SMQ-V047 N-002_ligas_size.pdf - Journal of the Mexican Chemical ...

120 Rev. Soc. Quím. Méx. Vol. 47, Núm. 2 (2003) Eduardo Díaz et al.
Fig. 3.
O
O
O
O
O
O
7 9a
O
O
O
O
O
7
9a'
O
O
O
O
O
O
O
O
1 9
O O
O
O
O
O
1
Scheme 3
O O
O
O
O
** *
O
** *
**
*
**
*
O
O
O
O
9'
309, (M + 2) m/z 311, (M + 4) m/z 313, and (M + 6) m/z
316]. The proton NMR spectrum showed a one proton doublet
of doublet δ = 7.12 (J = 15.5, 10.5 Hz) and an one proton
doublet of doublet at δ = 6.41 (J = 0.5, 15.5) for CH-10 and
CH-11 respectively. A new methylene signal appeared at δ =
4.22 instead of the usual methyl ketone singlet (δ = 2.31)
observed in the 1 HNMR spectrum of starting β-ionone 1 (Fig.
3).
Additionally, we were able to observe a doublet of doublet
at δ = 2.40 (J = 10.5, 0.5, CH-2) and three methyl singlets
at δ = 1.30, 0.95 and 0.78 for C-7, C-8, and C-9 respectively.
The 1D 13 C NMR and DEPT edited spectra allowed the
assignment of protonated carbons as four methines at δ =
148.0 (C-10), 129.1 (C-11), 48.1 (C-2) and 32.8 (C-6) respectively.
Three methylenes at δ = 47.2, (C-13), 35.1 (C-4) and
15.9 (C-5). Three methyl signals were also observed at δ =
29.4, 22.5, 19.7 for C-8, C-7 and C-9 respectively. The assignment
of the non protonated carbons at δ = 190.5 (C-12), 72.8
(C-14), 32.0 (C-3) and 29.8 (C-1) was performed using the
COLOC [18] spectrum.
The formation of compounds 10 and 11 may be inferred
through isomerization [22-26] of the bond C6-C1 from compound
1' to 1 respectively and then the dichlorocarbene addition
to the new formed double bond.
On the other hand, the role of the catalyst used in this
work, play an important role in the ratio of the products
obtained as well as the versatility of the structures and yield.
Graphics 1 and 2 are self explained and show the behaviour of
the different catalyst and ratio of products.
O
O
O
O
O
O
Conclusions
Scheme 4
-1
11 6.0 Kcal mol
O
O
135.0 Kcal mol -1
O
-1
135.5 Kcal mol
The successful use of several ammonium quaternary catalyst
in the phase transfer reactions enabled us to obtain some interesting
derivatives from the starting material (β-Ionone). The
structures of the formed compounds where fully elucidated