thermal conductivity detector and a glass columns 3 m×4 mm
filled with 10% polymethylsiloxaneꢀ1000 (PMSꢀ1000) on Inerꢀ
tonꢀSuper 0.125—0.150 mm using helium as a carrier gas.
Lithium bis(trimethylsilyl)amide (7) was synthesized by the
known procedure.14
Scheme 4
Yields and ratios of the products were determined as earlier
described.15
Conditions: toluene, 100 C.
Sodium bis(trimethylsilyl)amide (1). To a mixture of sodium
(11.50 g, 500 mmol) and hexamethyldisilazane 8 (80.70 g,
500 mmol), 1,4ꢀdioxane (100 mL) was added. A fine suspension
of sodium was obtained by refluxing the above mixture with
magnetic stirring, then styrene (26.0 g, 250 mmol) was added
dropwise and the stirred reaction mixture was refluxed for 1 h.
Cooling the reaction mixture resulted in crystallization of sodiꢀ
um bis(trimethylsilyl)amide 1 as large needles. Solvent was reꢀ
moved, product was washed with hexane, collected by filtration,
and dried in vacuo (1 Torr) at 100 C for 3 h to give the title
product in the yield of 82.5 g (90%).
sodium (21)12 capable of producing the corresponding
complex 22.13 Decomposition of complex 22 induced by
hexamethyldisilazane 8 leads to amine 19, benzene 18,
and sodium iodide.
Scheme 5
Reaction of sodium bis(trimethylsilyl)amide (1) with bromobenꢀ
zene (4). To a solution of sodium bis(trimethylsilyl)amide 1
(49.5 g, 270 mmol) in toluene (250 mL), bromobenzene 4 (42.4 g,
270 mmol) was added dropwise at room temperature. Heating
the reaction mixture to reflux resulted in precipitation. The reꢀ
action mixture was refluxed for 4 h. Removal of the solvent and
subsequent vacuum distillation of the residue afforded N,Nꢀbisꢀ
(trimethylsilyl)aniline 2 (7.2 g) and N,2ꢀ(trimethylsilyl)aniline 3
(2.9 g).
N,NꢀBis(trimethylsilyl)aniline (2). B.p. 50 C (1 Torr),
nD19 1.4851 (cf. Ref. 16: b.p. 40—41 C (0.3 Torr), nD120 1.4846).
1H NMR, : 0.05 (s, 18 H, Me3Si); 6.88 (dd, 2 H, H(2), H(6),
J = 7.7 Hz, J = 1.1 Hz); 7.03 (tt, 1 H, H(4), J = 7.3 Hz,
J = 1.1 Hz); 7.18 (dd, 2 H, H(3), H(5), J = 7.7 Hz, J = 7.3 Hz).
13C NMR, : 2.1 (Me3SiN); 123.6 (C(4)); 128.4 (C(3), C(5));
130.23 (C(2), C(6)); 148.0 (C(1)). 29Si NMR, : 4.5. MS, m/z
(Irel (%)): 237 [M]+ (25), 222 [M – 15]+ (100), 206 (20), 150
[Me3SiPh]+ (10), 73 [Me3Si]+ (15).
N,2ꢀBis(trimethylsilyl)aniline (3). B.p. 85 C (2 Torr),
19
1
nD 1.5049. H NMR, : 0.27 (s, 9 H, Me3SiN); 0.31 (s, 9 H,
Me3SiC); 3.58 (br.s, 1 H, NH); 6.71 (d, 1 H, H(6), J = 8.0 Hz);
6.73 (ddd, 1 H, H(4), J = 8.0 Hz, J = 7.2 Hz, J = 0.7 Hz); 7.18
(ddd, 1 H, H(5), J = 8.0 Hz, J = 7.2 Hz, J = 1.5 Hz); 7.28 (dd, 1 H,
H(3), J = 7.2 Hz, J = 1.5 Hz). 13C NMR, : –0.6 (Me3SiC);
0.2 (Me3SiN); 115.2 (C(6)); 117.6 (C(4)); 125.1 (C(2)); 130.4 (C(5));
135.3 (C(3)); 152.4 (C(1)). 29Si NMR, : 2.6 (Me3SiN); –6.3
(Me3SiC). MS, m/z (Irel (%)): 237 [M]+ (100), 222 [M – 15]+
(80), 206 (25), 164 (10), 150 [Me3SiPh]+ (15), 73 [Me3Si]+ (80).
Found (%): C, 60.72; H, 9.80; N, 5.88; Si, 23.60. C12H23NSi2.
Calculated (%): C, 60.69; H, 9.76; N, 5.90; Si, 23.65.
Thus, the reaction of sodium bis(trimethylsilyl)amide 1
with iodobenzene 9 differs sharply from the similar reacꢀ
tion with halobenzenes 4—6 (Hal = Br, Cl, F), which is
due apparently to the formation of the corresponding
iodineꢀate complexes upon the reaction. This reaction can
be regarded as a relatively convenient synthetic procedure
towards oꢀiodoaniline and its N,Nꢀdisilyl derivative.

2094
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015
Lis et al.
