Solubility of Agomelatine Crystal Form I and Form II in Pure Solvents

Publication Date (Web): October 19, 2015. Copyright © 2015 American Chemical Society. *E-mail: [email protected]. Fax: +86 (0)21-64253255., *E-mail:...
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Solubility of Agomelatine Crystal Form I and Form II in Pure Solvents and (Isopropanol + Water) Mixtures Yan Liu, Huiru Gao, Fuzheng Ren,* and Guobin Ren* Laboratory of Pharmaceutical Crystal Engineering & Technology, School of pharmacy, East China University of Science and Technology, Shanghai 20037, People’s Republic of China ABSTRACT: Solubility of agomelatine crystal form II in five pure solvents and (isopropanol + water) binary mixtures was measured from 273.15 K to 313.15 K. The temperature and molar fraction of isopropanol were kept lower range to ensure that no polymorphic transformation would be observed during measuring solubility of form I, which would be determined by XRPD. Thus, solubility of form I was determined under temperature range (from 273.15 K to 293.15 K) in the same binary mixtures with lower molar fraction of isopropanol. All of experimental solubility were correlated by modified Apelblat equation. In addition, the change of molar enthalpy of agomelatine during dissolution was calculated by the empirical parameters of modified Apelblat equation. Furthermore, compared with solubility of form II in the same solvent system, solubility of form I is approximately twice higher than solubility of form II in isopropanol (xB = 0.0494 and 0.0642) + water binary mixtures under the temperature range (from 273.15 K to 293.15 K).

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INTRODUCTION

All experimental solubility of agomelatine were correlated by the modified Apelblat equation. The thermodynamic parameters the molar enthalpy during the dissolution was calculated based on the empirical parameters of the modified Apelblat equation.

Agomelatine (N-[2-(7-methoxy-1-naphthyl)ethyl]acetamide, Figure 1) (CAS registration no. 138112-76-2) is a new and

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EXPERIMENTAL SECTION Materials. Agomelatine (II) with a mass fraction purity of 0.99 is obtained from Jiangsu Jinkang Pharmaceutical Co. Ltd., China. Form I was prepared by recrystallization, verified by XRPD. All of the reagents used in solubility experiment were purchased from the Sinopharm Chemical Reagent Co., Ltd., China, and were of analytical reagent grade, with mass fraction purity is higher than 99.5 %. Also, deionized water was prepared

Figure 1. Structure of agomelatine.

novel non-SSRI potential treatment option for major depressive disorders, first produced by Servier pharmaceutical company in 2009.1,2 Agomelatine has several crystal forms,3 among which crystal forms I4 and II1 can be obtained via solution crystallization1 and mainly used in the pharmaceutical industry. Solubility of agomelatine forms I and II are essential and crucial for designing and controlling crystallization process. In addition, the difference between solubility of these two forms provides the drive for solvent−mediate transformation from form I to form II. Nevertheless, up till now, relative data have not been published in literature yet. In this work, the solubility of crystal form II agomelatine in pure 1-butanol, isopropanol, methyl acetate, acetone, methyl tertbutyl ether (MTBE) and (isopropanol + water) binary mixtures at temperature ranging from 273.15 K to 313.15 K under atmospheric pressure were measured using dynamic method by a laser monitoring observation technique. Meanwhile, the solubility of form I in (isopropanol + water) binary mixtures over temperature from 273.15 K to 293.15 K were experimentally determined by the same method. © XXXX American Chemical Society

Table 1. Description of Materials Used in This Paper initial mass fraction purity

chemical name

source

agomelatine (II)

Jiangsu Jinkang Pharmaceutical Co. Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China

1-butanol acetone methyl acetate isopropanol MTBE

0.99 0.995 0.995 0.995 0.995 0.995

deionized water

Received: July 13, 2015 Accepted: October 12, 2015

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double-jacketed glass vessel with a thermostatic bath. The laser monitoring system was similar to those used in literature,5−8 including a laser generator, a photoelectric convertor, and a light intensity display. The temperature was determined by a temperature probe with uncertainty of 0.01 K, and the vessel were stirred with an overhead stirrer. During measurement, a condenser used prevents solvent from evaporation. All of the materials were weighted by an analytical balance (Mettler Toledo XS105, Switzerland) with uncertainty of 0.01 mg. To determine the solubility of crystal form II agomelatine, a certain amount of solvent was introduced to the vessel first, and then preweighted solute was added. The solution was stirred continuously at fixed stirrer speed under the required temperature. The solute was added repeatedly until it could not dissolve completely within 30 min. Finally, the solution was regarded as a saturated one. The total addition was recorded and the range of the solubility could be determined. The solubility of form I was measured under the same procedure. In addition, X-ray powder diffraction (XRPD) was used to determine the crystal form (Figure 2). Also, no polymorphic transformation was observed during measurement. Each experiment was conducted at least three times. The averages were calculated and used to obtain the molar fraction

