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B. Przybył et al. / Journal of Molecular Structure 1048 (2013) 172–178
2.2.2. (ii) Methyl-3,5-dimethylbenzoate (4)
2.3. X-ray single crystal measurements and crystal structure analysis
To the crude acid chloride (3), methanol (25.0 ml) was added,
and heated under the reflux conditions for 2 h. The excess metha-
nol was evaporated in vacuo. The ester (4) was crystallized from
hexane yielding 2.98 g (55%), mp. = 26–29 °C.
Single crystal X-ray diffraction measurements of 1a and 1b
were carried out at 295 K on a four-circle KUMA KM4 diffractom-
eter equipped with two-dimensional CCD area detector. Graphite
monochromatized Mo K
a radiation (k = 0.71073 Å) and x-scan
technique ( = 1°) were used for data collection. Data collection
D
x
2.2.3. (iii) Methyl-3,5-bis(bromometylene)benzoate (5)
and reduction along with absorption correction were performed
using CrysAlis software package [23]. The structures were solved
by direct methods using SHELXS-97 [24], which revealed the
positions of almost all non-hydrogen atoms. The remaining atoms
were located from subsequent difference Fourier syntheses. The
The ester (4, 2.76 g, 0.0168 mol), N-bromosuccinimide (6.07 g,
0.0341 mol) and benzoyl peroxide (85 mg, 0.35 mmol) were placed
in 100 ml round-bottom flask. Then dried carbon tetrachloride
(25 ml) was added and heated under the reflux conditions for
3 h. After cooling to room temperature, the mixture was filtered
and the solvent was evaporated in vacuo to obtain the crude prod-
uct as residue (5.39 g). The crude product was crystallized from
hexane to yield the dibromide (5): 1.37 g (25%), mp. 94–98 °C.
1H NMR (300 MHz, CDCl3) d: 8.00 (s, 2H, arom. H); 7.61 (s, 1H,
arom. H); 4.50 (s, 4H, CH2Br); 3.93 ppm (s, 3H, COOCH3).
2.2.4. (iv) Methyl-3,5-bis[(diethoxyphosphoryl)methyl]benzoate (6)
The compound 5 (1.35 g, 4.19 mmol) and triethyl phosphite
(1.9 ml, 0.011 mol) were placed in 20 ml round-bottom flask of mi-
cro-distillation set and heated at 140 °C for 2 h. The reaction mix-
ture was chromatographed on silica gel column using ethyl acetate
as an eluent and the pure product 6 was obtained: 1.27 g (70%),
Rf = 0.06 (AcOEt, UV lamp for visualisation) mp. 71–74 °C.
1H NMR (300 MHz, CDCl3) d: 7.86 (s, 2H, arom. H); 7.48 (s, 1H,
3
arom. H); 4.03 (q, 8H, JHH 7.2 Hz, OACH2ACH3); 3.91 (s, 3H,
Fig. 1. Asymmetric unit of 1a showing the disordered acetone molecule, the
occupation factors of O11 and C11 as well as of O12 and C12 are equal to 0.5.
2
3
OACH3); 3.19 (d, 4H, JPH 21.9 Hz, CH2P); 1.26 ppm (t, 12H, JHH
7.2 Hz, OACH2ACH3). 31P{1H} NMR (121.5 MHz, CDCl3) d: 24.33 (s).
Table 2
2.2.5. (v) 3,5-Bis[(dihydroxyphosphoryl)methyl]benzoic acid (1)
The compound 6 (1.24 g, 2.84 mmol), deionized water (5.0 ml)
and 36% hydrochloric acid (5.0 ml) were placed in 50 ml round-
bottom flask and heated at 130 °C for 20 h. After cooling, the sol-
vent was evaporated in vacuo to dryness; obtained white solid
was dissolved in 5 ml of deionized water, which was evaporated
in vacuo again. 3,5-Bis[(dihydroxyphosphoryl)methyl]benzoic acid
(1) was obtained as white powder (0.854 g, 97%), mp. 245–250 °C.
