Citation: CAO Chen-Zhong, WU Ya-Xin. An Extended Istomin-Palm Model for Estimating the Enthalpies of Formation of the Two-Direction Extending Compounds R1-Y-R2[J]. Acta Physico-Chimica Sinica, ;2013, 29(01): 35-42. doi: 10.3866/PKU.WHXB201210261 shu

An Extended Istomin-Palm Model for Estimating the Enthalpies of Formation of the Two-Direction Extending Compounds R1-Y-R2

CAO Chen-Zhong ^1, ,
WU Ya-Xin ^1,2

1.
1 Hunan Provincial University Key Laboratory of QSAR/QSPR, Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan Province, P. R. China;
2 School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China

Received Date: 3 July 2012
Available Online: 26 October 2012
Fund Project: 国家自然科学基金(21072053) (21072053)湖南省教育厅科研基金(10K025)资助项目 (10K025)

Istomin and Palm proposed a model, Δ_fH⁰(RX)=h[R]+h[X]+φ[R]φ[X], (the h[R] and h[X] are the contributions of alkyl R and substituent X to the Δ_fH⁰(RX), respectively. φ[R]φ[X] represents the interaction of alkyl R and substituent X), to express the enthalpies of formation of monoderivatives of hydrocarbons Δ_fH⁰(RX). However, in two-direction extending compounds R1-Y-R2, the Y substituent is attached to two alkyl groups (R1 and R2), and the intramolecular interactions are more complicated than that in monosubstituted alkanes. Thus, the Istomin-Palm model must be modified. In this work, the interactions among Y, R1, and R2 contributing to the enthalpy of formation, Δ_fH⁰(R1-Y-R2), are divided into three parts: the interaction between R1Y and R2(φ[R2]φ[R1Y]), the interaction between YR2 and R1 (φ[R1]φ[YR2]), and the interaction between R1 and R2 (ψ[R1]ψ[R2]). These three interactions replace the φ[R]φ[X] term, and a new extended Istomin-Palm model, Δ_fH⁰(R1-Y-R2)=h[R1]+h[R2]+h[Y] +φ[R1]φ[YR2]+φ[R2]φ[R1Y]+ψ[R1]ψ[R2], is proposed. In this model, h[Y] is the contribution of substituent Y to Δ_fH⁰(R1-Y-R2). The h[R1] and h[R2] terms are the contributions of alkyls R1 and R2 to Δ_fH⁰(R1-Y-R2). The last three terms are the total contribution of interactions among Y, R1, and R2. Furthermore, the interaction potential index IPI(X) reported in our recent work (Wu, Y. X.; Cao, C. Z.; Yuan, H. Chin. J. Chem. Phys. 2012, 25 (2), 153.) was employed to express the intrinsic interaction of Y with alkyl groups (φ[Y]), and two general expressions were established to estimate Δ_fH⁰, in which one is for thioethers, secondary amines, ethers, and ketones, and the other is for esters. These two estimating equations give results, which are as accurate as G3 and G3MP2 models in calculating Δ_fH⁰ for R1-Y-R2 compounds. Moreover, our method avoids time consuming calculations.
- Enthalpy of formation,
- Substituent,
- Interaction,
- Two-direction extending compound,
- Interaction potential index
1. [1]
  
