2
0
2016
zac
nun
0
journal
Original
Zacconi, F. C.[Flavia C.]
Nunez, O. N.[Olga N.]
Cabrera, A. L.[Adolfo L.]
Valenzuela, L. M.[Loreto M.]
del Valle, J. M.[Jose M.]
de la Fuente, J. C.[Juan C.]
J. Chem. Thermodyn.
2016
2020-09-29
Synthesis and solubility measurement in supercritical carbon dioxide of two solid derivatives of 2-methylnaphthalene-1,4-dione (menadione): 2-(Benzylamino)-3-methylnaphthalene-1,4-dione and 3-(phenethylamino)-2-methylnaphthalene-1,4-dione
Synthesis of two solid derivatives of vitamin K3 (2-methylnaphthalene-1,4-dione or menadione), 2-(ben zylamino)-3-methylnaphthalene-1,4-dione and 3-(phenethylamino)-2-methylnaphthalene-1,4-dione was completed using a 1,4 Michael addition reaction at 323 K in an inert atmosphere, with reaction yields of 62% mol mol 1 and 71% mol mol 1, respectively, and a purity grade of 98% mol mol 1 for each component. Isothermal solubility (mole fraction) of each solid derivative in supercritical carbon dioxide was performed using an analytic-recirculation methodology, with direct determination of the molar composition of the carbon dioxide-rich phase by using high performance liquid chromatography, at temperatures of (313, 323 and 333) K and pressures from (8 28) MPa. Results indicated that the range of measured solubilities were from (59 10 6 to 368 10 6) mol mol 1 for solid 2-(benzylamino)-3-met hylnaphthalene-1,4-dione and from (40 10 6 to 205 10 6) mol mol 1 for solid 3-(phenethyla mino)-2-methylnaphthalene-1,4-dione. The experimental solubility was validated using three approaches, estimating the combined expanded uncertainty of measurement for each solubility data point, evaluating the thermodynamic consistency of the data utilizing a test based on the Gibbs Duhem equation, and verifying the self-consistency by correlating the experimental solubility values with a semi-empirical model as a function of temperature, pressure and pure carbon dioxide density.
Solubility
Menadione
Derivatives
Supercritical carbon dioxide
Modelling
10.1016/j.jct.2016.08.016
103
325-332
1
InChI=1S/C18H15NO2/c1-12-16(19-11-13-7-3-2-4-8-13)18(21)15-10-6-5-9-14(15)17(12)20/h2-10,19H,11H2,1H3
UGGZASAXCCJYCN-UHFFFAOYSA-N
2-(benzylamino)-3-methylnaphthalene-1,4-dione
2-methyl-3-((phenylmethyl)amino)-1,4-naphthalenedione
C18H15NO2
1
Synthesized by the authors
1
90
1
Gas chromatography
2
Liquid chromatography
3
98
2
NMR (proton)
2
InChI=1S/C19H17NO2/c1-13-17(20-12-11-14-7-3-2-4-8-14)19(22)16-10-6-5-9-15(16)18(13)21/h2-10,20H,11-12H2,1H3
GLLARDMZNLQQGH-UHFFFAOYSA-N
3-(phenethylamino)-2-methylnaphthalene-1,4-dione
2-methyl-3-(phenethylamino)naphthalene-1,4-dione
C19H17NO2
1
Synthesized by the authors
1
91
2
Gas chromatography
2
Liquid chromatography
3
98
2
NMR (proton)
3
InChI=1S/CO2/c2-1-3
CURLTUGMZLYLDI-UHFFFAOYSA-N
carbon dioxide
CO2
1
Commercial source
1
99.99
4
Stated by supplier
1
1
1
Principal objective of the work
AB
TRC
2/2/2017
1
Normal melting temperature, K
VISOBS
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
Liquid
Air at 1 atmosphere
1
364.8
4
1
2.6
2
2
1
Principal objective of the work
AB
TRC
2/2/2017
1
Normal melting temperature, K
VISOBS
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
Liquid
Air at 1 atmosphere
1
365.7
4
1
1.6
3
3
1
1
1
Principal objective of the work
AB
TRC
2/2/2017
1
Mole fraction
Chromatography
1
Fluid (supercritical or subcritical phases)
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Fluid (supercritical or subcritical phases)
Crystal
1
1
Temperature, K
Fluid (supercritical or subcritical phases)
2
Pressure, kPa
Fluid (supercritical or subcritical phases)
1
313
3
2
8950
3
1
5.9e-05
2
1
3e-05
1
313
3
2
11840
4
1
0.000158
3
1
3.3e-05
1
313
3
2
15260
4
1
0.000244
3
1
4.1e-05
1
313
3
2
17280
4
1
0.00028
3
1
4.4e-05
1
313
3
2
18970
4
1
0.000301
3
1
4.5e-05
1
323
3
2
9820
3
1
8.6e-05
2
1
3.9e-05
1
323
3
2
14900
3
1
0.00024
3
1
4.1e-05
1
323
3
2
16950
4
1
0.000266
3
1
4.5e-05
1
323
3
2
21460
4
1
0.000341
3
1
5.1e-05
1
323
3
2
28400
3
1
0.000368
3
1
5.3e-05
1
333
3
2
12160
4
1
9.1e-05
2
1
3.4e-05
1
333
3
2
15080
4
1
0.000192
3
1
4e-05
1
333
3
2
16920
4
1
0.000256
3
1
4.5e-05
1
333
3
2
20170
4
1
0.000338
3
1
5.4e-05
1
333
3
2
25080
4
1
0.000367
3
1
5.5e-05
4
2
1
3
1
Principal objective of the work
AB
TRC
2/2/2017
1
Mole fraction
Chromatography
2
Fluid (supercritical or subcritical phases)
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Fluid (supercritical or subcritical phases)
Crystal
2
1
Temperature, K
Fluid (supercritical or subcritical phases)
2
Pressure, kPa
Fluid (supercritical or subcritical phases)
1
313
3
2
8400
2
1
4e-05
2
1
3.6e-05
1
313
3
2
14820
4
1
9.2e-05
2
1
2.7e-05
1
313
3
2
16830
4
1
0.000107
3
1
2.9e-05
1
313
3
2
19900
3
1
0.000118
3
1
3e-05
1
313
3
2
22560
4
1
0.000128
3
1
3.1e-05
1
323
3
2
9240
3
1
4.4e-05
2
1
3.9e-05
1
323
3
2
11800
3
1
4.7e-05
2
1
2.5e-05
1
323
3
2
14420
4
1
8.7e-05
2
1
2.8e-05
1
323
3
2
17280
4
1
0.000123
3
1
3.2e-05
1
323
3
2
19580
4
1
0.000117
3
1
3.1e-05
1
333
3
2
10490
4
1
5.7e-05
2
1
3.9e-05
1
333
3
2
14150
4
1
7.2e-05
2
1
2.8e-05
1
333
3
2
16890
4
1
0.000124
3
1
3.4e-05
1
333
3
2
21540
4
1
0.000189
3
1
4.2e-05
1
333
3
2
24350
4
1
0.000205
3
1
4.4e-05