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BAꢀAꢀI et al., Orient. J. Chem., Vol. 29(4), 1611-1614 (2013)
Scheme 1: Synthesis Salicylaldehyde by Mg(OMe) in under grinding
2
-
1
1
EꢁPERIMENTAL
IR(KBr, cm ): IR:2770(W), 1740(C=O) H NMR
300 MHz, CDCl , ppm) δ: 2/1(S,3H),6/2-6/6 (d,
(
3
1
3
Melting points were measured on an 2H),7(s,1H) , 9/4 (S, 1H), 10/7 (S,1H), C NMR
Electrothermal 9100 apparatus.Elemental analyses (75 MHz, CDCl , ppm) δ: 18.3 , 116.5, 119 , 122,
for C, H, and N were performed using a Heraeus 137.5, 142.5, 163.5, 195.5, [M] found 136.05;
CHNO-Rapid analyzer. IR spectra were measured calc.136.07.
3
+
.
on a Shimadzu IR-460 spectrometer.1H and 13C
NMR spectra were measured with a Bruker DRX-300
0
2-hydroxy-3-methylbenzaldehyd, mp:58 C,
-
1
1
Avance instrument with CDCl as solvent at 300 and IR(KBr, cm ): IR:2770, 1740 H NMR (300 MHz,
3
7
5 MHz, respectively.Mass spectra were recorded on CDCl , ppm) δ: 1/95(S,3H),6/2-6/6 (d, 2H),6/8(s,1H)
3
a Finnigan-Matt 8430 mass spectrometer operating , 9/3 (S, 1H), 10/9 (S,1H).
at an ionization potential of 70 eV. Phenols and 2-hydroxy-4-methylbenzaldehyd, mp:
0
-1
1
Paraformaldehyde, were obtained from Fluka and 60.5 C, IR(KBr, cm ):2780, 1660, H NMR (300 MHz,
were used without further purification. Magnesium CDCl , ppm) ´: 1/95(S,3H),6/2-6/4 (d, 2H),7(s,1H) ,
3
13
Methoxide was prepared by known methods.
9/3 (S, 1H), 10/5 (S,1H), C NMR (75 MHz, CDCl3,
ppm) δ: 22.4, 118, 119, 121.5, 134, 149 (4-C), 162,
A aromatic Phenol 1 (0.1 mol), magnesium 196.
methoxide (5 gr ), and the mixture was grinding
0
to 1 minute at room temperature. A slurry of
2-hydroxy-5-Boromobenzaldehyd mp:75 C,
6
-1
1
paraformaldehyde powder (4 gr) in under grinding IR(KBr, cm ):2780, 1670, H NMR (300 MHz, CDCl ,
3
was added in small portions over 2 min to the ppm) δ: 6/4-6/9 (d, 2H),7/5(s,1H) , 9/7 (S, 1H), 10/7
reaction mixture. Stirring was continued at r.t for 8 (S,1H).
min, after which added slowly to 10% sulfuric acid
(
20 ml g). The resulting mixture was stirred for 10
2-hydroxy-3,5-dimethyl benzaldehyd, mp:
0
-1
1
min, after which the aqueous layer was separated 62 C, IR(KBr, cm ): 2760, 1660, H NMR (300 MHz,
and extracted with ethyl acetate (2 × 100 ml). The CDCl , ppm) δ:1/8(S,6H),6/3-6/4 (m, 2H), 9/3 (S, 1H),
3
combined organic layers and extracts were washed 10/7 (S,1H)
with 10% sulfuric acid (20 ml) and water (20 ml)
and evaporated under reduced pressure to give the
salicyaldehyde 3.
RESULTS AND DISCUSSION
The production in high yield (Table 1)
Salicylaldehyde, mp:43 C, IR(KBr, cm ): of Salicylaldhyde derivatives (2) by means of
760, 1740. H NMR (300 MHz, CDCl , ppm) δ: two successive ortho-regioselective reactions on
/75(m,4H), 9/9(S, 1H), 11/1 (S,1H), C NMR (75 Phenol of the distribution of the products. In order
0
-1
1
2
7
3
13
MHz, CDCl , ppm) δ: 117.45, 119.74, 120.53, to control the complexity of this reaction and direct
3
+.
1
33.64, 136.88 , 161.45, 196.53.[M] found 122.040; it towards synthetic utility, we studied the reactions
calc.122.098.
of formaldehyde with magnesium phenoxides which,
as shown by Robert Aldred and co tend to react
-hydroxy-5-methylbenzaldehyd, mp:56 C, regioselectively with several reagents .
0
7
2