  (1) Wiberg, K. B.;Waldron, R. F. J. Am. Chem. Soc. 1991, 113,7 697. doi: 10.1021/ja00020a036
2. [2]
  (2) Laurencelle, N.; Pacey, P. D. J. Am. Chem. Soc. 1993, 115, 625.doi: 10.1021/ja00055a035
3. [3]
  (3) Milburn, R. K.; Rodriquez, C. F.; Hopkinson, A. C. J. Phys.Chem. B 1997, 101, 1837. doi: 10.1021/jp962303e
4. [4]
  (4) Herndon,W. C.; Biedermann, P. U.; Agranat, I. J. Org. Chem.1998, 63, 7445. doi: 10.1021/jo981280s
5. [5]
  (5) Zheng, K. C.; Kuang, D. B.; Yun, F. C.; He, F. ActaPhys. -Chim. Sin. 2000, 16, 133. [郑康成, 匡代彬, 云逢存,何峰. 物理化学学报, 2000, 16, 133.] doi: 10.3866/PKU.W HXB20000208
6. [6]
  (6) Zheng, K. C.; Zhang, Z. Q.; Shen, Y.; Yun, F. C. ActaPhys. -Chim. Sin. 2001, 17, 448. [郑康成, 张仲钦, 沈勇,云逢存. 物理化学学报, 2001, 17, 448.] doi: 10.3866/PKU.W HXB20010514
7. [7]
  (7) Sorkhabi, O.; Qi, F.; Rizvi, A. H.; Suits, A. G. J. Am. Chem. Soc.2001, 123, 671. doi: 10.1021/ja0017312
8. [8]
  (8) Yang, F.;Wang, Z.; Huang, Y.; Ding, X. J. Chem. Inf. Comput.Sci. 2003, 43, 753. doi: 10.1021/ci025663+
9. [9]
  (9) Yang, F.;Wang, Z.; Huang, Y.; Zhou, P. J. Chem. Inf. Comput.Sci. 2003, 43, 1337. doi: 10.1021/ci0340512
10. [10]
  (10) Exner, O.; Böhm, S. J. Comput. Chem. 2004, 25, 1979. doi: 1 0.1002/jcc.v25:16
11. [11]
  (11) Emel'yanenko, V. N.; Kabo, G. J.; Verevkin, S. P. J. Chem. Eng.Data 2006, 51, 79. doi: 10.1021/je050230z
12. [12]
  (12) Cao, C. Z.; Liu, J. L. Acta Phys. -Chim. Sin. 2007, 23, 955.[ 曹晨忠, 刘金玲. 物理化学学报, 2007, 23, 955.] doi: 10.3866/P KU.WHXB20070632
13. [13]
  (13) Bond, D. J. Org. Chem. 2007, 72, 7313. doi: 10.1021/jo071213a
14. [14]
  (14) Thalladi, V. R.;Weiss, H. C.; Blalser, D.; Boese, R.; Nangia, A.;D esiraju, G. R. J. Am. Chem. Soc. 1998, 120, 8702. doi: 1 0.1021/ja981198e
15. [15]
  (15) Glaser, R. J. Org. Chem. 2001, 66, 771. doi: 10.1021/jo001241s
16. [16]
  (16) Ju, X. H.; Li, Y. M.; Xiao, H. M. J. Phys. Chem. A 2005, 109,9 34. doi: 10.1021/jp045071p
17. [17]
  (17) Gung, B.W.; Zou, Y.; Xu, Z.; Amicangelo, J. C.; Irwin, D. G.;M a, S.; Zhou, H. C. J. Org. Chem. 2008, 73, 689. doi: 10.1021/j o702170j
18. [18]
  (18) Mathieu, D. J. Chem. Theory Comput. 2012, 8, 1295. doi: 1 0.1021/ct2006083
19. [19]
  (19) Jabloński, M. J. Phys. Chem. A 2012, 116, 3753. doi: 10.1021/j p300993b
20. [20]
  (20) (a) Istomin, B. I.; Palm, V. A. Reakts. Sposobnost Organ.Soedin. (Tartu) 1971, 8, 845.
21. [21]
  (b) Istomin, B. I.; Palm, V. A. Reakts. Sposobnost Organ.Soedin. (Tartu) 1972, 9, 433.
22. [22]
  (c) Istomin, B. I.; Palm, V. A. Reakts. Sposobnost Organ.Soedin. (Tartu) 1972, 9, 469.
23. [23]
  (d) Istomin, B. I.; Palm, V. A. Reakts. Sposobnost Organ.Soedin. (Tartu) 1972, 9, 847.
24. [24]
  (21) Cao, C. Z.; Gao, S. Acta Phys. -Chim. Sin. 2005, 21, 1028.[ 曹晨忠, 高硕. 物理化学学报, 2005, 21, 1028.] doi: 10.3866/P KU.WHXB20050917
25. [25]
  (22) Cao, C. Z.; Gao, S.; Zeng, R. J. J. Mol. Struct. -Theochem 2005,728, 85. doi: 10.1016/j.theochem.2005.05.008
26. [26]
  (23) Cao, C. Z. QSAR Comb. Sci. 2008, 27, 555.
27. [27]
  (24) Wu, Y. X.; Cao, C. Z.; Yuan, H. Chin. J. Chem. Phys. 2012, 25 (2), 153. doi: 10.1088/1674-0068/25/02/153-160
28. [28]
  (25) Cao, C. Z.; Li, Z. L. J. Chem. Inf. Comput. Sci. 1998, 38, 1. doi: 1 0.1021/ci9601729
29. [29]
  (26) Cao, C. Z. Substituent Effects in Organic Chemistry; ScienceP ress: Beijing, 2003. [曹晨忠. 有机化学中的取代基效应. 北京 : 科学出版社, 2003.]
30. [30]
  (27) Cao, C. Z.; Liu, L. J. Chem. Inf. Comput. Sci. 2004, 44, 678.d oi: 10.1021/ci034266b
31. [31]
  (28) Haynes,W. M. CRC Handbook of Chemistry and Physics, 91ste d.; CRC Press: Boca Raton, FL, 2010-2011.
32. [32]
  (29) Domalski, E. S.; Hearing, E. D. J. Phys. Chem. Ref. Data 1993,22, 805. doi: 10.1063/1.555927
1. [1]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
2. [2]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
3. [3]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
4. [4]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
5. [5]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
6. [6]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
7. [7]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
8. [8]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
9. [9]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
10. [10]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
11. [11]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
12. [12]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
13. [13]
  Geyang Song , Dong Xue , Gang Li . Recent Advances in Transition Metal-Catalyzed Synthesis of Anilines from Aryl Halides. University Chemistry, 2024, 39(2): 321-329. doi: 10.3866/PKU.DXHX202308030
14. [14]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
15. [15]
  Aidang Lu , Yunting Liu , Yanjun Jiang . Comprehensive Organic Chemistry Experiment: Synthesis and Characterization of Triazolopyrimidine Compounds. University Chemistry, 2024, 39(8): 241-246. doi: 10.3866/PKU.DXHX202401029
16. [16]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
17. [17]
  Linhan Tian , Changsheng Lu . Discussion on Sextuple Bonding in Diatomic Motifs of Chromium Family Elements. University Chemistry, 2024, 39(8): 395-402. doi: 10.3866/PKU.DXHX202401056
18. [18]
  Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, 2025, 40(3): 10-15. doi: 10.12461/PKU.DXHX202402058
19. [19]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
20. [20]
  Jinfeng Chu , Lan Jin , Yu-Fei Song . Exploration and Practice of Flipped Classroom in Inorganic Chemistry Experiment: a Case Study on the Preparation of Inorganic Crystalline Compounds. University Chemistry, 2024, 39(2): 248-254. doi: 10.3866/PKU.DXHX202308016

Get Citation

PDF

XML

Metrics

PDF Downloads(635)
Abstract views(1966)
HTML views(67)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142