Figure 2. XRPD pattern of agomelatine form I after solubility experiment.

in the lab by Ming-che D 24 UV. Detailed information on the materials is shown in Table 1. Apparatus and Procedures. All solubility were measured by laser monitoring observation in a 100 mL cylindrical

Table 2. Mole Fraction Solubility, x1, of Agomelatine (II) in Pure Organic Solvents with the Temperature Range from (273.15 to 313.15) K under 0.1 MPaa 1-butanol T

10 ·x1

10

175.1 222.8 274.8 305.2 374.4 450.9 546.2 686.4 855.4

182.1 216.7 259.4 312.2 377.5 458.5 559.1 684.3 840.3 Isopropanol

4

·x1cal

4

Acetone 100·(x1 −

x1cal)/x1

K 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 T

T

293.15 298.15 303.15 308.15 313.15

350.9 428.6 522.0 634.3 759.0

359.1 434.1 523.4 629.7 755.7 methyl acetate

T

104·x1

104·x1cal

100·(x1 − x1cal)/x1

104·x1

104·x1cal

111.2 141.0 162.7 197.3 231.7 295.7 365.2 497.3 569.7 10 ·x1 4

114.1 135.3 162.2 196.6 240.7 297.5 370.7 465.5 588.8 Acetone 10

·x1cal

4

100·(x1 − x1cal)/x1 −2.59 4.05 0.28 0.36 −3.88 −0.59 −1.49 6.39 −3.35 100·(x1 −

160.8 202.9 250.5 298.4

164.0 200.3 243.9 296.3

−2.34 −1.28 −0.28 0.73 0.44 100·(x1 − x1cal)/x1

K 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

174.7 189.3 224.0 263.3 326.8 374.9 470.4 566.9 681.0

T

104·x1

104·x1cal

100·(x1 − x1cal)/x1

170.0 195.1 226.7 266.6 316.8 380.3 460.6 562.7 692.7 MTBE

2.69 −3.08 −1.24 −1.24 3.04 −1.44 2.08 0.74 −1.73

32.42 32.70 38.70 50.92 57.95 72.53 84.41 106.0 128.2

30.69 35.28 41.11 48.52 57.95 69.97 85.34 105.1 130.5

5.33 −7.88 −6.23 4.72 0.00 3.53 −1.11 0.90 −1.79

K 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

x1cal)/x1

K 273.15 278.15 283.15 288.15

104·x1cal

K −4.03 2.73 5.59 −2.29 −0.82 −1.68 −2.37 0.32 1.77

K 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

10 ·x1

T

4

−1.99 1.30 2.64 0.70

a

Standard uncertainties u for temperature T and pressure P are u(T) = 0.01 K and u(P) = 5 kPa. The relative standard uncertainty u for the mole fraction solubility is ur(x) = 5 %. B

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Table 4. Change of Enthalpy of Agomelatine Crystal Form II during Dissolution in Pure Solvents T

ΔHod

K

kJ·mol−1 1-Butanol

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 Isopropanol

Figure 3. Mole fraction solubility (x1) of agomelatine crystal form II in pure organic solvents from 273.15 K to 313.15 K: ■, MTBE; ●, 1-butanol; ▲, isopropanol; ▼, methyl acetate; ◀, acetone.

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

Table 3. Parameters and Fitting Errors of Equation 3 for Agomelatine Crystal from II in Different Solvents solvent

A

B

C

104 RMSD

1-butanol isopropanol acetone methyl acetate MTBE

−243.87 −364.30 −84.80 −359.19 −388.76

7747.71 12794.98 786.24 13012.52 14155.57

37.70 55.79 13.87 54.81 59.03

9.66 13.04 4.68 7.10 1.97

21.20 22.77 24.34 25.91 27.47 29.04 30.61 32.17 33.74 20.32 22.64 24.96 27.28 29.60 31.92 34.23 36.55 38.87 Acetone

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

solubility, x1, based on eq 1. Also, the relative standard uncertainty of molar fraction solubility was estimated as 5 %. The composition of isopropanol, xB, in (isopropanol + water) binary mixtures would be calculated on eq 2. And the relative standard uncertainty of molar fraction of isopropanol was estimated as 0.5 % x1 =

(mA /MA ) (mA /MA ) + (mB /MB) + (mC /MC)

(1)

xB =

(mB /MB) (mB /MB) + (mC /MC)

(2)

24.96 25.54 26.12 26.69 27.27 27.85 28.42 29.00 29.58 Methyl Acetate

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

where mA, mB, and mC represent the mass of the solute, the organic solvent, and water, respectively. MA, MB, and MC are the respective molecular masses.

