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3-[(Phenylsulfonyl)methyl]aniline hydrochloride
 
 
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3-[(Benzylsulfonyl)methyl]aniline hydrochloride

Department of Chemistry, MS 6400, One University Plaza, Southeast Missouri State University, Cape Girardeau, MO, USA
*
Author to whom correspondence should be addressed.
Molbank 2006, 2006(5), M503; https://doi.org/10.3390/M503
Submission received: 6 July 2006 / Accepted: 1 August 2006 / Published: 1 September 2006

Keywords:
nitro; amine; reduction

In the course of our work to prepare inhibitors of the enzyme dihydrofolate reductase, we desired to prepare sulfone analogues of some similar sulfides [1,2]. The previously reported nitrosulfone [3] was not able to be reduced to the amine by using catalytic hydrogenation with a palladium on carbon catalyst, with tin and hydrochloric acid [4], or with iron and acetic acid in ethanol [5]. Therefore, the nitrosulfone, 1, was converted into the acetamide, 2, using iron in acetic acid [5]. The acetamide, 2, was hydrolyzed to the desired aniline, 3, using concentrated hydrochloric acid and ethanol. Unfortunately for us, the aniline was not able to be converted into the desired triazine by the reported procedure [2].
Molbank 2006 m503 i001
In round bottom flask 1-nitro-3-[(benzylsulfonyl)methyl]benzene, 1 (1.504 g, 5.162 mmoles), iron filings (2.017 g, 36.12 mmoles), and 75 mL of concentrated acetic acid were combined and refluxed for 4 hours. After allowing the reaction to cool, 150 mL of water was added. However, the product of the reaction became insoluble. Therefore, 90 mL dichloromethane was added. The reaction mixture was then filtered to remove unreacted iron. The organic and aqueous layers were separated. The aqueous layer was extracted two more times with dichloromethane. The organic extracts were combined and dried with anhydrous magnesium sulfate. The dichloromethane was removed with the rotavap to yield 1.439 g (4.74 mmoles) of 3-[(benzylsulfonyl)methyl]acetanilide, 2. The percent yield for the reaction was 92%.
Melting Point: 180-182oC
IR (cm-1): 3248, 1655, 1541, 1443, 1296, 1284, 1116, 785, 719, 693.
1H-NMR (300 MHz, DMSO-d6): δ= 10.0 (1H, singlet), 7.6 (2H, multiplet), 7.4 (5H, multiplet), 7.3 (1H, triplet, J = 7.7 Hz), 7.0 (1H, doublet, J = 7.7 Hz), 4.5 (2H, singlet), 4.4 (2H, singlet), 2.0 (3H, singlet).
13C-NMR (75 MHz, DMSO-d6): δ= 168.9, 139.9, 131.7, 129.3, 129.0, 128.90, 128.87, 128.6, 126.3, 122.0, 119.4, 58.0, 57.9, 24.5.
GC-MS [E.I., m/z (relative intensity)]: 148 (100), 106 (92), 91 (70), 239 (58), 197 (52), 77 (28), 79 (21), 196 (16), 303 (M+, 8).
In a round bottom flask 3-[(benzylsulfonyl)methyl)acetanilide, 2 (1.372 g, 4.52 mmoles), 8 mL of 95% ethanol, and 2 mL of concentrated hydrochloric acid were combined and refluxed for 4.5 hours. The amide dissolved in the hot ethanol forming a yellow solution. After about 1 hour, a precipitate began to form. The reaction mixture was allowed to cool, and the precipitate was collected by vacuum filtration. The precipitate was washed with three portions of cold 95% ethanol to yield 1.113 g (3.92 mmoles) of 3-[(benzylsulfonyl)methyl]aniline hydrochloride, 3, was collected. The percent yield of the reaction was 87%.
Melting Point: 225 oC (decomposed)
IR (cm-1): 2881 (br), 1536, 1519, 1311, 1291, 1276, 1135, 1120, 761, 724, 709, 690, 683.
1H-NMR (300 MHz, DMSO-d6): δ= 7.5 – 7.2 (9H, multiplet), 4.55 (2H, singlet), 4.50 (2H, singlet), 3.7 (3H, broad singlet).
13C-NMR (75 MHz, DMSO-d6): δ= 132.7, 131.2, 130.3, 129.8, 129.7, 128.5, 128.4, 127.9, 125.2, 122.9, 57.7, 56.9.
GC-MS [E.I., m/z (relative intensity), free base]: 106 (100), 261 (M+, 56), 197 (48), 91 (16), 79 (12), 77(12).

Supplementary Materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgment

The authors thank the Grants and Research Funding Committee of Southeast Missouri State University for financial support.

References

  1. Selassie, C. D.; Guo, Z.-r.; Hansch, C.; Khwaja, T. A.; Pentacost, S. A Comparison of the Inhibition of Growth of Methotrexate-Resistant and -Sensitive Leukemia Cells in Culture by Triazines. Evidence of a New Mechanism of Cell Resistance to Methotrexate. J. Med. Chem. 1982, 25, 157–161. [Google Scholar] [CrossRef] [PubMed]
  2. Hansch, C.; Hathaway, B. A.; Guo, Z.-r.; Selassie, C. D.; Dietrich, S. W.; Blaney, J. M.; Langridge, R.; Volz, K. W.; Kaufman, B. T. Crystallography, QSAR, and Molecular Graphics in a Comparative Analysis of the Inhibition of Dihydrofolate Reductase from Chicken Liver and L. casei by 4,6-Diamino- 1,2-dihydro-2,2-dimethyl-1-(x-phenyl)-s-triazines. J. Med. Chem. 1984, 27, 129–143. [Google Scholar] [CrossRef] [PubMed]
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  5. Owsley, D. C.; Bloomfield, J. J. The Reduction of Nitroarenes with Iron/Acetic Acid. Synthesis 1977, 118–120. [Google Scholar] [CrossRef]

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MDPI and ACS Style

Grohmann, D.G.; Hathaway, B.A. 3-[(Benzylsulfonyl)methyl]aniline hydrochloride. Molbank 2006, 2006, M503. https://doi.org/10.3390/M503

AMA Style

Grohmann DG, Hathaway BA. 3-[(Benzylsulfonyl)methyl]aniline hydrochloride. Molbank. 2006; 2006(5):M503. https://doi.org/10.3390/M503

Chicago/Turabian Style

Grohmann, Daniel G., and Bruce A. Hathaway. 2006. "3-[(Benzylsulfonyl)methyl]aniline hydrochloride" Molbank 2006, no. 5: M503. https://doi.org/10.3390/M503

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