Solubility of Acetoguanamine in Twelve Neat Solvents from

1 day ago - By using the shake-flask method, the acetoguanamine solubilities in water, acetonitrile, methanol, n-butanol, isopropanol, isobutanol, eth...
0 downloads 0 Views 643KB Size
Download PDF
Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

pubs.acs.org/jced

Solubility of Acetoguanamine in Twelve Neat Solvents from 283.15 to 323.15 K Wenzhi Yao,† Nan Song,† Ju Xie,‡ Hongkun Zhao,*,‡ and Xinbao Li*,† †

Downloaded via NOTTINGHAM TRENT UNIV on September 5, 2019 at 14:42:35 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

School of Environmental & Municipal Engineering, North China University of Water Resources and Electric Power, Zhengzhou, He’nan 450046, People’s Republic of China ‡ College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, People’s Republic of China ABSTRACT: By using the shake-flask method, the acetoguanamine solubilities in water, acetonitrile, methanol, n-butanol, isopropanol, isobutanol, ethanol, n-propanol, N,N-dimethylformamide (DMF), 1,4-dioxane, ethyl acetate, and ethylene glycol (EG) were acquired over the temperatures from 283.15 to 323.15 K at ambient pressure (p = 101.2 kPa). The mole fraction of acetoguanamine in equilibrated liquor increased as the temperature increased and followed the order in different solvents: DMF > EG > ethyl acetate > 1,4-dioxane > n-butanol > isobutanol > n-propanol > isopropanol > ethanol > methanol > water > acetonitrile. The acquired solubility was correlated via the Apelblat equation. The largest root-mean-square deviation value and largest relative average deviation were, respectively, 28.12 × 10−6 and 2.38 × 10−2.

■

INTRODUCTION The information of thermodynamic aspects on phase equilibrium is commonly used to design the purification process in lots of areas, for example, pharmaceutical, food, chemical, material, and petrochemical.1−3 The solute solubility in solvents is of crucial importance to get high-purity products using the crystallization process, where the solvent selection is necessary because the solvent affects the quality and yield of the final product.4,5 For the process of crystallization operation, the solubility of solid in pure or solvent mixtures has a significant effect on the crystal habits and the drug delivery, bioavailability, and efficacy in the pharmaceutical products. Because of the significance of the solubility in industry, a lot of solubility measurement has been performed. Triazine compounds are very useful in pharmaceutical industry as the side chain of antibiotics and as coupling agents for the peptide synthesis, as well as in formulating fungicides and bactericides.6,7 As a result, the research upon applications of aminotriazine derivatives has become one of the study hotspots. As an important triazine compound, acetoguanamine (structure given in Figure 1; CAS reg. no. 542-02-9) is employed as an intermediate for the pharmaceuticals and as a flexibilizer and modifier of formaldehyde resins.8,9 Regardless of its pharmacological significance, little attention has been

paid upon the thermodynamic aspects of acetoguanamine in neat and solvent mixtures. In practice, acetoguanamine is manufactured by using acetonitrile as raw materials. Acetonitrile acts as not only a raw material, but also a solvent.10−13 Therefore, the acetoguanamine solubility in the acetonitrile has direct effect upon the yield of the reaction product. On the other hand, the quality of final acetoguanamine depends on the solution crystallization procedure because of its effect on the crystal habit, particle size, and purity of the product. Additionally, the information on solubility allows us to deeply understand the molecule interactions between acetoguanamine and the solvent. However, no work relating to the acetoguanamine solubility has yet been conducted. With the purpose of selecting suitable solvents to improve the acetoguanamine purity through the crystallization process and optimize the reaction conditions, the aims of the present work are to (1) experimentally determine the acetoguanamine solubility in pure acetonitrile and methanol, ethanol, isopropanol, isobutanol, n-propanol, n-butanol, N,N-dimethylformamide (DMF), 1,4-dioxane, water, ethyl acetate, and ethylene glycol (EG) at several temperatures; and (2) mathematically correlate the experimental solubility using the Apelblat equation.14−16

■

EMPIRICAL CORRELATION OF THE SOLUBILITY In the present paper, the Apelblat equation is used to mathematically describe the solubility of acetoguanamine. This equation suggested by Apelblat and Manzurola14−16 provides more precise description of the solid solubility in many pure solvents and is described as Received: June 23, 2019 Accepted: August 22, 2019

Figure 1. Chemical structure of acetoguanamine. © XXXX American Chemical Society

A

DOI: 10.1021/acs.jced.9b00593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Detailed Information on the Solvents and Acetoguanamine chemicals

CAS reg. no.

molar mass g·mol−1

acetoguanamine

542-02-9

125.1

methanol ethanol isopropanol isobutanol n-propanol

67-56-1 64-17-5 67-63-0 78-83-1 71-23-8

32.04 46.07 60.10 74.12 60.10

n-butanol DMF acetonitrile 1,4-dioxane ethyl acetate EG water

71-36-3 68-12-2 75-05-8 123-91-1 141-78-6 107-21-1 7732-18-5

74.12 73.09 41.05 88.11 88.11 62.07 18.02

source

initial mass fraction purity

Sigma Chemical Co., Ltd.

