Synthesis and bioactivity of some novel 5-arylmethylideneamino-1,3,4- thiadiazole-2-ylthioacetanilide derivatives

Article abstract of DOI:10.1080/10426507.2013.787995

Some novel of 5-arylmethylideneamino-1,3,4-thiadiazole-2-ylsulfanyl acetamide derivatives were synthesized by the S-alkylation of 5-arylmethylideneamino-2-mercapto-1,3,4-thiadiazoles with chloroacetyl anilide under solid-liquid phase transfer catalysis us

Full text of DOI:10.1080/10426507.2013.787995

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis and bioactivity of some novel 5-
arylmethylideneamino-1,3,4-thiadiazole-2-
ylthioacetanilide derivatives
a
a
a
a
Wen-Long Yang , Wen-Li Wang , You-Ming Zhang & Tai-Bao Wei
a
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of
China; Key Laboratory of Polymer Materials of Gansu Province; College of Chemistry and
Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. China
Accepted author version posted online: 08 Apr 2013.
To cite this article: Phosphorus, Sulfur, and Silicon and the Related Elements (2013): Synthesis and bioactivity of some novel
-arylmethylideneamino-1,3,4-thiadiazole-2-ylthioacetanilide derivatives, Phosphorus, Sulfur, and Silicon and the Related
5
Elements, DOI: 10.1080/10426507.2013.787995
To link to this article: http://dx.doi.org/10.1080/10426507.2013.787995
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ACCEPTED MANUSCRIPT
Synthesis and bioactivity of some novel
-arylmethylideneamino-1,3,4-thiadiazole-2-ylthioacetanilide derivatives
5
Wen-Long Yang, Wen-Li Wang, You-Ming Zhang, Tai-Bao Wei
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China;
Key Laboratory of Polymer Materials of Gansu Province; College of Chemistry and Chemical
Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. China
ABSTRACT: Some novel of 5-arylmethylideneamino-1,3,4-thiadiazole-2-ylsulfanyl acetamide
derivatives were synthesized by the S-alkylation of
5
-arylmethylideneamino-2-mercapto-1,3,4-thiadiazoles with chloroacetyl anilide under

E-mail: weitaibao@126.com; Tel: 0931-7970394
1
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solid-liquid phase transfer catalysis using polyethylene glycol-400 (PEG-400) catalyst in the
presence of potassium carbonate. Some of the title compounds were investigated for plant
growth-regulating activity. They were found to enhance root elongation remarkably at a low
concentration.
KEYWORDS: 5-arylmethylideneamino-1,3,4-thiadiazole-2-ylthioacetamides; phase transfer
catalysis; bioactivity
INTRODUCTION
1
,3,4-Thiadiazole and its heterocyclic derivatives are an important class of bioactive molecules
1
that are widely used because of their membrane affinity as well as anticancer, anti-Helicobacter
2
3
4
5
6
pylori, antibacterial, CNS depressing, anticonvulsant, antimicrobial, anti-inflammatory,
7
carbonic anhydrase inhibiting, and corrosion inhibiting activities. These compounds have been
8
used in dyes and pharmaceuticals, and used as building blocks for the synthesis of organic
9
semiconductors. They also serve as useful rigid subunits in macrocyclic receptors or molecular
1
0,11
12
recognition
and plant growth-regulating activity. Thus, given the wide application range of
1
,3,4-thiadiazole and its heterocyclic derivatives in the fields of industrial, agricultural, and
medicinal chemistry, they are increasingly gaining the attention of scientists.
A literature survey reveals that some Schiff compounds containing a 1,3,4-thiadiazole ring have
1
3
good biological activities. Other studies show that the incorporation of various substitutes into
heterocyclic ring systems considerably augments the biological activities, and that amide agents
2
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1
4,15
16
also have good bioactivity.
In view of these findings and in continuation of our research we
designed and synthesized a novel series of amide-substituted fused Schiff 1,3,4-thiadiazole
systems as potential biological agents based on cumulative activity. Their plant growth-regulating
activities were then examined.
In this paper, we report a mild and efficient method for the synthesis of
1
,3,4-thiadiazole-5-ylthioacetamide derivatives using the environmentally friendly polyethylene
glycol-400 (PEG-400) as a catalyst.
RESULTS AND DISCUSSION
The reaction sequence leading to the formation of the title compounds are shown in Scheme 1.
