Synthesis and characterization of cyclopentyl methyl ketazine

doi:10.7523/j.issn.2095-6134.2021.05.002

Abstract

Abstract: In this paper, a new ketazine compound (C₁₄N₂H₂₄) was synthesized from cyclopentyl methyl ketone and hydrazine hydrate. After the separation and purification of the product, the structure of cyclopentyl methyl ketazinewas determined by ¹H NMR,¹³C NMR, and IR spectra. With Gaussian 09 computation, the structure (1E, 2E) of the product was proved to be the most stable molecular configuration. Furthermore, the basic physical and chemical properties of cyclopentyl methyl ketazine under atmospheric pressure were measured, including boiling point (T_b, 238.4℃), melting point (T_m, -38.2℃), density (ρ, 0.910-0.969 g·cm^-3), dynamic viscosity (η,2.35-13.17 mPa·s), and specific heat capacity (C_p, 2.97-3.63 J·g^-1·℃^-1). The thermal expansion coefficient (α, 8.26×10^-4-8.75×10^-4℃^-1) was calculated according to its density.The results show that ρ and η have a positive correlation with temperature while C_p and α have a negative correlation with temperature. The obtained data and correlation formula are very valuable for the industrial application of cyclopentyl methyl ketazine.

Key words: cyclopentyl methyl ketone, cyclopentyl methyl ketazine, infrared, density, specific heat capacity

CLC Number:

ZHAO Peng, ZHAO Wenzhao, XIA Yangfeng, LIU Long, ZHANG Yanqiang. Synthesis and characterization of cyclopentyl methyl ketazine[J]. Journal of University of Chinese Academy of Sciences, 2021, 38(5): 583-589.

