Boronate Derivatives of Functionally Diverse Catechols: Stability Studies
Abstract
:1. Introduction
Parent compound | Compound No | Amount used mg (mmol) | Benzeneboronic acidmg (mmol) | Data corresponding benzeneboronates | |||||
---|---|---|---|---|---|---|---|---|---|
Amount recovered mg a(% crude yield) | m.p. °C | Mol Formula (Mol. Wt) | Analysis | MS | |||||
Found | Calc. | M+ (%) b | |||||||
Methyl 3,4-dihydroxybenzoate c | 1 | 831 | 629.5 | 1050 | C14H11BO4 | C, 65.90 | C, 66.14 | 254 | |
Methyl -3,4-dihydroxy-phenylacetate | 2 | 300 | 203 | 400 | C15H11BO4 | C, 67.20 | C, 67.16 | 268 | |
Methyl 3,4-dihydroxydihydro-cinnamate | 3 | 500 | 317 | 680 | C16H15BO4 | C, 68.24 | C, 68.09 | 282 | |
Methyl 3,4-dihydroxycinnamate | 4 | 263 | 170 | 349 | C16H13BO4 | C, 68.7 | C, 68.57 | 280 | |
N-Acetyldopamine | 5 | 977 | 612 | 1405 | C16H16BNO3 | C, 68.0 | C, 68.33 | 281 | |
Estra-1,3,5(10)-triene-3,4-diol i | 6 | 22 | 10 | 28 | 176-177 j | C24H27BO2 | C, 80.42 | C, 80.45 j | 358 |
4-Methyl-7,8-dihydroxy-coumarin k | 7 | 260 | 165 | 370 | 191-193 l | C16H11BO4 | l | 278 |
- a GLC analysis (GC column as in b) of these crude products showed in each case a single peak corresponding to their benzeneboronate derivatives. Traces of excess benzeneboronic acid (eluted as triphenylboroxine) were also observed.
- b Mass spectral data were recorded at electron energy 20 eV, using an LKB 9000 GC-MS instrument, fitted with a glass column (2 m × 4 mm, i.d.) of 1% OV-1 on Gas Chrom Q (100–120 mesh). The flash heater was at 250 °C, the molecular separator at 270 °C, and ion source at 265 °C. The helium carrier gas flow rate was 30 mL/min. The trap current was 60 mA, filament current 4 A and accelerating voltage 3.5 KV. In Table 1 the abundances for the ion are shown in brackets ( ).
- c The isomeric methyl 2,3-dihydroxybenzoate did not react fully with benzeneboronic acid, as judged by GLC. On recrystallisation of the crude reaction mixture, from acetone-hexane; the recovered material was largely benzeneboronic acid. Vacuum sublimation of the crude product, also failed to yield any cyclic ester.
- d Recrystallisation from acetone-hexane; m.p. 107–108.5 °C; then vacuum sublimation: yield a middle fraction which was collected.
- e Vacuum sublimation at 55 °C/0.01 torr.
- f Vacuum sublimation at 55 °C/0.01 torr, yielded fine white crystals.
- g Recrystallisation from acetone-hexane; m.p. 125–127 °C; then followed by vacuum sublimation; a middle fraction was collected.
- h Vacuum sublimation at 130 °C/torr; m.p. 157–160 °C, a second sublimation yielded fine white crystals.
- i The isomeric 2-hydroxy-17-deoxoestrone benzeneboronate vacuum sublimation at 140 °C/0.01 torr; yielded a viscous gum, which failed to crystallize from acetone, EtOAc or hexane. Trituration in hexane at low temperature yielded a semi-solid product, which crystallized on standing m.p. 244–247 °C. GC showed traces of benzeneboronic acid. GC-MS, M+358 (100%), a satisfactory micro-analysis or HRMS was not adequate for this compound. This is due to partial hydrolysis on storage. The 1H-NMR showed satisfactory results.
- j Recrystallisation from acetone; then vacuum sublimation at 160 °C/0.01 torr. The sublimed material was recrystallised twice from acetone. High resolution MS, C24H27BO2, requires 358.2810; found 358.2104.
- k The isomeric 4-methyl-6,7-dihydroxycoumarin benzeneboronate was formed and showed GC-MS peak with M+ 278 (100%) but attempts to isolate pure crystals were unsuccessful.
- l Two recrystallisation from CHCl3-hexane, then vacuum sublimation at 140 °C/0.01 torr, gave a middle fraction which was recrystallised from EtOAc-hexane. GLC analysis for this product showed the presence of ca. 0.1% of benzeneboronic acid: the micro-analysis was not satisfactory for carbon. High resolution MS, C16H11BO4, requires 278.0672; found 278.0750.
2. Results and Discussion
3. Experimental
General
4. Conclusions
Acknowledgements
References
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Ketuly, K.A.; Hadi, A.H.A. Boronate Derivatives of Functionally Diverse Catechols: Stability Studies. Molecules 2010, 15, 2347-2356. https://doi.org/10.3390/molecules15042347
Ketuly KA, Hadi AHA. Boronate Derivatives of Functionally Diverse Catechols: Stability Studies. Molecules. 2010; 15(4):2347-2356. https://doi.org/10.3390/molecules15042347
Chicago/Turabian StyleKetuly, Kamal Aziz, and A. Hamid A. Hadi. 2010. "Boronate Derivatives of Functionally Diverse Catechols: Stability Studies" Molecules 15, no. 4: 2347-2356. https://doi.org/10.3390/molecules15042347