L. Djako6itch et al. / Journal of Organometallic Chemistry 592 (1999) 225–234
233
4.2.4.4. Data for R=OCH3, isolated yield 39% as a
MHz: 147.66 (CꢀN, C6
116.26 (p-C6H4N); 112.43 (o-C6
21.78 (CH3); 12.40 (C6 H3CH2N). C11H17N, Mw 163.14.
6
H4N); 128.91 (m-C6
6
H5N);
yellow oil. 1H-NMR, CDCl3, 400.13 MHz: 6.79 (d,
6
6
H5N); 44.08 (C6 H2N);
3
3J=9.0 Hz, 2H, m-C6H4
6
N); 6.46 (d, J=9.0 Hz, 2H,
6
o-C6H4
1.87 (m, 4H, NCH2CH2
13C-NMR, CDCl3, 100.62 MHz: 160.02 (p-C6
151.08 (CꢀN, C6H4N); 117.02 (m-C6H5N); 114.29 (o-
C6H5N); 55.96 (CH3); 54.27 (CH2N); 26.97
(CH2CH2N); 25.92 (C
6
N); 3.92 (m, 4H, NCH2
); 1.74 (m, 2H, NCH2CH2CH2
H4N);
6
); 3.34 (s, 3H, CH3
6
O);
MS: m/z (%): [M+] 163 (28), [M+−CH3] 148 (37),
[M+−C2H5] 134 (35), [M+−C2H5−CH2] 120 (68).
The other para-products described in this paper
could not be isolated as a pure compound. We could
isolate the mixture of the para- and meta-aniline
derivatives with a ‘purity’ ]88%. The NMR of this
mixture was recorded in order to have an additional
analytical method for the determination of the ratio
para-/meta-. The mixture was then used to calibrate the
GLC and the GLC–MS in order to determine GLC
yields by the internal standard method. The MS ob-
tained by GLC–MS for the para-isomer are given
below.
6
6
).
6
6
6
6
6
6
6
6 H2CH2CH2N). C12H17NO, Mw
191.13. MS: m/z (%): [M+] 191 (33), [M+−CH3] 176
(35); [M+−C4H8] 135 (52), [M+−C5H10N] 121 (12).
4.2.4.5. Data for R=NO2, isolated yield 41% as an
1
orange 6iscous oil. H-NMR, CDCl3, 400.13 MHz: 8.07
3
3
(d, J=9.0 Hz, 2H, m-C6H4
2H, o-C6H4N); 3.32 (m, 4H, NCH2
NCH2CH2); 1.81 (m, 2H, NCH2CH2CH2
CDCl3, 100.62 MHz: 150.67 (CꢀN, C6
(p-C6H4N); 125.15 (m-C6
54.02 (CH2N); 27.28 (C
6 N); 6.87 (d, J=9.0 Hz,
6
6 ); 1.91 (m, 4H,
6
6
). 13C-NMR,
H4N); 141.47
6
4.2.5.3. Data for R=CH3O. C11H17NO, Mw 179.13.
MS: m/z (%): [M+] 179 (25), [M+−CH3] 163 (32),
[M+−C2H5] 149 (42), [M+−C2H5−CH2] 135 (67),
[M+−N(C2H5)2+H] 107 (71).
6
6
H5N); 115.14 (o-C6
H2CH2N); 25.92 (C
6
H5N);
H2-
6
6
6
CH2CH2N). C11H14N2O2, Mw 206.11. MS: m/z (%):
[M+] 205 (28); [M+−NO2] 159 (49); [M+−C4H8] 150
(62).
4.2.5.4. Data for R=F. C10H14NF, Mw 167.11. MS:
m/z (%): [M+] 166 (21), [M+−F] 147 (31), [M+−
C2H5] 137 (39), [M+−C2H5−CH2] 123 (71).
