4492 Organometallics, Vol. 15, No. 21, 1996
Castel et al.
103.83, 121.59, 123.58, 124.25, 125.66, 133.00, 133.74, 136.32,
158.73, 160.20 (C10H6); Li NMR (77.77 MHz, THF-d8) δ 0.86
hydrolysis, extraction and concentration, analysis of the
residue by H NMR confirmed the formation of 4a (86%) and
7
1
(s) ppm.
3a (16%).
2c (red solution) (55%): 1H NMR (200.13 MHz, THF-d8) δ
3.50 (s, 6H, OCH3), 5.58 (s, 1H, GeH), 6.61 (d, J ) 7.3 Hz, 2H,
P r ep a r a tion of 4a . A solution of 8.7 mmol of t-BuLi (1.7
M in pentane) was added to 3a (2 g, 6.2 mmol) in 10 mL of
THF at -40 °C. The mixture was stirred at -40 °C for 40
min and treated with an excess of MeI (see above). Analysis
of the residue by 1H NMR showed the presence of 4a (96%).
4a was then distilled: Bp 68 °C/0.003 mmHg; 1H NMR (CDCl3)
δ 0.76 (s, 6H, CH3), 3.61 (s, 3H, OCH3), 6.74 (dd, J ) 6.3 Hz,
J ) 2.5 Hz, 1H, C10H6), 7.24-7.51 (m, 8H, C6H5, C10H6), 7.62
(dd, J ) 6.9 Hz, J ) 1.7 Hz, 1H, C10H6), 7.81 (dd, J ) 7.8 Hz,
J ) 1.8 Hz, 1H, C10H6); 13C NMR (50.32 MHz, CDCl3, {1H}) δ
0.58 (CH3), 53.88 (OCH3), 127.77, 127.84, 133.30, 144.27
(C6H5), 104.27, 121.36, 125.68, 125.82, 129.21, 134.36, 134.55,
135.30, 156.00 (C10H6); MS (EI, 70eV) m/z ) 338 ((M+), 12%),
323 ((M - CH3), 85%), 308 ((M - 2 CH3), 48%), 261 ((M -
C
10H6), 6.95 (d of d, J ) 7.8 Hz, J ) 7.1 Hz, 2H, C10H6), 7.12
(d of d, J ) 7.6 Hz, J ) 8 Hz, 2H, C10H6), 7.24-7.43 (m, 4H,
10H6), 7.92 (d, J ) 6.7 Hz, 2H, C10H6); 13C NMR (50.32 MHz,
C
THF-d8, {1H}) δ 55.59 (OCH3), 105.00, 122.20, 123.99, 126.01,
133.52, 135.13, 136.30, 160.40, 160.76 (C10H6); 7Li NMR (77.77
MHz, THF-d8) δ 0.98 (s) ppm.
2d (yellow solution) (90%): 1H NMR (200.13 MHz, THF-
d8) δ 3.88 (s, 3H, OCH3), 4.60 (s, 1H, GeH), 6.80-8.00 (m, 6H,
C6H4); 13C NMR (50.32 MHz, THF-d8, {1H}) δ 55.33 (OCH3),
109.08, 120.67, 125.59, 139.78, 146.82, 164.26 (C6H4).
Rea ction of 2a -d w ith MeI. An excess of MeI (100%) was
added to a solution of (organohydrogermyl)lithium at the
temperature used for their preparation (2a , 20 °C; 2b-2d -40
°C). The mixture was allowed to warm to ambient tempera-
ture for 1 h. After hydrolysis, extraction, and concentration,
the residue yielded the following.
C6H5), 12%), 293 ((M - 3CH3), 31%). Anal. Calcd for C19H20
GeO: C, 67.72; H, 5.98. Found: C, 68.23; H, 6.38.
