(
)
B. Wrackmeyer et al.rJournal of Organometallic Chemistry 552 1998 247–254
253
Ž
.
mixture of 1.18 g 8 mmol of 2,5-diallylpyrrole in 100
ml of THF. The mixture was stirred at room tempera-
ture for 15 h. After that all volatile material was re-
mixture was stirred at room temperature for 24 h. Then
the solvent was removed in vacuo and the residue was
taken up in hexane. After filtration, fractional distilla-
y1
Ž
Ž . Ž
tion gave 0.37 g 90% of 10 b.p. 1208Cr10 Torr;
moved in vacuo. The oily yellowish residue 3.2 g;
100% was identified as the pure H NMR: )95%
compound 5. For the preparation of 4 0.8 g 6.4 mmol
of 9-BBN in 30 ml of THF were used. The excess of
colourless liquid as a mixture of isomers. 1H NMR
.
1
.
Ž1
.
.
1
Ž
Ž
.
w
Ž1
C6 D6, 250 MHz d H J H, H s6.69 m H-1;
.
x
Ž .
X
Ž .
Ž .
Ž .
Ž .
Ž .
5.82 m H-2; 3.93 m H-8a; 2.20 m H-2 ; 2.00 m
X
y4
Ž
Ž .
Ž .
Ž .
2,5-diallylpyrrole was removed in vacuo 10
Torr,
H-3; 1.70 m H-4rH-7; 1.40 m H-3 ; 1.32r1.12 m
1
1
.
Ž
.
Ž .
w
x
Ž .
room temperature . 5: H NMR C6 D6, 250 MHz d H
H-8; 0.99 t 7.0 CH3; 0.84 m H-5; 0.58 m H-3;
1
X
w
Ž1
J H, H s7.11 br NH ; 5.99 d 2.6 Hz H-
.
x
w x
Ž
.
Ž .
w
x Ž
Ž .
0.50r0.32 m H-6rH-1.
.
Ž .
w
x
Ž
.
1rH-2 ; 2.48 t 7.7 Hz H-3rH-8 ; overlapping mul-
4.7. Crystal structure determination of 3
Ž
tiplets at 2.00–1.18 H-4rH-5rH-6rH-7r9-BBN
.
Ž
.
groups .
The neat sample of 3, C10 H14 BN, MG 150.03 was
sealed in a 0.3 mm Lindemann capillary and cooled on
a Siemens–Nicolet R3 four circle diffractometer until a
polycrystalline material emerged below the melting point
at 245 K. A cylindric single crystal was grown by
means of a miniature zone melting procedure applying
( )
4.3. g-Picoline adduct of 3 6
Ž
Ž
.
.
After dissolving of 100 mg 0.63 mmol of 3 in 0.5
ml of C6 D6 in an NMR tube 5 mm o.d. , g-picoline
was added at room temperature, and the formation of
the adduct became evident from the 11 B and 13C NMR
w
x
Ž .
an IR laser beam 27 . The cell dimensions as8.419 2 ,
˚
Ž .
Ž .
Ž .
bs15.618 2 , cs15.812 3 A, as119.41 3 , bs
Ž
.
data Table 1 . After removing the C6 D6 in vacuo, a
colourless solid was left which was recrystallized from
3
˚
Ž .
Ž .
Ž .
91.38 3 , gs94.60 3 8, Vs1800.5 6 A , were deter-
Ž .
1
mined at 133 2 K with graphite monochromated MoKa
1
Ž
.
Ž
.
hexane m.p. 828C . H NMR C6 D6, 250 MHz d H
1
X
X
X
X
radiation. Triclinic space group P1 with Zs8, density
w
Ž1
J H, H s7.46 m H-2 rH-6 ; 7.16 m H-3 rH-5 ;
.
x
Ž .
Ž .
calc. s1.173 Mg my3, ms0.067 mmy1, 3514 inten-
Ž
.
Ž . Ž . Ž .
w
x
5.77 s H-1rH-2; 2.58 t 6.3 H-3rH-8; 2.37 s
Ž
.
sities collected 2Qmax s 408 , 3348 independent
Ž
.
Ž .
CH3; 1.31 quint. H-4rH-7; 0.76 t H-5rH-6.
