62
C. Breschi et al. / Journal of Organometallic Chemistry 607 (2000) 57–63
(12.6H, s, CMe3, 7b); 1.57 (12.6H, s, CMe3, 7b); 7.12
(1.4H, dd, J32=8, J34=2, H3, 7b); 7.20 (1.8H, s, H1,
7a); 7.51 (1.4H, d, H2, 7b); 7.62 (1.4H, d, H4, 7b). Lit.
[30,35].
Fig. 2.
4.3.6. 1,3,5-Trimethylsilylbenzene (8a), and
(2H, m, H3+H4, 2b); 7.04 (1H, d, J23=6.5, H2, 2b).
1,2,4-trimethylsilylbenzene (8b), from
trimethylsilylacetylene (run 11, Table 3, 8a:8b=5:95)
GC-MS (m/z)=294 [M+]. 1H-NMR (CDCl3): l 0.23
(17.1H, s, SiMe3, 8b); 0.26 (2.7H, s, SiMe3, 8a); 0.42
(17.1H, s, SiMe3, 8b); 0.45 (17.1H, s, SiMe3, 8b); 6.75
(0.3H, s, H1, 8a); 7.49 (1.9H, dd, J32=7.5, J34=1.5,
H3, 8b); 7.66 (1.9H, d, H2, 8b); 7.84 (1.9H, d, H4, 8b).
Anal. Calc. for C15H30Si3: C, 61.14; H, 10.26. Found:
C, 61.03; H, 10.11%. Lit. 8a [25].
Lit. [33].
4.3.1. 1,3,5-Tri-sec-butylbenzene (3a), and
1,2,4-tri-sec-butylbenzene (3b), from
3-methyl-1-pentyne (run 6, Table 3, 3a:3b=53:47)
GC-MS (m/z)=246 [M+]. 1H-NMR (CDCl3): l 0.81
(18H, t, J=7.6, CH2CH3); 1.20 (18H, d, J=7.8,
CHCH3); 1.57 (12H, m, CHCH2CH3); 2.53 (4H, m,
PhCH, 3a+3b); 2.95 (2H, m, PhCH, 3b); 6.78 (3H, s,
H1, 3a); 6.95 (m, 2H, H3+H4, 3b); 7.11 (1H, d,
J23=6.5, H2, 3b). Lit. [34].
4.3.7. 1,3,5-Triphenylbenzene (9a), and
1,2,4-triphenylbenzene (9b), from phenylacetylene (run
12, Table 3, 9a:9b=65:35)
GC-MS (m/z)=306 [M+]. 1H-NMR (C6D6): l 6.85–
7.30 (30H, m, C6H5, 9a+9b); 7.35 (0.7H, d, J23=5,
H2, 9b); 7.49 (0.7H, m, H3, 9b); 7.65 (0.7H, d, J34=1.8,
H4, 9b); 7.74 (3.9H, s, H1, 9a). Lit. [25,36].
4.3.2. 1,3,5-Tri(2-methylbutyl)benzene (4a) and
1,2,4-tri(2-methylbutyl)benzene (4b), from
4-methyl-1-hexyne (run 7, Table 3, 4a:4b=45:55)
GC-MS (m/z)=288 [M+]. 1H-NMR (CDCl3): l
0.75–1.05 (36H, m, CHCH3+CH2CH3); 1.20–1.60
(18H, m, CHCH3+CH2CH3); 2.30 (6H, m, PhCHH);
2.60 (6H, m, PhCHH); 6.73 (2.7H, s, H1, 4a); 6.88 (m,
2.2H, H3+H4, 4b); 7.0 (1.1H, d, J23=6.5, H2, 4b).
Anal. Calc. for C21H36: C, 87.41; H, 12.59. Found: C,
87.29; H, 12.40%. Lit. [33].
4.3.8. Hexamethylbenzene (10), from 2-butyne (run 13,
Table 3)
1
MS (m/z)=162 [M+]. H-NMR (CDCl3): l 2.21 (s,
CH3). M.p.=162°C.
4.3.9. Hexaethylbenzene (11), from 3-hexyne (run 14,
Table 3)
4.3.3. 1,3,5-Tri(3-methylpentyl)benzene (5a), and
1,2,4-tri(3-methylpentyl)benzene (5b), from
MS (m/z)=246 [M+]. 1H-NMR (CDCl3): l 1.27
(18H, t, J=8, CH2CH3); 2.75 (12H, q, CH2CH3).
M.p.=130°C. Lit. [37].
5-methyl-1-heptyne (run 8, Table 3, 5a:5b=52:48)
GC-MS (m/z)=330 [M+]. H-NMR (CDCl3): l 0.9
1
(36H, m, CHCH3+CH2CH3); 1.10–1.95 (30H, m,
CH2CH(CH3)CH2CH3); 2.5 (12H, m, PhCH2); 6.78
(3H, s, H1, 5a); 6.92 (m, 2H, H3+H4, 5b); 7.0 (1H, d,
J23=6.5, H2, 5b). Anal. Calc. for C24H42: C, 87.19; H,
12.81. Found: C, 87.01; H, 12.63. Lit [33].
4.3.10. Hexaphenylbenzene (12), from diphenylacetylene
(run 15, Table 3)
1
MS (m/z)=534 [M+]. H-NMR (CDCl3): l 6.81 (s,
C6H5). M.p.=462°C. Lit. [37].
4.3.11. 2-(5-Hexynyl)-5,6,7,8-tetrahydronaphthalene
(13), from 1,7-octadiyne
4.3.4. 1,3,5-Tri(4-methylhexyl)benzene (6a), and
1,2,4-tri(4-methylhexyl)benzene (6b) from
GC-MS (m/z)=212 [M+]. 1H-NMR (CDCl3, Fig.
2): l 1.57 (2H, m, Hh); 1.72 (2H, m, Hg); 1.78 (4H, m,
Ha); 1.93 (1H, t, Jli=2.5, Hl); 2.20 (2H, dt, Jih=7.5,
Hi); 2.55 (2H, t, Jfg=7.8, H f); 2.74 (4H, m, Hb); 6.87
(1H, s, Hc); 6.89 (1H, d, Jed=7, He), 6.96 (1H, d, Hd).
Lit. [38].
6-methyl-1-octyne (run 9, Table 3, 6a:6b=48:52)
1
GC-MS (m/z)=372 [M+]. H-NMR (CDCl3): l 0.8
(36H, m, CHCH3+CH2CH3); 1.0–1.70 (42H, m,
CH2CH2CH(CH3)CH2CH3); 2.5 (12H, t, J=7.7,
PhCH2CH2); 6.8 (3H, s, H1, 6a); 6.95 (m, 2H, H3+H4,
6b); 7.05 (1H, d, J23=6.5, H2, 6b). Anal. Calc. for
C27H48: C, 87.02; H, 12.98. Found: C, 86.89; H,
12.81%.
References
4.3.5. 1,3,5-Tri-tert-butylbenzene (7a), and
1,2,4-tri-tert-butylbenzene (7b), from
tert-butylacetylene (run 10, Table 3, 7a:7b=30:70)
GC-MS (m/z)=246 [M+]. 1H-NMR (CDCl3): l 1.30
(12.6H, s, CMe3, 7b); 1.34 (16.2H, s, CMe3, 7a); 1.54
[1] B. Bogdanovic, M. Kroner, G. Wilke, Annalen 669 (1966) 1.
[2] J. Chatt, L. Venanzi, Nature (London) 177 (1956) 852.
[3] P. Pertici, G. Vitulli, Comments Inorg. Chem. 11 (1991) 175.
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