Sinopharm Chemical Reagent Co., Ltd.

final mass fraction purity

purification method

analytical method

0.982

0.995

recrystallization

HPLCa

0.997 0.994 0.995 0.994 0.995

0.997 0.994 0.995 0.994 0.995

none none none none none

GCb GC GC GC GC

0.994 0.995 0.996 0.995 0.994 0.995

0.994 0.995 0.996 0.995 0.994 0.995

none none none none none none distillation

GC GC GC GC GC GC conductivity meter

conductivity EG > ethyl acetate > 1,4-dioxane > n-butanol > isobutanol > n-propanol > isopropanol > ethanol > methanol > water > acetonitrile. The solubility values in DMF are approximately 10 times of that in acetonitrile. For the systems of acetoguanamine + water and acetoguanamine + alcohol, the solubility magnitude is in agreement with the changing tendency of polarity of the solvents with the exception of isobutanol and EG. The polarities of solvents are likely to be an important factor to affect acetoguanamine solubility in alcohols and water. Acetoguanamine displays approximate the symmetrical struc-

current and the tube voltage were respectively, 30 mA and 40 kV. The obtained data were gathered from (2θ) 10° to 50°.

■

RESULTS AND DISCUSSION XRD Analysis. The patterns of XRD for raw material acetoguanamine and the solids in equilibrium with liquid are given in Figure 2. As can be observed that for the solvent of water, acetonitrile, methanol, ethanol, isopropanol, n-butanol, 1,4-dioxane, ethyl acetate, the XRD patterns of the solids equilibrated with their corresponding solvents have the identical characteristic peaks with that of the raw acetoguanamine. Accordingly, no polymorph transformation or solvate formation takes place under the experimental conditions for these solvents. However, for the solvents of DMF, EG, isobutanol, and n-propanol, the determined XRD patterns of the solids equilibrated with their corresponding solvents show some different characteristics compared with that of the other solvents. Obviously, acetoguanamine DMF (EG, isobutanol and n-propanol) solvate formation occurs in the experiment which involves NH groups of the acetoguanamine as donors and the O atom of the solvent as acceptors. The case is confirmed by the previous works.20−26 As described by C

DOI: 10.1021/acs.jced.9b00593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

The values of RAD are no more than 2.38%. Therefore, this model is applicable in mathematically describing the acetoguanamine solubility in the twelve neat solvents at the temperatures from 283.15 to 323.15 K under 101.2 kPa.

■

CONCLUSIONS The acetoguanamine solubilities in the twelve pure solvents were achieved though the shake-flask method from 283.15 to 323.15 K under the pressure of p = 101.2 kPa. They increased with the increasing temperature and ranked as DMF > EG > ethyl acetate > 1,4-dioxane > n-butanol > isobutanol > npropanol > isopropanol > ethanol > methanol > water > acetonitrile. The determined mole fraction solubilities were fitted by the Apelblat equation. The highest values of rmsd and RAD were, respectively, 28.12 × 10−6 and 2.38 × 10−2.

Figure 3. Mole fraction solubility (x) of acetoguanamine in several pure solvents. ★, DMF; □, EG; ☆, ethyl acetate; ○, 1,4-dioxane; ◆, n-butanol; ◀, isobutanol; ▲, n-propanol; ▼, isopropanol; ●, ethanol; ■, methanol; ▽, water; ▶, acetonitrile. , calculated curves with the Apelblat equation.