References

[1] 顾春思,王涛,田恒水.过氧化氢法合成丁酮连氮的工艺研究[J]. 化学试剂,2018, 40(1):89-92.
[2] 段江丽,孙孟展,裴文.酮连氮化合物的合成及其应用研究进展[J]. 化工生产与技术,2009, 16(4):38-43.
[3] Sengul A, Kurt O, Buyukgungor O. A 2D network silver coordination polymer with the multimodal ligand 2-pyrazyl methyl ketazine[J]. Structural Chemistry, 2011, 22(4):925-929.
[4] Tamaru Y, Harada T, Yoshida Z. Novel rearrangement of ketazine dianion:new synthetic route to pyrrole, tetrahydropyridazine, and pyrazole[J]. The Journal of Organic Chemistry, 1978, 43(17):3370-3374.
[5] 李文连.稀土有机配合物发光研究的新进展[J]. 化学通报,1991(8):1-9.
[6] 王宏晓,商士斌,王丹,等.改进水性聚氨酯性能的方法研究进展[J]. 林产化学与工业,2010, 30(1):123-126.
[7] Wang C H, Cohen S G. Mercaptan catalysis in thermoneutral free radical exchange[J]. Journal of the American Chemical Society, 1957, 79(8):1924-1929.
[8] Baldwin J E, Bottaro J C. A general synthesis of pyrroles from aldehydes and ketones[J]. Journal of the Chemical Society, Chemical Communications, 1982(11):624-625.
[9] Verner J, Potacek M. Criss-cross cycloadditions on ketazines derived from alicyclic ketones[J].Molecules, 2006, 11(1):34-42.
[10] Shang Z, Reiner J, Chang J, et al. Oxidative cyclization of aldazines with bis (trifluoroacetoxy) iodobenzene[J]. Tetrahedron Letters, 2005, 46(15):2701-2704.
[11] Robev S K. Phthalazine derivatives from aromatic aldazines[J]. Tetrahedron Letters, 1981, 22(4):345-348.
[12] Evans S, Gearhart R C, Guggenberger L J, et al. Reactions of azines with electron-deficient alkynes. Formation of 1, 5-dihydropyrazolo[1, 2-a] pyrazoles,α,β-unsaturated azines, and N-allyl- and N-propenylpyrazoles[J]. The Journal of Organic Chemistry, 1977, 42(3):452-458.
[13] 尤彩霞. 吡唑啉、异噁唑啉类衍生物的合成及应用研究[D]. 兰州:兰州理工大学,2016.
[14] Kishore J, Thiyagarajan S, Gunanathan C. Ruthenium (Ⅱ)-catalysed direct synthesis of ketazines using secondary alcohols[J]. Chemical Communications, 2019, 55(31):4542-4545.
[15] 刁正坤.己酮连氮合成工艺的改进研究[J]. 四川化工与腐蚀控制,1998(6):2-3.
[16] 中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.化学试剂沸点测定通用方法:GB/T 616-2006[S]. 北京:中国标准出版社,2006.
[17] Stephens P J, Devlin F J, Chabalowski C F N, et al. Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields[J]. The Journal of Physical Chemistry, 1994, 98(45):11623-11627.
[18] 武志坚,孟庆波. La2C分子的MP2及密度泛函理论研究[J]. 原子与分子物理学报,1998, 15(3):383-385.
[19] Liu L, He C, Wang H, et al. Synthesis and characterization of ethylenediaminium nitrophenolate[J]. Journal of Molecular Structure, 2011, 989(1-3):136-143.
[20] Katritzky A R, Singh S, Kirichenko K, et al. 1-Butyl-3-methylimidazolium 3, 5-dinitro-1, 2, 4-triazolate:a novel ionic liquid containing a rigid, planar energetic anion[J]. Chemical Communications, 2005(7):868-870.
[21] Mathis D, Blanchet P, Landry V, et al. Thermal characterization of bio-based phase changing materials in decorative wood-based panels for thermal energy storage[J]. Green Energy & Environment, 2019, 4(1):56-65.
[22] 苏小琴,龙伟,刘秀兰,等.差示扫描量热仪的影响因素及测试技术[J]. 分析仪器,2019(4):74-79.
[23] 吴锐,林兰,严菁,等.差示扫描量热熔点分析法的应用性分析[J]. 化学试剂,2020, 42(3):285-290.
[24] Kuduva S S, Sarma J A R P, Katz A K, et al. Melting-points of the meta-and para-isomers of anisylpinacolone[J]. Journal of Physical Organic Chemistry, 2000, 13(11):719-728.
[25] Hulse R J, Basu R S, Singh R R, et al. Physical properties of HCFO-1233zd (E)[J]. Journal of Chemical & Engineering Data, 2012, 57(12):3581-3586.
[26] Ben Ghanem O, Mutalib M I A, Lévêque J M, et al. Studies on the physicochemical properties of ionic liquids based on 1-octyl-3-methylimidazolium amino acids[J]. Journal of Chemical & Engineering Data, 2015, 60(6):1756-1763.
[27] Sanchez L G, Espel J R, Onink F, et al. Density, viscosity, and surface tension of synthesis grade imidazolium, pyridinium, and pyrrolidinium based room temperature ionic liquids[J]. Journal of Chemical & Engineering Data, 2009, 54(10):2803-2812.
[28] Marcinkowski Ł, Kloskowski A, Namieśnik J. Physical and thermophysical properties of 1-hexyl-1, 4-diaza[2.2. 2] bicyclooctanium bis (trifluoromethylsulfonyl) imide ionic liquid[J]. Journal of Chemical & Engineering Data, 2014, 59(3):585-591.
[29] Pokorný V, Serra P B P, Fulem M, et al. Heat Capacity and Phase Behavior of Selected Oligo (ethylene glycol) s[J]. Journal of Chemical & Engineering Data, 2019, 64(6):2742-2749.
[30] Gómez E, Calvar N, Domínguez Á, et al. Thermal analysis and heat capacities of 1-alkyl-3-methylimidazolium ionic liquids with NTf^2-, TFO^-, and DCA^- anions[J]. Industrial & Engineering Chemistry Research, 2013, 52(5):2103-2110.
[31] Riesen R, Widmann G, Truttmann R. Alternating thermal analysis techniques[J]. Thermochimica Acta, 1996, 272:27-39.
[32] Krishnan R V, Nagarajan K. Evaluation of heat capacity measurements by temperature modulated differential scanning calorimetry[J]. Journal of Thermal Analysis and Calorimetry, 2010, 102(3):1135-1140.