Reaction of sodium bis(trimethylsilyl)amide (1) with iodobenzꢀ
ene (9) in THF. To a solution of sodium bis(trimethylsilyl)amide 1
(18.3 g, 100 mmol) in THF (90 mL), iodobenzene 9 (20.4 g,
100 mmol) was added dropwise at room temperature. Heating
the reaction mixture to reflux resulted in precipitation. The reꢀ
action mixture was refluxed for 4 h. Vacuum distillation afforded
a mixture of N,Nꢀbis(trimethylsilyl)aniline 2 and 2ꢀiodoꢀN,Nꢀ
bis(trimethylsilyl)aniline with b.p. 48—100 C (1 Torr), yield
6.1 g, ratio 2 : 10 = 3.6 : 1. Compound 10 (0.75 g) was isolated by
vacuum distillation.
The main results were obtained on the material and
technical base of the Baikal Analytical Center for Collecꢀ
tive Use of the Siberian Branch of the Russian Academy of
Sciences.
This work was financially supported by the Council on
Grants of the President of the Russian Federation (Proꢀ
gram for State Support of Leading Scientific Schools,
Grant NShꢀ3649.2014.3).
2ꢀIodoꢀN,Nꢀbis(trimethylsilyl)aniline (10). Oily liquid, b.p.
105 C (1 Torr). 1H NMR, : 0.12 (s, 18 H, Me3Si); 6.76 (td, 1 H,
H(4), J = 7.6 Hz, J = 1.6 Hz); 6.89 (dd, 1 H, H(6), J = 7.8 Hz,
J = 1.5 Hz); 7.21 (td, 1 H, H(5), J = 7.5 Hz, J = 1.5 Hz); 7.82 (dd,
1 H, H(3), J = 7.9 Hz, J = 1.5 Hz). 13C NMR, : 2.1 (Me3SiN);
95.4 (C(2)); 122.7 (C(4)); 122.8 (C(6)); 126.8 (C(5)); 140.1
(C(3)); 151.0 (C(1)). 29Si NMR, : 6.4. MS, m/z (Irel (%)): 363
[M]+ (9), 348 [M – Me]+ (55), 221 [M – Me – I]+ (100), 206
[M – 2 Me – I]+ (43), 73 [Me3Si]+ (23). Found (%): C, 39.71;
H, 6.13; I, 34.85; N, 3.80; Si, 15.51. C12H22INSi2. Calculatꢀ
ed (%): C, 39.66; H, 6.10; I, 34.92; N, 3.85; Si, 15.46.
Reaction of sodium bis(trimethylsilyl)amide (1) with iodobenzꢀ
ene 9 in hexamethyldisilazane (7). A dry ampule flushed with dry
argon was charged with compound 1 (3.2 g, 17.4 mmol), iodoꢀ
benzene 9 (3.56 g, 17.4 mmol), and hexamethyldisilazane (7)
(15 mL). After freeze—pump—thaw degassing, the ampule was
sealed. The reaction was carried out at 130 C for 4 h. Vacuum
distillation afforded a mixture of compounds 2, 3, and 10 with
b.p. 53—106 C (1 Torr), yield 1.9 g, ratio 2 : 3 : 10 = 15 : 1.7 : 1.
Reaction of sodium bis(trimethylsilyl)amide (1) with iodobenzꢀ
ene (9) in toluene. To a solution of compound 1 (18.3 g, 100 mmol)
in toluene (100 mL), iodobenzene 9 (20.4 g, 100 mmol) was
added dropwise at room temperature. Heating the reaction mixꢀ
ture to reflux resulted in precipitation. The reaction mixture was
refluxed for 4 h. Vacuum distillation afforded a mixture of comꢀ
pounds 2, 10, and N,Nꢀbis(trimethylsilyl)benzylamine (19) with
b.p. 45—110 C (1 Torr), yield 9.2 g, ratio 2 : 10 : 19 = 7 : 2 : 4.3.
Compound 19 was also synthesized by counter synthesis as earliꢀ
er described.17 NMR and mass spectra of compound 19 coincide
with those of an authentic sample.
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17. M. J. Barany, R. P. Hammer, R. B. Merrifield, G. Barany,
J. Am. Chem. Soc., 2005, 127, 508.
NꢀBenzylꢀN,Nꢀbis(trimethylsilyl)amine (19). 1H NMR, :
0.08 (s, 18 H, Me3Si); 4.09 (s, 2 H, CH2); 7.17 (m, 1 H, C(4));
7.26 (m, 4 H). 13C NMR, : 1.9 (Me3Si); 48.5 (CH2); 125.8
(C(3), C(5)); 126.0 (C(2), C(6)); 127.8 (C(4)); 143.6 (C(1)). 29Si
NMR, : 7.2. MS, m/z (Irel (%)): 251 [M]+ (16), 236 [M – Me]+
(100), 174 [M – C6H5]+ (32), 162 [M – CH2 – C6H5]+ (100),
148 [M – Me – CH2 – C6H5]+ (33), 135 [M – 2 Me – CH2 –
– C6H5]+ (45), 73 [Me3Si]+ (67).
Received March 30, 2015