-
Rea ction of 1b w ith 2 n -Bu Li. A solution of 1.7 mmol of
n-BuLi (1.6 M in hexane) was added to 1b in 2 mL of ether at
-20 °C. After 8 min at this temperature, an excess of MeI
was added. The mixture was allowed to warm to ambient
temperature during 1 h and then concentrated. The residue
was treated with 10 mL of CH2Cl2. After decantation from
LiI, the solution was evaporated leading to a white powder
identified as 5b: 0.11 g (28%); mp 155-165 °C; 1H NMR
(CDCl3) δ 1.54 (s, 3H, CH3), 2.25 (s, 9H, p-CH3 and o-CH3),
3.38 (s, 3H, OCH3), 6.75 (dd, J ) 1.8 Hz, J ) 6.9 Hz, 1H,
C10H6), 6.76 (s, 2H, C6H2), 7.24-7.66 (m, 3H, C10H6), 7.87 (dd,
J ) 1.4 Hz, J ) 8.2 Hz, 1H, C10H6), 8.18 (dd, J ) 1.4 Hz, J )
6.9 Hz, 1H, C10H6); 13C NMR (50.32 MHz, CDCl3, {1H}) δ 16.35
(CH3), 21.02 (p-CH3), 23.80 (o-CH3), 54.07 (OCH3), 129.35,
134.87, 138.88, 141.08 (C6H2), 104.33, 121.79, 125.69, 127.04,
129.49, 134.17, 136.36, 137.68, 154.21 (C10H6); MS (DCI, CH4)
m/z ) 493 ((MH)+, 2%), 477 ((M - CH4), 3%), 461 ((M - CH3-
3a (51%): viscous oil which slowly precipitated white
crystals at 20 °C; mp 51-53 °C; 1H NMR (CDCl3) δ 0.79 (d, J
) 3.1 Hz, 3H, GeCH3), 3.67 (s, 3H, OCH3), 5.42 (q, J ) 3.1 Hz,
1H, GeH), 6.77 (dd, J ) 6.1 Hz, J ) 2.2 Hz, 1H, C10H6), 7.24-
7.52 (m, 8H, C6H5, C10H6), 7.68 (dd, J ) 6.9 Hz, J ) 1.5 Hz,
1H, C10H6), 7.83 (dd, J ) 7.9 Hz, J ) 1.6 Hz, 1H, C10H6); 13C
NMR (50.32 MHz, CDCl3, {1H}) δ -2.21 (CH3Ge), 54.07
(OCH3), 127.98, 128.12, 133.98, 141.02 (C6H5), 104.49, 121.31,
125.77, 126.01, 129.36, 131.01, 132.49, 135.13, 135.55, 155.96
(C10H6); IR (pure) 2043.9, 1991.4 (GeH); MS (EI, 70 eV) m/z )
324 ((M+), 26%), 309 ((M - CH3), 100%), 231 ((M - CH3
-
C6H6), 40%), 200 ((M - CH3 - C6H6 - OCH3, 11%). Anal.
Calcd for C18H18GeO: C, 66.94; H, 5.62. Found: C, 66.70; H,
5.68.
3b (47%): viscous oil; bp 80 °C/0.01 mmHg (with partial
1
decomposition); H NMR (CDCl3) δ 0.76 (d, J ) 3.4 Hz, 3H,
OH), 2%), 365 ((M - HI), 100%). Anal. Calcd for C21H23
GeIO: C, 51.38; H, 4.72. Found: C, 50.82; H, 4.80.
-
GeCH3), 2.29 (s, 9H, o-CH3 and p-CH3), 3.67 (s, 3H, OCH3),
5.66 (q, J ) 3.4 Hz, 1H, GeH), 6.78 (dd, J ) 6.1 Hz, J ) 2.7
Hz, 1H, C10H6), 6.84 (s, 2H, C6H2), 7.24-7.53 (m, 3H, C10H6),
7.61 (dd, J ) 6.9 Hz, J ) 1.6 Hz, 1H, C10H6), 7.78 (dd, J ) 7.9
Hz, J ) 1.7 Hz, 1H, C10H6); 13C NMR (50.32 MHz, CDCl3, {1H})
δ -0.43 (GeCH3), 21.14 (p-CH3), 24.32 (o-CH3), 54.22 (OCH3),
128.45, 134.55, 137.87, 143.41 (C6H2), 104.57, 121.32, 125.69,
126.11, 128.98, 131.12, 133.56, 135.24, 135.95, 156.51 (C10H6);
IR (pure) 2062.0, 1980.5 (GeH); MS (EI, 70 eV) m/z 366 ((M+),
6%), 351 ((M - CH3), 100%), 336 ((M - 2CH3), 29%), 247 ((M
- C9H11), 26%), 232 ((M - CH3 - C9H11), 38%).
Rea ction of 3b w ith MeI. The mixture of 3b (0.064 g (0.13
mmol), 5 mL of MeI, and a catalytic quantity of AIBN (2,2′-
azobis(2-methylpropionitrile)) was heated at 80 °C for 48 h.