17
2
2
-Chloroacetanilide 1 can be obtained in good to excellent yield according to our previous work.
1
8
-Amino-5-mercapto-1,3,4-thiadiazoles 2 were prepared in good yield according to literature,
and then reacted with aldehydes to give corresponding
5
5
-arylmethylideneamino-2-mercapto-1,3,4-thiadiazoles 3.
-Arylmethylideneamino-1,3,4-thiadiazole-2-ylthioacetamide derivatives 4 and 5 were
synthesized from 1 and 3 by refluxing with K
2
CO and PEG-400 in acetone for 1.5 h. This method
3
had the advantages of simple operation, short reaction times, and high yields.
EXPERIMENTAL
All regents were purchased and used without further purification. Melting points were measured
on an X-4 digital melting-point apparatus and uncorrected. IR spectra were recorded in KBr on an
3
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1
Alpha Centauri FT-IR spectrophotometer, and HNMR spectra were recorded on a
Mercuryplux-400, Varian instrument (400 MHz) using DMSO-d as solvent (operating at
00MHz for H, and 100MHz for C) and TMS as an internal reference. Elemental analysis was
6
1
13
4
performed on a PE-2400 CHN instrument.
General procedure for the synthesis of 5-arylmethylideneamino-1,3,4-thiadiazole
-
2-ylthioacetanilide derivatives
The syntheses of 4 and 5 were carried out by adding K
2
CO (2 mmol) to a mixture of 3 (2 mmol)
3
and 15 ml of acetone. The resulting mixture was then stirred at ambient temperature until 3
completely dissolved. After sequentially adding PEG-400 (0.2 mmol) and 1 (2 mmol), the mixture
was refluxed for 1.5 h. After evaporating and reclaiming the solvent in a vacuum, the crude
products were obtained and the mixture was cooled to ambient temperature. The crude product
was then filtered and washed with 10 mL of distilled water three times. The pure products were
2
acquired by recrystallization from DMF-EtOH-H O. The chemical structure of all title compounds
1
13
were characterized by FT-IR, H NMR, C NMR, and elemental analyses. The Supplemental
1
13
Materials contains a representative H and C NMR spectrum for 5e (Figures S 1 and S 2)
Physical and Spectroscopic Data for the Title Compounds
4
2
a, N-(3-nitrophenyl)-5-(4-methyloxyphenylmethylideneamino)-1,3,4-thiadiazole-
-ylthioacetamide. Yield 90%, m.p. 192-194 ºC. IR (KBr): 3249 (N-H), 1686 (C=O), 1562
-1
1
(
CH=N), 1391 (S-CH
2
), 674 cm (C-S-C). H NMR : δ 3.74 (s, 3H, OCH
3
), 4.37 (s, 2H, SCH ),
2
4
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1
3
7
1
5
.24 (m, 8H, ArH), 8.80 (s, 1H, CH=N), 10.76 (s, 1H, NH). C NMR (DMSO-d6, 100MHz): δ
92.0, 168.2, 164.2, 163.1, 160.1, 148.7, 140.5, 132.5, 131.0, 127.9, 125.8, 118.8, 115.3, 114.8,
5.9, 39.6. Anal. Calcd. For C18 : C, 50.34; H, 3.52; N, 16.31. Found: C, 50.31; H, 3.55;
H
15
N
5
O S
4 2
N, 16.29.
4
2
b, N-(3-nitrophenyl)-5-(2-hydroxyphenylmethylideneamino)-1,3,4-thiadiazole-
-ylthioacetamide. Yield 90%, m.p. 228-230 ºC. IR (KBr): 3436 (O-H), 3285 (N-H), 1661
-1
1
(
C=O), 1530 (CH=N), 1386 (S-CH
2
), 672 cm (C-S-C). H NMR : δ 4.36 (s, 2H, SCH ), 7.47 (m,
2
1
3
8
1
3
1
4
2
H, ArH), 8.63 (s, 1H, CH=N), 8.78 (s, 1H, OH), 10.92 (s, 1H, NH). C NMR : δ 170.0, 167.0,
66.1, 160.7, 160.3, 148.3, 139.9, 130.7, 130.4, 129.2, 125.1, 122.3, 118.1, 116.9, 116.5, 113.2,
8.6. Anal. Calcd. For C17
6.88.
H
13
N
5
O
4
S : C, 49.15; H, 3.15; N, 16.86. Found: C, 49.17; H, 3.11; N,
2
c, N-(3-nitrophenyl)-5-(4-hydroxyphenylmethylideneamino)-1,3,4-thiadiazole-
-ylthioacetamide. Yield 95%, m.p. 175-176 ºC. IR (KBr): 3336 (O-H), 3295 (N-H), 1687
-1
1
(
C=O), 1521 (CH=N), 1348 (S-CH
2
), 670 cm (C-S-C). H NMR : δ 4.36 (s, 2H, SCH ), 7.17 (m,
2
1
3
8
1
H, ArH), 8.00 (s, 1H, CH=N), 8.84 (s, 1H, OH), 10.32 (s, 1H, NH). C NMR : δ 170.0, 168.2,
66.7, 160.8, 160.1, 148.0, 139.9, 130.4, 129.9, 127.7, 125.1, 118.1, 116.0, 113.2, 38.9. Anal.
Calcd For C17
H
13
N
5
4
O S
2
: C, 49.15; H, 3.15; N, 16.86. Found: C, 49.13; H, 3.17; N, 16.83.
4
1
d, N-(3-nitrophenyl)-5-(3-methyloxy-4-hydroxyphenylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 87%, m.p. 216-218 ºC. IR (KBr): 3433 (O-H), 3289
5
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1
1
(
N-H), 1653 (C=O), 1579 (CH=N), 1386 (S-CH
OCH ), 4.37 (s, 2H, SCH ), 7.45 (m, 7H, ArH), 8.64 (s, 1H, CH=N), 8.73 (s, 1H, OH), 10.91(s,
H, NH). C NMR : δ 174.6, 168.7, 166.1, 161.5, 152.9, 148.2, 148.0, 139.8, 130.4, 126.9,
2
), 699 cm (C-S-C). H NMR : δ 3.80 (s, 3H,
3
2
13
1
1
3
4
1
25.9, 125.1, 118.2, 115.7, 113.3, 111.1, 56.0, 38.8. Anal. Calcd. For C18
.39; N, 15.72. Found: C, 48.51; H, 3.42; N, 15.70.
H
15
N
5
O
5
2
S : C, 48.53; H,
e, N-(3-nitrophenyl)-5-(4-N,N-dimethylaminophenylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 90%, m.p.>270 ºC. IR (KBr): 3241 (N-H), 1616
-
1
1
(
C=O), 1584 (CH=N), 1352 (S-CH
2
), 687 cm (C-S-C). H NMR : δ 3.36 (s, 6H, CH
3
), 4.37 (s,
), 7.36 (m, 8H, ArH), 8.61 (s, 1H, CH=N), 10.90 (s, 1H , NH ). C NMR : δ 175.2,
67.9, 165.3, 160.4, 153.9, 151.8, 130.3, 129.9, 123.6, 121.5, 115.5, 114.6, 114.4, 64.7, 40.1, 38.8.
: C, 51.57; H, 4.10; N, 18.99. Found: C, 51.54; H, 4.12; N, 18.97.
f, N-(3-nitrophenyl)-5-(2-furylmethylideneamino)-1,3,4-thiadiazole- 2-ylthioacetamide.
Yield 90%, m.p. 212-214 ºC. IR (KBr): 3253 (N-H), 1681 (C=O), 1549 (CH=N), 1393 (S-CH
1
3
2
1
H, SCH
2
Anal. Calcd. For C19
H
18
N
6
O S
3 2
4
2
),
), 7.18 (m, 3H, Furyl), 7.80 (m, 4H, ArH), 9.06
s, 1H, CH=N), 10.91 (s, 1H, NH). C NMR : δ 176.7, 171.0, 166.7, 149.1, 148.0, 146.5, 143.9,
-1
1
6
79 cm (C-S-C). H NMR : δ 4.37 (s, 2H, SCH
2
1
3
(
1
2
4
1
39.9, 130.4, 125.1, 118.2, 113.2, 109.9, 109.5, 38.9. Anal. Calcd. For C15
.85; N, 17.99. Found: C, 46.25; H, 2.88; N, 17.97.
H
11
N
5
O
4
S : C, 46.27; H,
2
g, N-(3-nitrophenyl)-5-(5-(4-bromophenyl)-2-furylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 88%, m.p. 234-235 ºC. IR (KBr): 3245 (N-H), 1688
6
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1
1
(
C=O), 1594 (CH=N), 1385 (S-CH
2
), 673 cm (C-S-C). H NMR : δ 4.37 (s, 2H, SCH
2
), 7.67 (m,
H, Furyl), 7.85 (m, 8H, ArH), 8.70 (s, 1H, CH=N), 10.83 (s, 1H, NH). C NMR : δ 169.1,
66.3, 162.3, 155.1, 148.4, 148.0, 142.1, 139.8, 133.5, 130.4, 130.3, 128.2, 127.4, 124.6, 118.2,
13.2, 109.3, 104.6, 38.9. Anal. Calcd. For C21 Br: C, 46.33; H, 2.59; N, 12.86. Found:
1
3
2
1
1
H N
14 5
O
S
4 2
C, 46.31; H, 2.61; N, 12.83.
4
1
h, N,N'-di(3-nitrophenyl)-5,5'-(1,2-phenylenedimethylideneamino-
,3,4-thiadiazole-2-ylthioacetamide). Yield 78%, m.p. 164-165 ºC. IR (KBr): 3265 (N-H), 1629
-1
1
(
C=O), 1530 (CH=N), 1347 (S-CH
2
), 669 cm (C-S-C). H NMR : δ 4.36 (s, 4H, SCH ), 7.69 (m,
2
1
3
1
1
2H, ArH), 8.65 (s, 2H, CH=N), 10.90 (s, 2H, NH). C NMR : δ 173.1, 168.2, 165.2, 160.1,
48.6, 139.5, 134.1, 131.8, 130.1, 129.3, 127.7, 116.4, 115.5, 38.7. Anal. Calcd. For
C
28
H
20
N
10
O
6
4
S : C, 46.66; H, 2.80; N, 19.43. Found: C, 46.68; H, 2.82; N, 19.40.
4
1
i N,N'-di(3-nitrophenyl)-5,5'-(1,3-phenylenedimethylideneamino-
,3,4-thiadiazole-2-ylthioacetamide). Yield 78%, m.p. 182-184 ºC. IR (KBr): 3280 (N-H), 1696
-1
1
(
C=O), 1529 (CH=N), 1351 (S-CH
2
), 694 cm (C-S-C). H NMR : δ 4.36 (s, 4H, SCH ), 7.69 (m,
2
1
3
1
1
2H, ArH), 8.65 (s, 2H, CH=N), 10.90 (s, 2H, NH). C NMR : δ 172.5, 168.6, 164.1, 160.3,
48.9, 139.4, 133.9, 131.6, 129.0, 128.8, 128.5, 127.7, 116.7, 115.1, 38.9. Anal. Calcd. For
C
28
H
20
N
10
O
6
4
S : C, 46.66; H, 2.80; N, 19.43. Found: C, 46.64; H, 2.78; N, 19.46.
5
1
a, N-(3-methylphenyl)-5-(4-methyloxyphenylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 81%, m.p. 165-167 ºC. IR (KBr): 3187 (N-H), 1665
7
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1
1
(
C=O), 1561 (CH=N), 1378 (S-CH
H, OCH ), 4.86 (s, 2H, SCH ), 7.16 (m, 8H, ArH), 8.12 (s, 1H, CH=N), 10.13 (s, 1H, NH). C
NMR : δ 182.0, 168.2, 164.2, 163.1, 160.1, 140.5, 138.5, 130.2, 128.7, 126.2, 124.9, 121.3,
18.8, 114.4, 55.9, 38.6, 21.3. Anal. Calcd. For C19 : C, 57.27; H, 4.55; N, 14.06. Found:
C, 57.29; H, 4.52; N, 14.08.
2
), 699 cm (C-S-C). H NMR : δ 2.31 (s, 3H, CH
3
), 3.73 (s,
1
3
3
3
2
1
H
18
N
4
O
S
2 2
5
2
1
b, N-(3-methylphenyl)-5-(2-hydroxyphenylmethylideneamino)-1,3,4-thiadiazole-
-ylthioacetamide. Yield 68%, m.p. 122-124 ºC. IR (KBr): 3432(O-H), 3262 (N-H), 1659 (C=O),
-
1
1
551 (CH=N), 1369 (S-CH
), 6.98 (m, 8H, ArH), 8.53 (s, 1H, CH=N), 8.77 (s, 1H, OH), 10.95 (s, 1H, NH). C NMR :
δ 175.0, 167.3, 166.7, 162.7, 160.3, 149.4, 138.7, 138.1, 130.4, 128.6, 124.3, 122.3, 119.7, 116.3,
2
), 686 cm (C-S-C). H NMR : δ 2.31 (s, 3H, CH
3
), 4.39 (s, 2H,
13
SCH
2
1
5
5
16.5, 113.2, 38.7, 21.2. Anal. Calcd. For C18
6.20; H, 4.22; N, 14.55.
H
16
N
4
O
2
S : C, 56.23; H, 4.19; N, 14.57. Found: C,
2
c, N-(3-methylphenyl)-5-(4-hydroxyphenylmethylideneamino)-1,3,4-thiadiazole
-
2-ylthioacetamide. Yield 82%, m.p. 154-155 ºC. IR (KBr): 3330(O-H), 3286 (N-H), 1654
-
1
1
(
C=O), 1503 (CH=N), 1318 (S-CH
H, SCH ), 7.15 (m, 8H, ArH), 8.05 (s, 1H, CH=N), 8.86 (s, 1H, OH), 10.15 (s, 1H, NH). C
NMR : δ 170.0, 167.0, 165.7, 160.7, 160.3, 138.7, 138.1, 130.4, 128.6, 124.3, 122.3, 119.7,
2
), 682 cm (C-S-C). H NMR : δ 2.28 (s, 3H, CH ), 3.97 (s,
3
1
3
2
2
1
5
18.2, 116.3, 38.7, 21.2. Anal. Calcd. For C18
6.25; H, 4.21; N, 14.54.
H
16
N
4
O
2
2
S : C, 56.23; H, 4.19; N, 14.57. Found: C,
8
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5
1
d, N-(3-methylphenyl)-5-(3-methyloxy-4-hydroxyphenylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 78%, m.p. >270 ºC. IR (KBr): 3340(O-H), 3259
-1
1
(
N-H), 1643 (C=O), 1509 (CH=N), 1402 (S-CH
2
), 634 cm (C-S-C). H NMR : δ 2.33 (s, 3H,
CH
3
), 3.63 (s, 3H, OCH
3
), 4.39 (s, 2H, SCH
2
), 7.13 (m, 7H, ArH), 8.61 (s, 1H, CH=N), 8.75 (s, 1H,
1
3
OH), 10.14 (s, 1H, NH). C NMR : δ 174.2, 168.5, 165.1, 160.5, 151.5, 148.2, 138.6, 138.1,
28.9, 126.9, 125.9, 122.8, 121.1, 118.2, 117.7, 114.3, 56.2, 38.7, 22.3. Anal. Calcd. For
: C, 55.06; H, 4.38; N, 13.52. Found: C, 55.09; H, 4.36; N, 13.49.
1
C
19
H
18
N
4
O S
3 2
5
1
e, N-(3-methylphenyl)-5-(4-N,N-dimethylaminophenylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide. Yield 85%, m.p. 221-222 ºC. IR (KBr): 3204 (N-H), 1611
-1
1
(
C=O), 1580 (CH=N), 1312 (S-CH
2
), 637 cm (C-S-C). H NMR : δ 2.28 (s, 3H, CH
3
), 3.33 (s,
1
3
6
H, CH
3
), 4.27 (s, 2H, SCH
2
), 7.13 (m, 8H, ArH), 8.61 (s, 1H, CH=N), 10.29 (s, 1H, NH). C
NMR : δ 175.2, 167.8, 165.1, 160.4, 153.9, 138.6, 138.0, 132.3, 128.6, 124.3, 121.5, 119.6,
16.3, 111.5, 40.1, 38.9, 21.1. Anal. Calcd. For C20 OS : C, 58.37; H, 5.14; N, 17.02. Found:
C, 58.35; H, 5.17; N, 17.00.
f, N-(3-methylphenyl)-5-(2-furylmethylideneamino)-1,3,4-thiadiazole- 2-ylthioacetamide.
Yield 85%, m.p. >270 ºC. IR (KBr): 3233 (N-H), 1625 (C=O), 1531 (CH=N), 1372 (S-CH ), 670
), 6.92 (m, 3H, Furyl), 7.36 (m,
H, ArH), 8.11 (s, 1H, CH=N), 10.61 (s, 1H, NH). C NMR : δ 176.1, 170.0, 165.7, 148.2,
1
H
21
N
5
2
5
2
-1
1
cm (C-S-C). H NMR : δ 2.28 (s, 3H, CH
3
), 4.37 (s, 2H, SCH
2
1
3
4
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1
46.5, 143.9, 138.6, 138.4, 128.8, 124.2, 121.2, 118.5, 109.8, 109.5, 38.6, 21.3. Anal. Calcd. For
: C, 53. 62; H, 3.94; N, 15.63. Found: C, 53. 59; H, 3.96; N, 15.61.
C
16
H
14
N
4
O S
2 2
5
1
g, N-(3-methylphenyl)-5-(5-(4-bromophenyl)-2-furylmethylideneamino)-
,3,4-thiadiazole-2-ylthioacetamide). Yield 78%, m.p. >270 ºC. IR (KBr): 3230 (N-H), 1641
-1
1
(
C=O), 1514 (CH=N), 1402 (S-CH
2
), 633 cm (C-S-C). H NMR : δ 2.28 (s, 3H, CH
3
), 4.36 (s,
1
3
2
H, SCH
2
), 7.66 (m, 2H, Furyl), 7.84 (m, 8H, ArH), 8.68 (s, 1H, CH=N), 10.63 (s, 1H, NH). C
NMR : δ 169.0, 165.3, 162.3, 155.1, 148.4, 146.0, 138.5, 138.3, 132.1, 130.1, 129.4, 128.3,
24.2, 123.4, 121.6, 118.2, 107.3, 104.6, 38.6, 21.3. Anal. Calcd. For C22 Br: C, 51.47;
H, 3.34; N, 10.91. Found: C, 51.50; H, 3.32; N, 10.94.
1
H
17
N
4
O S
2 2
5
1
h N,N'-di(3-methylphenyl)-5,5'-(1,2-phenylenedimethylideneamino-
,3,4-thiadiazole-2-ylthioacetamide). Yield 80%, m.p. >270 ºC. IR (KBr): 3284 (N-H), 1653
-
1
1
(
C=O), 1504 (CH=N), 1319 (S-CH
2
), 642 cm (C-S-C). H NMR : δ 2.29 (s, 6H, CH
3
), 4.01 (s,
), 7.15 (m, 12H, ArH), 8.65 (s, 2H, CH=N), 10.31 (s, 2H, NH). C NMR : δ 170.0,
68.2, 165.7, 160.1, 138.6, 138.5, 134.0, 131.2, 130.1, 128.6, 124.2, 121.3, 119.6, 38.7, 21.1. Anal.
: C, 54.69; H, 3.98; N, 17.01. Found: C, 54.71; H, 3.95; N, 17.04.
i N,N'-di(3-methylphenyl)-5,5'-(1,3-phenylenedimethylideneamino-
,3,4-thiadiazole-2-ylthioacetamide). Yield 80%, m.p. 138-140 ºC. IR (KBr): 3293 (N-H), 1670
1
3
4
1
H, SCH
2
Calcd. For C30
H
26
N
8
O S
2 4
5
1
-1
1
(
C=O), 1548 (CH=N), 1368 (S-CH
2
), 688 cm (C-S-C). H NMR : δ 2.29 (s, 6H, CH
3
), 4.26 (s,
1
3
4
H, SCH
2
), 7.48 (m, 12H, ArH), 8.64 (s, 2H, CH=N), 10.40 (s, 2H, NH). C NMR : δ 172.5,
1
0
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1
2
1
5
1
68.6, 164.1, 160.3, 138.9, 138.4, 133.9, 131.5, 129.0, 128.9, 128.5, 124.7, 121.2, 118.1, 38.9,
1.2. Anal. Calcd. For C30
7.03.
H
26
N
8
O
2
4
S : C, 54.69; H, 3.98; N, 17.01. Found: C, 54.66; H, 3.96; N,
j N,N'-di(3-methylphenyl)-5,5'-(1,4-phenylenedimethylideneamino-
,3,4-thiadiazole-2-ylthioacetamide). Yield 82%, m.p. 232-234 ºC. IR (KBr): 3273 (N-H), 1660
-
1
1
(
C=O), 1546 (CH=N), 1370 (S-CH
2
), 691 cm (C-S-C). H NMR : δ 2.30 (s, 6H, CH
3
), 4.33 (s,
), 7.43 (m, 12H, ArH), 8.15 (s, 2H, CH=N), 10.26 (s, 2H, NH). C NMR : δ 170.7,
68.6, 166.4, 164.1, 139.4, 138.7, 136.0, 129.3, 128.8, 124.9, 120.3, 117.0, 39.6, 21.9. Anal.
: C, 54.69; H, 3.98; N, 17.01. Found: C, 54.67; H, 3.95; N, 17.00.
1
3
4
1
H, SCH
2
Calcd. For C30
H
26
N
8
O S
2 4
BIOLOGICAL ACTIVITY
Some of the synthesized compounds were investigated for plant growth regulation activity. The
plate culture method was adopted, and the compound solutions were prepared in the concentration
of 100, 10, 1, 0.1, 0.01, and 0.001 ppm. Rapeseeds were cultured in a 10 cm flat utensil with 10 mL
of different solution and a circular filter paper. Then, the roots were allowed to grow at room
temperature. The root length was obtained after 4 d. The percentage plant growth activity was
calculated according to the following equation: Percentage plant growth activity = (N-N
00%, where N is the root length cultured in compound solution, and N is the root length cultured
in distilled water under the same condition.
1
)/N
1
×
1
1
1
1
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The results, as shown in Table S 1 (Supplemental Materials), indicated that all of the tested
compounds displayed good inhibition activities against the root growth of tested weeds at high
concentration of 100 ppm, while displayed enhancing root elongation activity at a low
concentration of 1 to 0.001 ppm. For example, compound 4f displayed 36.42% enhancing root a
elongation activity at a low concentration of 0.001 ppm. When compared with heteroauxing it is
seen that the compounds have obvious inhibition of root elongation at high concentration of 100
ppm, while they show remarkable enhancement in root elongation at the low concentration.
CONCLUSION
In summary, we describe a simple, efficient, straightforward method for the synthesis of
N-benzylideneamino-1,3,4-thiadiazole-2-ylsulfanyl acetamide derivatives. The ambient
conditions, high reaction rates, excellent product yields, and easy work-up procedure which using
of PEG-400 as a phase transfer catalyst not only make this methodology promoter, but also make it
significant under the umbrella of environmentally greener and safer processes. In addition, some
of the title compounds have considerable promoting activities on the rapeseeds growth.
ACKNOWLEDGEMENT
This work was supported by the National Natural Science Foundation of china (NSFC) (No.
2
1064006 and No. 21161018), the Natural Science Foundation of Gansu Province
1
2
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(
1010RJZA018) and the Program for Changjian Scholars and innovative Research Team in
University of Ministry of Education of China (IRT1177).
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[
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0, 1903-1905.
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1
1
4
:R =m-NO
2
; 5: R =m-CH
3
R: 4-CH
3
O-C
6
H
4
-(a) 2-OHC
6
H
4
-(b) 4-OHC
6
H
4
-(c) 3-CH
3
O-4-OHC
6
H
3
-(d)
(
H C) N
3 2
Br
Ar=
O
O
(
e)
(f)
(g)
(
h)
(i)
(j)
SCHEME 1
Supplemental Materials
1
6
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Biological Activity
Table S 1: Plant Growth regulating activity (%) data
a
Plant growth activity (%)
Compound
0
.001
1
00 mg/L
10 mg/L
1 mg/L
0.1 mg/L 0.01 mg/L
mg/L
10.4
4
b
-100
-100
-100
-100
-100
-100
-100
-55.04
-64.67
-12.33
-25.1
41.42
36.37
15.29
44.7
24.08
67.24
15.88
6.17
43.73
40.32
35.09
6.83
4
c
21.00
4.43
4
d
4
e
4.13
4
f
7.58
33.16
52.02
-33.66
29.29
30.54
77.65
42.15
-10.54
73.99
36.42
-3.08
27.15
4
g
-60.89
-66.67
Heteroauxin
2
a The solution was prepared in the proportion of H O:DMF=99.5:0.5, and 0.1 g Tween 80 was added to
induce dissolution of the compound.
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7
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1
Figure S 1: H NMR of 5e
1
8
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1
3
Figure S 2: C NMR of 5e
1
9
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