4.2.4.6. Data for R=CH3CO, isolated yield 36% as an
1
orange 6iscous oil. H-NMR, CDCl3, 400.13 MHz: 7.79
3
3
(d, J=8.3 Hz, 2H, m-C6H4
2H, o-C6H4N); 3.34 (m, 4H, NCH2
NCH2CH2); 2.48 (s, 3H, CH3); 1.77 (m, 2H,
NCH2CH2CH2
). 13C-NMR, CDCl3, 100.62 MHz:
196.56 (CO); 149.92 (CꢀN, C6
124.92 (p-C6H4N); 114.33 (o-C6
26.04 (CH2CH2N); 25.12 (C
(C
6
N); 6.92 (d, J=8.3 Hz,
4.2.5.5. Data for R=NO2. C10H14N2O2, Mw 194.11.
MS: m/z (%): [M+] 194 (18), [M+−NO2] 148 (35),
[M+−C2H5] 165 (32), [M+−C2H5−CH2] 151 (69).
6
6
); 1.89 (m, 4H,
6
6
6
6
H4N); 129.63 (m-C6
6
H5N);
6 H2N);
4.2.5.6. Data for R=CH3CO. C12H17NO, Mw 191.13.
MS: m/z (%): [M+] 190 (17), [M+−CH3] 175 (41),
[M+−C2H5] 161 (36), [M+−CH3CO] 148 (62), [M+
−C2H5−CH2] 147 (53).
6
6
H5N); 51.09 (C
6 H2CH2CH2N); 26.27
6
6
H3CO). C13H17NO, Mw 203.13. MS: m/z (%): [M+]
202 (32); [M+−CH3] 187 (52); [M+−CH3CO] 159
(68); [M+−C4H8] 146 (62).
4.2.5. Characterisation of the aniline deri6ati6es of the
diethyl amine: p-RC6H4N(C2H5)2
Acknowledgements
We are grateful to the European Community (Marie-
Curie, TMR program) for a research grant to L.D., the
Technische Universita¨t of Mu¨nchen and the Fonds der
Chemischen Industrie (Germany) for support. We ac-
knowledge Degussa AG (Germany) for the donation of
PdCl2 and catalyst support.
4.2.5.1. Data for R=H, isolated yield 52% as a slightly
yellow oil. H-NMR, CDCl3, 400.13 MHz: 7.35 (m, 2H,
1
C6H5
1.26 (m, 6H, NCH2CH3
MHz: 147.53 (CꢀN, C6
115.20 (p-C6H5N); 111.66 (o-C6
12.32 (C
6
N); 6.82 (m, 3H, C6H5
6 N); 3.43 (m, 4H, NCH6 2);
6
). 13C-NMR, CDCl3, 100.62
6
H5N); 128.98 (m-C6
6
H5N);
6 H2N);
6
6
H5N); 44.03 (C
6
H3CH2N). C10H15N, Mw 149.12. MS: m/z (%):
[M+] 149 (25), [M+−CH3] 134 (42), [M+−C2H5] 120
(21), [M+−C2H5−CH2] 106 (47), [M+−N(C2H5)2+
H] 77 (69).
References
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Int. Ed. Engl. 34 (1995) 1348. (b) M. Beller, Angew. Chem. Int.
Ed. Engl. 34 (1995) 1316. (c) M.S. Driver, J.F. Hartwig, J. Am.
Chem. Soc. 118 (1996) 7217. (d) J.P. Wolfe, R.A. Rennels, S.L.
Buchwald, Tetrahedron 52 (1996) 7525. (e) J.F. Hartwig, Angew.
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meier, in: M. Beller, C. Bolm (Eds.), Transition Metals for
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4.2.5.2. Data for R=CH3, isolated yield 47% as a
1
slightly yellow oil. H-NMR, CDCl3, 400.13 MHz: 7.18
3
3
(d, J=8.5 Hz, 2H, m-C6H4
2H, o-C6H4N); 3.28 (m, 4H, NCH2
1.22 (m, 6H, NCH2CH3
). 13C-NMR, CDCl3, 100.62
6
N); 6.58 (d, J=8.5 Hz,
6
6
); 2.41 (s, 3H, CH3);
6
6