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16.28 18.56 20.84 23.12 25.40 27.67 29.95 32.23 34.51 MTBE

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

RESULTS AND DISCUSSION Agomelatine (II) in Pure Solvent. The solubilities of form II in pure 1-butanol, isopropanol, methyl acetate, acetone, and MTBE under different temperatures are listed in Table 2 and shown in Figure 3. From Table 2 and Figure 3, it can be easily seen that the solubility of agomelatine (II) increases with increase of temperature in these five pure solvent within the temperature range (273.15 K to 313.15 K). At a fixed temperature, the solubility order meets the following: 1-butanol > acetone > methyl acetate > isopropanol > MTBE. The dissolving behavior is affected by several factors including temperature, the characters of solvent, and intermolecular interaction.9,10 Agomelatine has hydroxyl group and acylamino group. 1-Butanol and isopropanol have hydroxyl groups, whereas acetone and methyl acetate have acyl groups and ester groups, respectively. Thus, there are hydrogen bonding interactions

16.36 18.82 21.27 23.72 26.18 28.63 31.08 33.54 35.99

between solute molecules and solvent molecules in solution. The combination of polarity and hydrogen bonding interactions result in different dissolving capacity. The temperature dependence solubility of agomelatine (II) was correlated by Apelblat equation8,11 B ln x1 = A + + C ln T (3) T C

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Table 5. Mole Fraction Solubility, x1, of Agomelatine Crystal Form I in (Isopropanol (xB) + Water (xC)) Binary Mixture with the Temperature Range from (273.15 to 293.15) K and Molar Fraction Solubility of Form II Binary Isopropanol (xB) + Water (xC) with the Temperature Range from (273.15 to 313.15) K under 0.1 MPaa solubility data of crystal form I 104·x1

xB

T

0.0494

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15

104·x1cal

solubility data of crystal form II 100·(x1 − x1cal)/x1

xB

K

0.0642

T

0.0494

273.15 278.15

104·x1

104·x1cal

100·(x1 − x1cal)/x1

0.5543 0.9245 1.383 2.345 3.500 5.833 8.859 1.040 1.693 2.786 4.203 6.704 10.21 14.86 26.23 43.17 16.27 18.59 24.92 31.24 44.12 60.83 81.46 113.6 150.5

0.5805 0.9104 1.432 2.260 3.576 5.668 8.998 1.078 1.684 2.640 4.153 6.550 10.35 16.40 26.00 41.29 15.53 19.53 25.04 32.70 43.43 58.59 80.20 111.2 156.2

−4.72 1.53 −3.59 3.62 −2.18 2.83 −1.58 −3.62 0.54 5.22 1.19 2.31 −1.39 −10.30 0.87 4.35 4.49 −5.02 −0.47 −4.66 1.57 3.69 1.55 2.03 −3.79

K 0.3523 0.3477 0.4139 0.4348 0.5813 0.5488 0.6867 0.6987 0.8921 0.8972 1.179 1.161 1.460 1.515 2.054 1.992 2.618 2.638 1.970 1.883 2.465 2.491 3.046 3.285 4.481 4.319 5.175 5.662 7.800 7.402 10.45 9.651 12.87 12.55 15.27 16.27 solubility data of crystal form II 104·x1

xB

T

104·x1cal

1.30 −5.05 5.60 −1.75 −0.56 1.52 −3.76 3.01 −0.76 4.42 −1.07 −7.85 3.62 −9.41 5.11 7.68 2.53 −6.57

0.0642

0.1330

100·(x1 − x1cal)/x1

K 0.2344 0.3934

0.2389 0.3716

−1.94 5.55

283.15 288.15 293.15 298.15 303.15 308.15 313.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

a Standard uncertainties u for temperature T and pressure P are u(T) = 0.01K and u(P) = 5 kPa. The relative standard uncertainty u for the mole fraction of isopropanol xB and solubilities x are ur(xB) = 0.5 % and ur(x) = 5 %.

Figure 4. Mole fraction solubility (x1) of agomelatine in crystal form I in (isopropanol (xB) + water (xC)) binary mixture from 273.15 K to 293.15 K: ■, xB = 0.0494; ●, xB = 0.0642.