2
2
Ž
Ž
.
.
Ž
Ž
2 ..
,
Ž
Rint
F
s0.1544 , 3005 observed Fo G2s F
Ž
.
structure solution Direct Methods and refinement 434
4.4. Reaction of 3 with acetic acid to 7 and with
trifluoromethylsulfonic acid to 8
.
parameters, H atoms as rigid groups with Siemens-
Ž
.
SHELX Version 5.1 , R1s0.0454, wR2s0.1169,
The reactions were carried out under the same condi-
GOFs1.053, residual electron density 0.189 and
y3
˚
tions as described for 6, and the results were deduced
y0.322 e A
.
from consistent 11 B and C NMR data Table 3 . H
NMR data confirm that 7 is in fast equilibrium with 3,
and therefore, the syn- and anti isomers cannot be
13
1
Ž
.
Acknowledgements
1
distinguished. In the case of 8, the H NMR spectra
Support of this work by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie is
gratefully acknowledged.
confirm the results of 13C NMR spectra that both iso-
Ž
.
mers are present in a ratio of 2:1 without assignment .
The starting material 3 was recovered almost quantita-
tively by fractional distillation.
References
4 .5 . L ith iu m -8 b -a za -5 a -b o r a ta -5 -b u ty l-
3,4,5,5a,6,7,8,8b-octahydro-acenaphthylene 9
w x
Ž .
H. Bellut, R. Koster, Liebigs Ann. Chem. 738 1970 32–57.
¨
1
w x
2
P. Szarvas, J. Emri, P. Gyory, Acta Chim. Acad. Sci. Hung. 64
¨
Ž
.
1970 203.
Ž
.
w x
3
A solution of 1 g 6.3 mmol of 3 in 10 ml of hexane
J. Emri, P. Gyory, P. Szarvas, Z. Anorg. Allgem. Chem. 400
¨
n
Ž
.
1973 321.
Ž
was cooled to y788C and 10.8 ml of BuLi 1.6 M in
w x
4
P. Szarvas, P. Gyory, J. Emri, Acta Chim. Acad. Sci. Hung. 70
¨
.
hexane was added after 1 min. The mixture became
Ž
.
1974 1.
Ž
.
white. Filtration gave 1.3 g 92% of 9 as a white
w x
5
B. Wrackmeyer, H.E. Maisel, B. Schwarze, W. Milius, R.
1
n
Ž
Ž
.
.
w
Ž1
powder. H NMR C6 D6rTHF 1:1 , 258C
J H,
Ž
.
Koster, J. Organomet. Chem. 1997 in press.
¨
1
.
x
Ž . Ž
.
Ž .
Ž . Ž
w x
6
H : 5.21 s H-1rH-2 ; 2.41 m r2.31 m H-3rH-
B. Wrackmeyer, B. Schwarze, I. Ordung, J. Organomet. Chem.
X
Ž
.
1997 in the press.
.
Ž .
Ž .
Ž .
Ž . Ž
Ž . Ž
8 ; 1.68 m r1.42 m r1.14 m H-4rH-7rH-2 rH-
X
w x
7
Ž
.
B. Wrackmeyer, B. Schwarze, J. Organomet. Chem. 1997 in
.
.
Ž .
w
x
3 ; 0.15 m r0.00 m H-5rH-6 ; 0.76 t 6.9 Hz
the press.
X
Ž
.
Ž . Ž
.
CH3 ; 0.48 m H-1 .
w x
8
R. Koster, G. Bruno, P. Binger, Justus Liebigs Ann. Chem. 644
¨
Ž
.
1961 1.
4.6. Protonation of 9: 2-pyrrole-borane adducts 10
w x
Ž .
9
x
B. Wrackmeyer, J. Organomet. Chem. 117 1976 313.
w
Ž
.
10 R. Koster, in: R. Koster Ed. , Houben-Weyl, Methoden der
¨
¨
Ž
.
Acetic acid 0.12 ml, 2 mmol was added to a
Organischen Chemie, XIIIr3a, Organoborverbindungen,
Diorganohydroborane, Thieme, Stuttgart, 1982, pp. 322–54.
Ž
.
solution of 0.43 of 9 2 mmol in 5 ml of THF and the