After concentration under vacuum, the analysis of the trans-
parent residue showed the formation of 5b (50%) with decom-
position.
Rea ction of 1d w ith 2 n -Bu Li. A solution of 1.8 mmol of
n-BuLi (1.6 M in hexane) was added to a solution of 1d (0.22
g, 0.75 mmol) in 2 mL of ether at -40 °C. After 1 h, an excess
of MeI was added and the mixture was treated using the same
conditions as those described above. Analysis of the residue
3c formed as a white powder. 1H NMR analysis showed
the presence of 3c (70%). Further recrystallizations did not
allow us to isolate pure 3c. 1H NMR (CDCl3): δ 0.80 (d, J )
2.8 Hz, 3H, GeCH3), 3.58 (s, 6H, OCH3), 5.76 (q, J ) 2.8 Hz,
1H, GeH), 6.76 (dd, J ) 2.4 Hz, J ) 6.3 Hz, 2H, C10H6), 7.24-
7.51 (m, 6H, C10H6), 7.62 (dd, J ) 1.5 Hz, J ) 6.8 Hz, 2H,
1
by H NMR showed the formation of 3d (51%) and 4d (49%).
Rea ction of 1d w ith 2 t-Bu Li. The same reaction was
realized with t-BuLi and led, after treatment with MeI, to a
mixture of 3d (41%) and 4d (59%).
10H6), 7.78 (dd, J ) 1.5 Hz, J ) 7.8 Hz, 2H, C10H6). 13C NMR
P r ep a r a tion of 4d . A solution of 1d (0.54 g, 2 mmol) in 5
mL of CCl4 with a catalytic quantity of AIBN was warmed at
reflux for 1 h. After concentration, a white powder identified
as (MeOC6H4)2GeCl2 (0.54 g, 75%) was obtained. This com-
pound was alkylated by MeMgI (20 mmol). After hydrolysis,
extraction, and concentration, 0.20 g (32%) of 4d was ob-
C
(50.32 MHz, CDCl3, {1H}): δ 0.88 (GeCH3), 54.11 (OCH3),
104.30, 121.21, 125.47, 125.99, 128.52, 134.75, 135.05, 136.47,
156.29 (C10H6). IR (Nujol): 2071.5, 2009.5 (GeH). MS (GC-
MS, EI, 30 eV): m/z 404 ((M+), 6%), 389 ((M - CH3), 100%),
374 ((M - 2CH3), 33%).
1
tained: Mp 68-72 °C; H NMR (CDCl3) δ 0.65 (s, 6H, CH3),
3d (64%) was obtained after crystallization from pentane:
Mp 45-46 °C; 1H NMR (CDCl3) δ 0.78 (d, J ) 3 Hz, 3H, CH3),
3.81 (s, 3H, OCH3), 5.17 (q, J ) 3 Hz, 1H, GeH), 6.84-7.44
(m, 4H, C6H4); 13C NMR (50.32 MHz, CDCl3, {1H}) δ -4.27
(CH3), 55.40 (OCH3), 109.94, 120.85, 126.04, 130.58, 136.08,
163.32 (C6H4); IR (Nujol) 2073 (GeH); MS (EI, 70 eV) m/z )
304 ((M+), 10%), 289 ((M - CH3), 30%). Anal. Calcd for
3.75 (s, 3H, OCH3), 6.79-7.31 (m, 4H, C6H4); 13C NMR (50.32
MHz, CDCl3, {1H}) δ -1.66 (CH3), 55.22 (OCH3), 109.75,
120.60, 128.46, 130.13, 135.25, 163.41 (C6H4); MS (EI, 70 eV)
m/z 318 ((M+), 8%), 303 ((M - CH3), 100%). Anal. Calcd for
C16H20GeO2: C, 60.64; H, 6.36. Found: C, 59.99; H, 6.26.
C
15H18GeO2: C, 59.43; H, 5.99. Found: C, 58.63; H, 6.14.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data, atom coordinates, thermal parameters, and bond dis-
tances and angles and ORTEP diagrams (11 pages). Ordering
information is given on any current masthead page.
Rea ction of 1a w ith 2 n -Bu Li. A solution of 2.5 mmol of
n-BuLi (1.6 M in hexane) was added to a solution of 1a (0.25
g, 0.8 mmol) in 1 mL of ether at -40 °C. The mixture was
stirring at -40 °C for 1 h, and an excess of MeI (0.2 mL) was
then added. The mixture was allowed to warm for 2 h. After
OM960299N