Figure 5. Mole fraction solubility (x1) of agomelatine in crystal form II in (isopropanol (xB) + water (xC)) binary mixture from 273.15 K to 313.15 K: ■, xB = 0.0494; ●, xB = 0.0642; ▲, xB = 0.1330.

where x1 is the mole fraction solubility of agomelatine (II), T is the absolute temperature. A, B, and C are empirical constants. The correlated values of A, B, and C of different pure solvents were listed in Table 3. The root-mean-square deviation (RMSD) is defined as follows:

cal where N is the number of experimental dots, and xexp 1,i and x(1,i) represent the experimental and calculated values of the solubility, respectively. The RMSD of different pure solvents were also listed in Table 3. And then the change of molar dissolution enthalpy ΔHod can be calculated by the following12 eq 5

N

RMSD =

⎡ ∂ln x1 ⎤ ΔHdo = RT ⎢ = R( −B + CT ) ⎣ ∂ln T ⎥⎦

2 ∑i = 1 (x1,exp i − x(1, i)cal)

N

(4) D

(5)

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The values of ΔHod was calculated and listed in Table 4. From Table 4, it is seen that all values of ΔHod are positive, which means the dissolution of crystal form II agomelatine is endothermic. Agomelatine (II + I) in Binary Solvent Mixture. The solubility of agomelatine forms I and II in (isopropanol + water) mixtures were measured in different temperatures, which are listed in Table 5 and shown in Figure 4 and Figure 5, respectively. The temperature dependence solubility of forms I and II in binary mixtures was correlated by Apelblat equation also. The correlated values of A, B, C, and RMSD of isopropanol−water binary mixtures were listed in Table 6. And the relative values of ΔHod was calculated by eq 5 and listed in Table 7. Because relatively higher temperature and solvent mixtures with higher dissolving capacity accelerates form I to form II transformation, the narrower temperature range and lower molar fraction of isopropanol in the solvent mixtures were selected for measuring the solubility of form I. From Table 5, the solubility of forms I and II both increase with temperature and molar fraction of isopropanol in the solvent mixtures. Also, compared with the solubility of form II, the solubility of form I is higher under the same condition, which indicates form II is more stable than form I in selected solvents and temperature range.

Table 6. Parameters and Fitting Errors of Equation 3 for Agomelatine Crystal Form I and Form II in (Isopropanol (xB) + Water) Binary Mixtures crystal form

xB

A

B

C

104 RMSD

form I

0.0494 0.0642 0.0494 0.0642 0.1330

−1057.14 −143.46 −404.02 −390.32 −575.762

37717.89 −1545.98 10693.18 10129.70 20760.71

161.99 25.05 63.14 61.34 87.93

0.03 0.50 0.08 0.82 2.32

form II

Table 7. Change of Enthalpy of Agomelatine Crystal Form I and II during Dissolution in (Isopropanol (xB) + Water (xC)) Binary Mixtures crystal form form I

xB 0.0494

0.0642

form II

0.0494

0.0642

0.1330

T

ΔHd

K

kJ·mol−1

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15

54.29 57.66 61.03 64.40 67.76 71.13 74.50 77.86 81.23 69.75 70.27 70.79 71.31 71.83 72.35 72.87 73.39 73.91 54.49 57.12 59.74 62.37 65.00 67.62 70.24 72.87 75.49 55.08 57.63 60.18 62.73 65.28 67.83 70.38 72.93 75.48 27.08 30.74 34.39 38.05 41.70 45.36 49.01 52.67 56.32

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CONCLUSIONS Using the laser monitoring technique, the solubility of agomelatine crystal form II in 1-butanol, isopropanol, methyl acetate, acetone, MTBE, and (isopropanol + water) binary mixtures at the temperature range (from 273.15 K to 313.15 K) were measured. Meanwhile, the solubility of form I in isopropanol + water binary mixtures at the temperature range (from 273.15 K to 293.15 K) also were determined. In addition, solubility data were correlated by modified Apelblat equation and the change of molar dissolution enthalpy ΔHod was calculated using empirical parameters in modified Apelblat equation. From the results, following conclusions can be drawn: (1) Among five selected pure solvents, the solubility of form II was sequenced as following: 1-butanol > acetone > methyl acetate > isopropanol > MTBE. (2) The solubility increased with both temperature and the molar fraction of isopropanol in binary mixtures. (3) The calculated solubility data by the Apelblat equation are in good agreement with the experimental values. (4) The thermodynamic parameter calculated ΔHod indicates the dissolution process is endothermic. (5) Compared with solubility of form II, solubility of form I is higher under the same condition, which indicates form II is more stable than form I in isopropanol−water binary mixtures and temperature range.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Fax: +86 (0)21-64253255. *E-mail: [email protected]. Fax: +86 (0)21-64253406. Author Contributions

Y.L. and H.G. contributed equally. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest. E

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ACKNOWLEDGMENTS The authors would like to thank the supports from the Shanghai Committee of Science and Technology (Grant 12DZ1930702). REFERENCES

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