■

AUTHOR INFORMATION

Corresponding Authors

ture, so its polarity is relative small. The solubility of acetoguanamine increases with the decreasing polarity of the solvents. The polarity of water is larger than that of the alcohols,27 so the solubility of acetoguanamine in water is smaller than that in these alcohols. The lower solubility in water may be resulted from its largest molecular polarity among selected water and alcohols. On the other hand, for the other solvents, the order of solubility magnitude is not strictly in agreement with the solvent descriptor. For instance, the acetoguanamine solubility in acetonitrile with moderate polarity is lowest among the studied solvents; and the solubility of acetoguanamine in DMF is highest. It appears that the polarity is not the sole factor to affect the acetoguanamine solubility in the selected solvents. By and large, it is very difficult to explain the solubility behavior of acetoguanamine tabulated in Table 2 in terms of one reason. Many factors may affect the case, for example, molecule polarity, solute−solvent interactions, molecular sizes and shapes, and solvent−solvent interactions and solute−solute interactions. Correlations of the Solubility of Acetoguanamine in Various Solvents. The attained parameters’ values of the Apelblat equation as well as the values of rmsd and RAD are tabulated in Table 3. In addition, the back-computed solubility values by the Apelblat equation are plotted in Figure 3. From Tables 2 and 3, the back-calculated solubility values of acetoguanamine in the twelve solvents agree very well with the experimental ones. The largest value of rmsd is 28.12 × 10−6, which is achieved for the acetoguanamine + DMF mixture.

*E-mail: [email protected]. Phone: +86 514 87975568. Fax: +86 514 87975244 (H.Z.). *E-mail address: [email protected] (X.L.). ORCID

Ju Xie: 0000-0002-0906-4452 Hongkun Zhao: 0000-0001-5972-8352 Xinbao Li: 0000-0001-9598-3027 Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The authors thank to the National Natural Science Foundation of China (project number: 41877118), Natural Science Foundation of Jiangsu Province of China (project number: BK20181479), and Natural Science Foundation of the Jiangsu Higher Education Institutions of China (project number: 17KJB610013) for their financial support.

■

REFERENCES

(1) Prausnitz, J. M.; Tavares, F. W. Thermodynamics of Fluid-Phase Equilibria for Standard Chemical Engineering Operations. AIChE J. 2004, 50, 739−761. (2) Xu, J.; Wang, Y.; Yuan, F.; Huang, Q.; Hao, H. Solid-liquid Equilibrium of L-Alanyl-L-glutamine Form II in Methanol + Water and Isopropanol + Water Systems. J. Mol. Liq. 2016, 219, 930−936. (3) Li, Y.; Li, C.; Chen, L. Determination of the Solubility, Dissolution Enthalpy and Entropy of N-Hydroxymethyl Acrylamide in Different Solvents. J. Mol. Liq. 2016, 224, 940−943.

Table 3. Parameters of the Apelblat Equation for Acetoguanamine Dissolved in the Studied Solvents solvent

A

B

C

100 RAD

106 rmsd

methanol ethanol n-propanol isopropanol n-butanol isobutanol acetonitrile EG DMF 1,4-dioxane ethyl acetate water

−36.097 −44.596 119.15 −26.423 −43.343 −78.091 −63.231 −146.98 −142.59 −142.57 −128.51 −11.025

−1889.76 −1345.49 −8584.67 −1989.69 −1015.7 532.86 −916.92 4042.47 3850.46 3614.01 3087.93 −3155.24

6.021 7.244 −17.17 4.467 6.949 12.107 10.127 22.242 21.625 21.668 19.536 2.323

1.62 2.04 2.38 1.03 1.60 1.04 1.42 0.98 1.33 1.20 0.95 1.43

7.81 8.65 15.22 7.24 13.41 11.50 3.08 13.01 28.12 15.24 14.78 4.24

D

DOI: 10.1021/acs.jced.9b00593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