1H NMR (300 MHz, d6-DMSO) d: 7.71 (s, 2H, arom. H); 7.33 (s,
Selected geometrical parameters (Å, °) of 1a and 1b.
1a
1b
CaAO4i
2.2944(11)
2.2944(11)
2.3150(10)
2.3150(10)
2.3960(10)
2.3960(10)
1.5117(11)
1.5070(10)
1.5693(11)
1.4911(11)
1.5454(11)
1.5540(11)
1.8009(15)
1.7954(14)
1.2142(17)
1.3138(18)
89.91(4)
CaAO4
CaAO2ii
CaAO2iii
CaAO7iv
CaAO7v
P1AO1
P1AO2
P1AO3
P2AO4
P2AO5
P2AO6
P1AC7
P2AC8
1.449(2)
1.547(2)
1.550(2)
1.495(2)
1.549(2)
1.555(2)
1.778(3)
1.782(3)
1.214(4)
1.319(4)
2
1H, arom. H); 2.98 (d, 4H, JPH 21 Hz, CH2P); 2.49 (s, 4H, POH).
31P{1H} NMR (121.5 MHz, d6-DMSO): d 21.32 (s). 13C{1H} NMR
(75.46 MHz, d6-DMSO): d 167.88 (s, COOH); 136.08–135.92(m),
134.93–134.79 (m), 130.88, 128.94 (aromatic); 35.51 (d, CH2AP,
1JPC = 132 Hz).
C9AO7
C9AO8
2.2.6. Crystallization of C9H12O8P2ꢁC3H6O (1a)
O4iACaAO2ii
O4ACaAO2ii
O4iACaAO7iv
O4ACaAO7iv
O2iiACaAO7iv
O2iiiACaAO7iv
O2AP1AO1
O2AP1AO3
O1AP1AO3
O4AP2AO5
O4AP2AO6
O5AP2AO6
C3AC8AP2
C1AC7AP1
O7AC9AO8
C6AC1AC7AP1
C4AC3AC8AP2
C4AC5AC9AO7
3,5-Bis[(dihydroxyphosphoryl)methyl]benzoic acid (1, 30 mg,
0.097 mmol) was placed in 10 ml glass vial and dissolved in
0.3 ml of deionized water. Then 6 ml of acetone was added, the vial
was closed and placed in a refrigerator for 3 days. Next the glass
vial was left in room temperature and after 1 day colourless single
crystals of 1a have been isolated.
90.09(4)
85.68(4)
94.32(4)
83.85(4)
96.15(4)
112.57(13)
105.60(13)
113.60(14)
112.20(14)
113.63(13)
105.11(14)
111.9(2)
111.8(2)
123.4(3)
ꢂ97.35(30)
87.27(31)
ꢂ163.49(31)
115.07(6)
106.52(6)
110.76(6)
115.07(6)
113.44(6)
101.46(6)
111.60(9)
112.58(9)
122.32(13)
93.49(16)
82.82(14)
ꢂ175.52(15)
2.2.7. Crystallization of C18H22O16P4Caꢁ2CH3OH (1b)
3,5-Bis[(dihydroxyphosphoryl)methyl]benzoic acid (1, 30 mg,
0.097 mmol) was placed in 10 ml glass vial and dissolved in
2.0 ml of deionized water and 5.0 ml of 0.020 mol/dm3 solution
of CaCl2 and 6 drops of methanol were added. The partially open
vial was left in room temperature. Colourless, longitudinal single
crystals suitable to X-ray measurements were obtained by slow
evaporation of the solvent, almost to dryness, at room temperature
(about 1 month).
Symmetry codes: (i) ꢂx + 1, ꢂy, ꢂz; (ii) ꢂx, ꢂy + 1, ꢂz + 1; (iii) x + 1, y, z ꢂ 1; (iv) ꢂx,
ꢂy + 1, ꢂz; (v) x + 1, y, z.