Journal Information

Journal ID (publisher-id): chemical

Title: Journal of the Korean Chemical Society

Translated Title (ko): 대한화학회지

ISSN (print): 1017-2548

ISSN (electronic): 2234-8530

Publisher: Korean Chemical Society대한화학회

Article Information

Copyright statement: Copyright © 2021, Korean Chemical Society

Copyright: 2021

Date received: 21 December 2020

Date accepted: 18 January 2021

Publication date (print): 20 April 2021

Volume: 65

Issue: 2

Pages: 1-7

Publisher ID: jkcs-65-s113

Synthesis of Asymmetric Pyrazoline Derivatives from Phenylthiophenechalcones; DFT Mechanistic Study

Asmaa Aboelnaga

Eman Mansour[*]

Hoda. A. Ahmed[†]

Mohamed Hagar[‡][*]

Department of Chemistry, Faculty of Women for Arts, Science and Education, Egypt, Ain Shams University, Cairo, P.O. Box 11566, Egypt.

[†] Faculty of Science, Department of Chemistry, Cairo University, Cairo 12613, Egypt.

[‡] Faculty of Science, Chemistry Department, Alexandria University, Alexandria 21321, Egypt.

Author notes:

Correspondence to: [*] E-mail: emanmansour211@yahoo.com

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FigureS1.

The geometrical structure of 3aii and 3bii.

jkcs-65-s113-f001.tif
FigureS2.

APT charges of 3aii and 3bii.

jkcs-65-s113-f002.tif
FigureS3.

The geometrical structures of the most stable conformers of pyrazole derivative 4a, b.

jkcs-65-s113-f003.tif
FigureS4.

Experimental Ultraviolet visible spectrum of the compounds 3a, b and 4a, b.

jkcs-65-s113-f004.tif
FigureS5.

1H NMR of 1-(biphenyl-4-yl)-3-(5-phenylthiophen-2-yl) prop-2-en-1-one (3a).

jkcs-65-s113-f005.tif
FigureS6.

1H NMR of 3-(5-phenylthiophen-2-yl)-1-(4-(piperidin-1-yl) phenyl) prop-2-en-1-one (3b).

jkcs-65-s113-f006.tif
FigureS7.

1H NMR of 5-(biphenyl-4-yl)-3-(5-phenylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (4a).

jkcs-65-s113-f007.tif
FigureS8.

1H NMR of 3-(5-phenylthiophen-2-yl)-5-(4-(piperidin-1-yl) phenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (4b).

jkcs-65-s113-f008.tif
FigureS9.

13C NMR of 3-(5-phenylthiophen-2-yl)-1-(4-(piperidin-1-yl) phenyl) prop-2-en-1-one (3b).

jkcs-65-s113-f009.tif
FigureS10.

13C NMR of 5-(biphenyl-4-yl)-3-(5-phenylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (4a).

jkcs-65-s113-f010.tif
TableS1.

Thermal parameters (Hartree/Particle) of 3a (i-iv) and 3b (i, ii)

Parameter 3ai 3aii 3aiii 3aiv 3bi 3bii
Ecorr 0.354267 0.354236 0.354051 0.354080 0.415871 0.412301
ZPVE -1436.525705 -1436.525925 -1436.522804 -1436.522877 -1455.855579 -1456.106969
Etot -1436.503716 -1436.503922 -1436.500689 -1436.500777 -1455.832396 -1456.083566
H -1436.502771 -1436.502978 -1436.499745 -1436.499833 -1455.831452 -1456.082622
G -1436.581677 -1436.581686 -1436.579320 -1436.579128 -1455.912580 -1456.163920
ΔH of 3a 0.12989 0.00000 2.02874 1.97352
ΔH of 3b 157.71811 0.00000
TableS2.

APT charges of 3aii and 3bii

Atoms 3aii 3bii
1 C 1.542513 1.694828
2 C -0.817673 -0.767780
3 O -0.884223 -0.926469
4 C 0.716468 0.628943
5 C -0.364727 -0.173074
6 C -0.317217 -0.811183
7 C 0.251588 0.103723
8 C -0.214063 -0.263964
9 C 0.156180 0.146624
10 S -0.089358 -0.017232
11 C 0.080135 0.153855
12 C or N -0.021715 -0.059755
13 C 0.006669 0.010964
14 C -0.045686 -0.071076
15 C -0.005776 0.008667
16 C -0.037949 -0.047131
17 C 0.079282 0.319468
18 C 0.109220 -0.404756
19 C -0.038199 0.989711
20 C -0.054161 -0.367081
21 C -0.036071 0.430065
22 C 0.102400 0.305929
23 C -0.042429 0.280923
24 C 0.010784 0.003678
25 C -0.045645 0.007774
26 C 0.001180 0.021064
27 C -0.041530 -1.196716
TableS3.

Thermal parameters (Hartree/Particle) of R and S of 4a (i-iv) and S of 4b (i, ii)

Parameter 4ai R 4ai S 4aii R 4aii S 4aiii R 4aiii S 4aiv R 4aiv S 4bi S 4bii S
Ecorr 0.4082 0.4097 0.4097 0.4098 0.4130 0.4098 0.4103 0.4097 0.4677 0.4678
ZPVE -1963.5430 -1963.5789 -1963.5792 -1963.5789 -1963.2749 -1963.5790 -1963.5914 -1963.5792 -1983.1615 -1983.1619
Etot -1963.5209 -1963.5530 -1963.5533 -1963.5530 -1963.2491 -1963.5531 -1963.5655 -1963.5533 -1983.1343 -1983.1347
H -1963.5200 -1963.5521 -1963.5523 -1963.5521 -1963.2481 -1963.5522 -1963.5646 -1963.5523 -1983.1333 -1983.1337
G -1963.5950 -1963.6397 -1963.6404 -1963.6393 -1963.3355 -1963.6398 -1963.6523 -1963.6404 -1983.2240 -1983.2239
TableS4.

Selected structure parameters of optimized geometry of stable S isomers of 4aiv and 4bii calculated by DFT B3LYP/6-311G method

Structural Parameters 4aiv S 4aiv R 4bii S
Ra)
C1-C2 1.46308 1.46000 1.46316
C2-C3 1.51963 1.52322 1.51954
C3-C4 1.55778 1.54662 1.55774
C4-N5 1.49955 1.49757 1.49971
N5-N6 1.40125 1.40918 1.40131
C2-N6 1.30099 1.29839 1.30098
C4-C7 1.50580 1.51094 1.50589
C10-C12 1.46448 1.46528
C22-C26 1.48797 1.48775
Aa)
C1-C2-C3 124.958 125.356 124.960
C1-C2-N6 121.549 122.030 121.549
N5-C4-C7 111.293 33.768 111.280
C4-C7-C8 129.384 129.180 129.366
C4-C7-S11 119.875 120.799 119.893
Da)
N5-C4-C7-S11 37.162 31.658 159.907
C3-C2-C1-C21 1.291 175.345 179.300
C9-C10-C12-C17 150.400 151.431 150.401

a) R, bond length ((Å); A bond angle (o); D, dihedral angle (o).