(4) Kolár,̌ P.; Shen, J.-W.; Tsuboi, A.; Ishikawa, T. Solvent Selection for Pharmaceuticals. Fluid Phase Equilib. 2002, 194−197, 771−782. (5) Hahnenkamp, I.; Graubner, G.; Gmehling, J. Measurement and Prediction of Solubilities of Active Pharmaceutical Ingredients. Int. J. Pharm. 2010, 388, 73−81. (6) Brzozowski, Z.; Sączewski, F.; Gdaniec, M. Synthesis, Structural Characterization and Antitumor Activity of Novel 2,4-Diamino-1,3,5triazine Derivatives. Eur. J. Med. Chem. 2000, 35, 1053−1064. (7) Deans, R.; Cooke, G.; Rotello, V. M. Model Systems for Flavoenzyme Activity. Regulation of Flavin Recognition via Modulation of Receptor Hydrogen-Bond Donor−Acceptor Properties. J. Org. Chem. 1997, 62, 836−839. (8) Tashiro, T.; Oiwa, M. Reactions of 2-Methoxy- and 2Substituted 4,6-Diamino-s-triazines with Formaldehyde: Kinetics and Adaptability of the Rate Constants to Hammett and Taft Equations. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 645−654. (9) Š ebenik, A.; Osredkar, U.; Ž igon, M. Step-growth Polymerization of Guanamines with Unsaturated Aldehydes. Polym. Bull. 1989, 22, 155−161. (10) Shi, G. G. Process for the Preparation of Acetoguanamine. CN Patent 108358861, Aug 3, 2018. (11) Li, J.; Liu, C. H.; Deng, C. Y.; Wang, S. P.; Chen, G.; Zhou, A. Y.; Zhao, Y.; Zhu, M. A Process for Preparing Acetoguanamine. CN Patent 102731420, Oct 17, 2012. (12) von Angerer, S. 1,3,5-Triazines and Phosphorus Analogues. Sci. Synth. 2004, 17, 449−583. (13) Smyrl, N. R.; Smithwick, R. W., III. Hydroxide-catalyzed Synthesis of Heterocyclic Aromatic Amine Derivatives from Nitriles. J. Heterocycl. Chem. 1982, 19, 493−496. (14) Wang, J.; Xu, A.; Xu, R. Solubility of 2-Nitro-p-phenylenediamine in Nine Pure Solvents and Mixture of (Methanol + N-Methyl2-pyrrolidone) from T = (283.15 to 318.15) K: Determination and Modelling. J. Chem. Thermodyn. 2017, 108, 45−58. (15) Wang, J.; Xu, R.; Xu, A. Solubility Determination and Thermodynamic Functions of 2-Clorophenothiazine in Nine Organic Solvents from T = 283.15 K to T = 318.15 K and Mixing Properties of Solutions. J. Chem. Thermodyn. 2017, 106, 132−144. (16) Wang, J.; Xu, R.; Xu, A.; Cong, Y. Thermodynamic Modelling for Solubility of 5-Chloro-1-methyl-4-nitroimidazole in Eleven Organic Solvents from T = (283.15 to 318.15) K. J. Chem. Thermodyn. 2017, 105, 58−70. (17) Jouyban, A.; Fakhree, M. A. A. Experimental, Computational Methods Pertaining to Drug Solubility. In Toxicity and Drug Testing; Acree, W. E., Jr., Ed.; InTech: Rijeka, Croatia, 2012; pp 187−218. (18) Chen, G.; Liang, J.; Han, J.; Zhao, H. Solubility Modeling, Solute-Solvent Interactions and Thermodynamic Dissolution Properties of P-Nitrophenylacetonitrile in Sixteen Mono-Solvents at Temperatures Ranging from 278.15 K to 333.15 K. J. Chem. Eng. Data 2019, 64, 315−323. (19) Zhao, H. Research on Synthesis of Acetoguanamine and Its Effect on Modification of Melamine Series Flame Retardant. Thesis for Master’s Degree, East China University of Science and Technology, 2009. (20) Kaczmarek, M.; Radecka-Paryzek, W.; Kubicki, M. 2,4Diamino-6-methyl-1,3,5-triazine Methanol Solvate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2008, 64, o269. (21) Xiao, Z.-H. 2,4-Diamino-6-methyl-1,3,5-triazine Ethanol Solvate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2008, 64, o411. (22) Sundaramoorthy, G.; Nirmalram, J. S.; Ebenezer, S.; Muthiah, P. T. Supramolecular Self Assemblies in Polymorphs/Solvates of Aminopyrimidine and Amino-s-Triazines Derivatives. J. Mol. Struct. 2014, 1075, 178−186. (23) Bhardwaj, R. M.; Oswald, I.; Florence, A. J. 6-Methyl-1,3,5triazine-2,4-diamine Butane-1,4-diol Monosolvate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2012, 68, o3377. (24) Portalone, G. Acetoguanamine N,N-Dimethylformamide Solvate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2008, 64, o1685. (25) Chen, C.; Zhang, K.; Sun, Y.; Xiang, S.; Geng, Y.; Liu, K.; Wang, L. Supramolecular Structural Motifs in Compounds of

Acetoguanamine and Various Carboxylic Acids: N-H···O Heterosynthons and N-H···N Homosynthons. J. Mol. Struct. 2018, 1170, 60−69. (26) Gao, D.; Lang, D.; Robinson, T. Computational Study of the Thermodynamic Stabilities of Hydrogen-Bonded Complexes in Solution. Theor. Chem. Acc. 2014, 133, 1577. (27) Smallwood, I. M. Handbook of Organic Solvent Properties; Wiley: London, 1996.

E

DOI: 10.1021/acs.jced.9b00593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX