s3-eu-west-1.amazonaws.com · Web viewTo a mixture of the synthesized acetyl/thioacetyl sulfonamide...

A facile method for regioselective synthesis of new N-acetyl/thioacetyl-(E)-

stilbene benzenesulfonamide derivatives via N-acetyl/thioacetyl sulfonamide

formation

Maryam Ahmadian-Moghaddam a , Ahmadreza Bekhradnia a, b*, and Monire Tatar a

aPharmaceutical Sciences Research Center, Department of Medicinal Chemistry, Mazandaran

University of Medical Sciences, Sari, Iran

bDepartment of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg,

Sweden

Email: abekhradnia@mazums.ac.ir

Supplemental Materials

General Procedure for the Synthesis of 4-bromobenzenesulfonyl chloride

In order to produce the desired sulfonyl chloride, TMSCl (15 mmol) and KNO3 (15 mmol) were

added to a mixture of 4-bromothiophenol (7 mmol) dissolved in dichloromethane (40 mL). The

glass vessel was then sealed and the reaction mixture was allowed to be stirred at 30˚C. The

progress of the reaction was monitored by TLC. After completion, the mixture was cooled to

room temperature and then filtered. The filtrate was washed with water and brined and dried

using anhydrous MgSO4. Finally, the solvent was evaporated to yield the desired sulfonyl

chloride.

Yield: 90%, mp: 74⁰C; 73-75 ˚C [lit.21], C6H4BrClO2S; MW: 255.3. IR (KBr,cm-1) νmax: 1166.4,

1374.4 (S=O). 1H-NMR (400 MHz, CDCl3): δ 7.7-8.0 (m, 4H, phenyl hydrogens).

13C-NMR (100 MHz, CDCl3): δ 128,130,133,143 (Aromatic carbons).

General procedure for the synthesis of the corresponding acetyl/thioacetyl sulfonamide

A solution of acetamide/thioacetamide (7 mmol) in acetonitrile (20 mL) was added gradually to a

solution of p-bromosulfonyl chloride (7 mmol) in acetonitrile (20 mL). The reaction vessel was

sealed and the mixture was stirred for 24 h at room temperature. The highly purified

corresponding acetyl/thioacetyl sulfonamide was obtained by the recrystallization of the desired

product in ethanol and water

N-Acetyl-4-bromobenzenesulfonamide

Yield: 90%, mp: 100 C; C⁰ 8H8BrNO3S; MW: 277.9. IR (KBr,cm-1) νmax : 1811.6 (C=O), 2872. 1

(sp3 C-H). 1H-NMR (400 MHz, CDCl3): δ 3.44 (s, 3H, -CH3), 7.36-7.43 (m, 4H, phenyl

hydrogens). 13C-NMR (100 MHz, CDCl3): δ 24.0 (CH3); 121.6, 129.4, 132.2, 135.7 (Aromatic

carbons); 170.3 (C=O).

N-Thioacetyl-4-bromobenzenesulfonamide

Yield: 91%, mp: 119 C;⁰ C8H8BrNO2S2; MW: 293.9. IR (KBr, cm-1) νmax : 1060.7 (C=S), 2871.7

(sp3 C-H), 3428.1 (N-H). 1H-NMR (400 MHz, CDCl3): δ 3.32 (s,3H,-CH3) , 7.36 (d, J=8.7 Hz,

2H, phenyl, H-3, H-5), 7.45 (d, J=8.7 Hz, 2H, phenyl, H-2, H-6).

General procedure for the synthesis of the stilbene derivatives

To a mixture of the synthesized acetyl/thioacetyl sulfonamide derivative (7 mmol), LiOAc-H2O

(1.5g, 22.7 mmol), LiCl (0.4 g, 9.4 mmol), Bu4N+Cl- (3.5 g, 12.5 mmol) and Pd(OAc)2 (50 mg) in

DMF, p-bromostyrene (6 mmol) was added gradually. The mixture was then heated for 18 hours

at a temperature of about 118˚C while being stirred. The resultant mixture was then cooled to

room temperature. After adding a saturated solution of sodium bicarbonate, the crude product

was extracted by ethyl acetate. The resulting mixture was dried with Na2SO4 and the organic

solvent evaporated under reduced pressure. Subsequent recrystallization of the crude product in

ethanol and water furnished the pure products

(E)-N-Acetyl/Thioacetyl–4-(2-(phenyl)ethenyl)benzenesulfonamide (7a-b)

7a: Yield: 73%; 1H-NMR (400 MHz, CDCl3): δ 2.40 (s, 3H, -CH3); 7.50-7.80 (m, 9H, phenyl

hydrogens); 7.85 (d, Jab=14 Hz, 1H, Ha); 7.95 (d, Jab=14 Hz, 1H, Hb). 13C-NMR (100 MHz,

CDCl3): δ 21.1 (CH3); 119.4, 121.7(Olefinic carbons); 125.2, 128.3, 130.5, 132.0, 137.1, 141.1,

149.1, 150.0 (Aromatic carbons); 168.2 (C=O). Elem. Anal. for (E)-N-Acetyl–4-(2-

(phenyl)ethenyl)benzenesulfonamide: C, 63.85%; N, 4.61%; H, 5.05%. Anal. Calcd.: C, 63.77%;

N. 4.65%; H, 5.02%.

7b: Yield: 75%, mp ~160 ˚C; C16H15NO2S2; MW: 317.4. 1H-NMR (400 MHz, CDCl3): δ 2.20 (s,

3H, -CH3); 7.36-7.44 (m, 9H, phenyl hydrogens); 7.56 (d, Jab=12 Hz, 1H, Ha); 7.65 (d, Jab=12

Hz, 1H, Hb). Elem. Anal. for (E)-N-Thioacetyl–4-(2-(phenyl)ethenyl) benzenesulfonamide is the

following: C, 60.59%; N, 4.39%; H, 4.79%. Anal. Calcd.: C, 60.56%; N.

4.1%; H, 4.76%.

(E)-N-Acetyl/Thioacetyl–4-(2-(methylphenyl)ethenyl)benzenesulfonamide (7c-d)

7c: Yield: 79%, mp ~ 170 ˚C; C17H17O3NS; MW: 309.95 IR (KBr,cm-1) νmax: 1643.1 (C=C). 1H-

NMR (400 MHz, CDCl3), δ 3.1-3.2 (s, 6H, -CH3); 7.35-7.5, 8.03-8.08 (8H, phenyl hydrogens);

8.1 (d, 1H, Ha, J=8.8); 8.3 (d, 1H, Hb, J =8.4).13C-NMR (100 MHz, CDCl3), δ 27, 48, 121, 125,

128, 131, 133, 145, 150, 150, 153; 172 (C=O). Elem. Anal. for (E)-N-Acetyl–4-(2-

(methylphenyl)ethenyl) benzenesulfonamide: C, 64.79%; N, 4.40%; H, 5.42%. Anal. Calcd.: C,

64.76%; N. 4.44%; H, 5.39%.

7d: Yield: 82%, mp ~160 ˚C; C17H18O2NS2; MW: 331. 1H-NMR (400 MHz, CDCl3), δ 2-3 (s, 6H,

-CH3); 7.46-74, 8.04-8.07 (8H, phenyl); 8.2 (d, 1H, Ha, J=10); 8.4 (d, 1H, Hb, J =10). Elem.

Anal. for (E)-N-Thioacetyl–4-(2-(methylphenyl)ethenyl) benzenesulfonamide: C, 61.58%; N,

4.25%; H, 5.11%. Anal. Calcd.: C, 61.63%; N. 4.23%; H, 5.13%.

(E)-N-Acetyl/Thioacetyl–4-(2-(methoxyphenyl)ethenyl)benzenesulfonamide(7e-f)

7e: Yield: 91%; 1H-NMR (400 MHz, CDCl3): δ 2.32 (s, 3H,-CH3); 7.15-7.25 (m, 4H, 4-

methoxyphenyl hydrogens); 7.33-7.55 (m, 4H, acetylsulfonamidophenyl hydrogens); 7.75 (d,

1H, Ha); 7.83 (d, 1H, Hb). 13C-NMR (100 MHz, CDCl3): δ 18.5 (CH3); 115.3, 118.2(Olefinic

carbons); 122.5, 126.8, 129.2, 130.1, 133.6, 139.3, 141.1, 143.5 (Aromatic carbons); 183.6

(C=O). Elem. Anal. for (E)-N-Acetyl–4-(2-(methoxyphenyl)ethenyl) benzenesulfonamide: C,

61.58%; N, 4.24%; H, 5.15%. Anal. Calcd.: C, 61.61%; N. 4.22%; H,

5.17%.

7f: Yield: 90%; 1H-NMR (400 MHz, CDCl3): δ 2.15 (s, 3H,-CH3); 7.10-7.23 (m, 4H, 4-

methoxyphenyl hydrogens); 7.28-7.48 (m, 4H, acetylsulfonamidophenyl hydrogens); 7.60 (d,

1H, Ha); 7.69 (d, 1H, Hb). 13C-NMR (100 MHz, CDCl3): δ 16.2 (CH3); 110.3, 114.5(Olefinic

(C=S). Elem. Anal. for (E)-N-Thioacetyl–4-(2-(methoxyphenyl)ethenyl) benzenesulfonamide: C,

58.73%; N, 3.99%; H, 4.95%. Anal. Calcd.: C, 58.76%; N. 4.03%; H,

4.93%.

(E)-N-Acetyl/Thioacetyl–4-(2-(4-chlorophenyl)ethenyl)benzenesulfonamide(7g-h)

7g: Yield: 90%, mp ~ 170 ˚C; C16H14ClNO3S; MW: 335.4. IR (KBr,cm-1) νmax: 1643.1 (C=C).

1H-NMR (400 MHz, CDCl3): δ 2.62 (s,3H,-CH3); 7.40-7.48 (m, 4H, 4-chlorophenyl hydrogens);

7.67-7.71 (m, 4H, acetylsulfonamidophenyl hydrogens); 7.98 (d, 1H, Ha); 8.19 (d, 1H, Hb); 10.09

(-NH). 13C-NMR (100 MHz, CDCl3): δ 25.6 (CH3); 119.7, 124.1(Olefinic carbons); 125.6, 127.9,

130.9, 131.7, 134.7, 150.1, 150.9, 153.3 (Aromatic carbons); 209.4 (C=O). Elem. Anal. for (E)-

N-Acetyl–4-(2-(4-chlorophenyl)ethenyl) benzenesulfonamide: C, 57.20%; N, 4.20%; H, 4.21%.

Anal. Calcd.: C, 57.23%; N. 4.17%; H, 4.20%.

7h: Yield: 85%; 1H-NMR (400 MHz, CDCl3): δ 2.81 (s, 3H,-CH3); 7.55-7.75 (m, 4H, 4-

chlorophenyl hydrogens); 7.85-8.00 (m, 4H, acetylsulfonamidophenyl hydrogens); 8.15 (d, 1H,

Ha); 8.27 (d, 1H, Hb). 13C-NMR (100 MHz, CDCl3): δ 27.1 (CH3); 123.5, 126.8(Olefinic

(C=S). Elem. Anal. for (E)-N-Thioacetyl–4-(2-(chlorophenyl)ethenyl) benzenesulfonamide: C,

54.58%; N, 4.04%; H, 4.05%. Anal. Calcd.: C, 54.61%; N. 3.98%; H, 4.01%.

(E)-N-Acetyl/Thioacetyl–4-(2-(fluorophenyl)ethenyl)benzenesulfonamide (7i-j)

7i: Yield: 72%; 1H-NMR (400 MHz, CDCl3): δ 2.85 (s,3H,-CH3); 7.58-7.70 (m, 4H, 4-

(C=O). Elem. Anal. for (E)-N-Acetyl–4-(2-(fluorophenyl)ethenyl) benzenesulfonamide: C,

60.22%; N, 4.41%; H, 4.44%. Anal. Calcd.: C, 60.18%; N. 4.38%; H, 4.42%.

7j: Yield: 70%; 1H-NMR (400 MHz, CDCl3): δ 2.85 (s,3H,-CH3); 7.60-7.77 (m, 4H, 4-

(C=S). Elem. Anal. for (E)-N-Thioacetyl–4-(2-(fluorophenyl)ethenyl) benzenesulfonamide: C,

57.26%; N, 4.22%; H, 4.22%. Anal. Calcd.: C, 57.29%; N. 4.17%; H, 4.20%.

(E)-N- Thioacetyl–4-(2-(butyl)ethenyl)benzenesulfonamide (7l)

Yield: 75%, mp ~ 160 ˚C; C14H19NO3S; MW: 281.3. 1H-NMR (250 MHz, DMSO): δ 0.92 (t,

3H,-CH3); 1.55 (s, 3H, -CH3); 6.16 (d, 1H, Ha); 5.55 (m, 1H, Hb); 1.55 (m, 1H, Hc); 1.25-1.34 (m,

4H, Hd, He); 7.51-7.59 (m, 4H, phenyl hydrogens); 8.90 (-NH).

(E)-N-Acetyl/Thioacetyl–4-((2-methyl-2-methoxycarbonyl)ethenyl) benzenesulfonamide (7m-n)

7m: Yield: 70%, mp ~ 150 ˚C. C13H15NO5S; MW: 297.2. 1H-NMR (250 MHz, DMSO): δ 0.94 (d,

3H, -CH3); 1.25 (s, 3H, -CH3); 1.55 (s, 3H, -CH3 ); 7.40-7.55 (m, 4H, phenyl hydrogens); 1.00

(s, 1H, Ha).

7n: Yield: 65%, mp ~ 150 ˚C. C13H15NO4S2; MW: 313.3. IR (KBr,cm-1) νmax: 1730.4 (C=O);

1638.2 (C=C); 1149.3-1388.0 (S=O); 3443.8 (N-H).

Figure S 1: Infrared spectrum of 4-bromobenzenesulfonyl chloride

Figure S 2: 1H-NMR spectrum of 4-bromobenzenesulfonyl chloride

Figure S 3: 13C-NMR spectrum of 4-bromobenzenesulfonyl chloride

Figure S 4: Infrared spectrum of N-thioacetyl-4-bromobenzenesulfonamide

Figure S 5: 1H-NMR spectrum of N-thioacetyl-4-bromobenzenesulfonamide

Figure S 6: Expanded 1H-NMR spectrum of

N-thioacetyl-4-bromobenzenesulfonamide

Figure S 7: Infrared spectrum of N-acetyl-4-bromobenzenesulfonamide

Figure S 8: 1H-NMR spectrum of N-acetyl-4-bromobenzenesulfonamide

Figure S 9: 13C-NMR spectrum of N-acetyl-4-bromobenzenesulfonamide

Figure S 10: 1H-NMR spectrum of Compound 7b:

(E)-N-thioacetyl–4-(2-(phenyl)ethenyl)benzenesulfonamide

Figure S 11: Expanded 1H-NMR spectrum of Compound 7b:

(E)-N-thioacetyl–4-(2-(phenyl)ethenyl)benzenesulfonamide

Figure S 12: Infrared spectrum of Compound 7g:

(E)-N-acetyl–4-(2-(4-chlorophenyl)ethenyl)benzenesulfonamide

Figure S 13: 1H-NMR spectrum of compound 7g:

Figure S 14: 13C-NMR spectrum of compound 7g:

Figure S 15: 1H-NMR spectrum of compound 7c:

(E)-N-acetyl–4-(2-(methylphenyl)ethenyl)benzenesulfonamide

Figure S 16: 1H-NMR spectrum of compound 7d:

(E)-N-thioacetyl–4-(2-(methylphenyl)ethenyl)benzenesulfonamide

Figure S 17: 1H-NMR spectrum of compound 7e:

(E)-N-acetyl–4-(2-(methoxyphenyl)ethenyl)benzenesulfonamide

Figure S 18: Infrared spectrum of compound 7n:

(E)-N- thioacetyl–4-((2-methyl-2-methoxycarbonyl)ethenyl)benzenesulfonamide

s3-eu-west-1.amazonaws.com · Web viewTo a mixture of the synthesized acetyl/thioacetyl sulfonamide...

Documents

Antiproliferative Effects of CDK4/6 Inhibition in ...EGTA, 10% Glycerol, 1% Triton X-100, 100 mmol/L NaF, 10 mmol/L Na 4P 2O 7 10 H 2O, 1 mmol/L Na 3VO 4,and 1 Complete Protease Inhibitor

l i n i c al C Isa and Mohamed Clin Case Rep 21 :9 f C I ... · low triglyceride of 0.1 mmol/l, low LDL 0.95 mmol/l but normal HDL 1.3 mmol/l. Alanine aminotransferase was high (123

& (3) VO · 2017-02-22 · (15 -E) 15 x 2.5g 1.5g 0.75g 0.75g • 3.0g • o.5g MADE IN JAPAN -tzyar3 1.5g 1.5g • 3.0g CMC-Ca, 521CMC-Na, (±X) E0120-5884-01 10129867

VOYAGEUR MINERALS LTD · todays market place •Allows Voyageur access to all industrial markets. Lithium Chloride LiCl •LiCl is converted into Li2CO3, Lithium Carbonate or into

69451 Weinheim, Germany - Wiley-VCH procedure for the reaction of alkenes with saccharin. In a glass tube, alkenes (1.2 mmol), saccharin (0.2 mmol), catalyst (0.02 mmol), Maleic anhydride

core.ac.uk · There is no statistically significant difference in changes of Mg concentration between 2 groups of patients mmol/l vs. mmol/l; p

ISSN: 1138-011X Scopus, EMBASE/Excerpta Medica, … · M. Cruz Hernández J. Moreno Hernando S. M. Pueschel ... dela, Research Director of ... (315 ± 123 mmol/mmol vs 245 ± 84 mmol/mmol),

LiCl-KCl−UCl Phase Diagram Studies...4 Alkali Chloride -UCl3Phase Diagrams LiCl-UCl3 NaCl-UCl3 KCl-UCl 3 RbCl-UCl3 CsCl-UCl3 With increasing alkali metal cation size, the stability

1 · Web viewTo a mixture of NH-containing heterocycles (1.0 mmol), K 2 CO 3 (1.0 mmol), CuCl catalyst (0.2 mmol), and 8mL DMSO, arenediazonium tetrafluoroborates (1.2 mmol) was added

THÔNG S˜ K˚ THU˛T/ SPECIFICATION 1.5G CVT 1.5E CVT 1.5E … Catalogue-2018.pdf · thay ĐỔi ĐỂ bỨt phÁ sedan chuẨn mỰc mỚi thÔng s˜ k˚ thu˛t/ specification 1.5g

添付バッファー Restriction Enzymes - NIPPON GENE...Restriction Enzymes 添付バッファー 10 × L Buffer 100 mmol/l Tris-HCl （pH 7.9） 100 mmol/l MgCl2 10 mmol/l DTT 10

static-content.springer.com10.1007... · Web view(20 mmol) and triethylamine (20 mmol) in dichloromethane (50 ml) was slowly added to a solution of anhydride 1a-d(20 mmol) in dichloromethane

POLYALKYLENEIMINES, THEIR DERIVATIVES AND ...18134678/...later, at the end of the reaction (method B). In all cases were used 10 mmol of DAP, 9.5 mmol of DBP and 1 mmol of MPEGI. Variation

Supporting Information · 10 1.2 KOH18(0.3) Ni(COD)2 (3) 94 92 2 General reaction conditions: General Procedure, 0.6-1 mmol of 1a, 0.5 mmol of 2a’, 0.005-0.025 mmol Ni(COD)2, 0.025-0.25

Supporting Information · 2012-09-20 · mmol), potassium iodide (181 mg, 1.09 mmol) and 18-crown-6 (288 mg, 1.09 mmol). The mixture was degassed with Ar three times and was put into

NCP ( mmol O 2 m -2 d -1 )

pH : 7,46 (air ambiant) PaCO 2 : 36 mm Hg CO 2 T : 23 mmol/l PaO 2 : 56 mm Hg Sat : 88 % Na + : 144 mmol/l K + : 4,2 mmol/l Cl - : 103 mmol/l CO 2 T :

140 mmol/L de sódio versos 77 mmol/L de sódio na terapia flúida de manutenção para crianças no Hospital: ensaio randomizado, controlado e cego 140 mmol/L

WaveSense JAZZ Wireless Owner's Guide mmol/L

LiCl-KCl−UCl Phase Diagram Studies - ne.anl.gov · rate for 46.6 mol% LiCl in KCl (duplicate experiments) Results: LiCl-KCl and LiCl-UCl Binary Systems LiCl-KCl results consistent