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Keywords:

  • conductometric studies;
  • kinetic measurements;
  • linear free energy relationship;
  • nucleophilic substitution;
  • phenacyl bromide derivatives;
  • reaction mechanism;
  • substituent effects;
  • transition state

The reaction of the substituted phenacyl bromides 1a–e and 2a–e with thioglycolic acid 3 and thiophenol 6 in methanol underwent nucleophilic substitution SN2 mechanism to give the corresponding 2-sulfanylacetic acid derivatives 4a–e, 5a–e and benzenethiol derivatives 9a–e, 10a–e. The reactants and products were identified by mass spectra, infrared and nuclear magnetic resonance. We measured the kinetics of these reactions conductometrically in methanol at a range of temperatures. The rates of the reactions were found to fit the Hammett equation and correlated with σ-Hammett values. The ρ values for thioglycolic acid were 1.22–1.21 in the case of 4-substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.39–0.35. The ρ values for thiophenol were 0.97–0.83 in the case of 4-substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.79–0.74. The Brønsted-type plot was linear with a α = −0.41 ± 0.03. The kinetic data and structure-reactivity relationships indicate that the reaction of 1a–e and 2a–e with thiol nucleophiles proceeds by a concerted mechanism. The plot of log k45 versus log k30, the plot log(kx,3-NO2/kH) versus log(kx/kH), and the Brønsted-type correlation indicate that the reactions of the thiol nucleophiles with the substituted phenacyl bromides 1a–e and 2a–e are attributed to the electronic nature of the substituents. Copyright © 2011 John Wiley & Sons, Ltd.

Featured Compounds

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  1. 1 - 36
Compound 3
Molecular Weight:92.117
Molecular Formula:C2H4O2S
InChIKey:CWERGRDVMFNCDR-UHFFFAOYSA-N
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Compound 4a
Molecular Weight:210.25
Molecular Formula:C10H10O3S
InChIKey:NNNVHZPLMZHPBQ-UHFFFAOYSA-N
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Compound 4b
Molecular Weight:289.146
Molecular Formula:C10H9BrO3S
InChIKey:UXTMAKHYTCABON-UHFFFAOYSA-N
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Compound 4c
Molecular Weight:244.695
Molecular Formula:C10H9ClO3S
InChIKey:JIYHIZUYCBNBNM-UHFFFAOYSA-N
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Compound 4d
Molecular Weight:224.276
Molecular Formula:C11H12O3S
InChIKey:GOWUDQFRVNFWSI-UHFFFAOYSA-N
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Compound 4e
Molecular Weight:240.276
Molecular Formula:C11H12O4S
InChIKey:NECONRMPZRBPOP-UHFFFAOYSA-N
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Compound 5a
Molecular Weight:255.247
Molecular Formula:C10H9NO5S
InChIKey:NQGQENYUQHYEND-UHFFFAOYSA-N
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Compound 5b
Molecular Weight:334.143
Molecular Formula:C10H8BrNO5S
InChIKey:DNHQHLHHNRFBID-UHFFFAOYSA-N
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Compound 5c
Molecular Weight:289.692
Molecular Formula:C10H8ClNO5S
InChIKey:JHEFCQPOKCBULJ-UHFFFAOYSA-N
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Compound 5d
Molecular Weight:269.274
Molecular Formula:C11H11NO5S
InChIKey:YMQJBZVCWKNMKB-UHFFFAOYSA-N
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Compound 5e
Molecular Weight:285.273
Molecular Formula:C11H11NO6S
InChIKey:BHWUHRKIPSRRFF-UHFFFAOYSA-N
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Compound 1a
Molecular Weight:199.045
Molecular Formula:C8H7BrO
InChIKey:LIGACIXOYTUXAW-UHFFFAOYSA-N
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Compound 1b
Molecular Weight:277.941
Molecular Formula:C8H6Br2O
InChIKey:FKJSFKCZZIXQIP-UHFFFAOYSA-N
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Compound 1c
Molecular Weight:233.49
Molecular Formula:C8H6BrClO
InChIKey:FLAYZKKEOIAALB-UHFFFAOYSA-N
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Compound 1d
Molecular Weight:213.071
Molecular Formula:C9H9BrO
InChIKey:KRVGXFREOJHJAX-UHFFFAOYSA-N
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Compound 1e
Molecular Weight:229.071
Molecular Formula:C9H9BrO2
InChIKey:XQJAHBHCLXUGEP-UHFFFAOYSA-N
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Compound 2a
Molecular Weight:244.042
Molecular Formula:C8H6BrNO3
InChIKey:GZHPNIQBPGUSSX-UHFFFAOYSA-N
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Compound 2b
Molecular Weight:322.938
Molecular Formula:C8H5Br2NO3
InChIKey:WMSIUGXDLWVWIG-UHFFFAOYSA-N
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Compound 2c
Molecular Weight:278.487
Molecular Formula:C8H5BrClNO3
InChIKey:FXNQTMRPLLNPQY-UHFFFAOYSA-N
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Compound 2d
Molecular Weight:258.069
Molecular Formula:C9H8BrNO3
InChIKey:DBMCVOBHUPAOMT-UHFFFAOYSA-N
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Compound 2e
Molecular Weight:274.068
Molecular Formula:C9H8BrNO4
InChIKey:CVPDMBUSCIDXCM-UHFFFAOYSA-N
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Compound 9a
Molecular Weight:228.309
Molecular Formula:C14H12OS
InChIKey:MRLUWCIEBHJONW-UHFFFAOYSA-N
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Compound 9b
Molecular Weight:307.206
Molecular Formula:C14H11BrOS
InChIKey:TVCNXZGMRAWXRL-UHFFFAOYSA-N
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Compound 9c
Molecular Weight:262.755
Molecular Formula:C14H11ClOS
InChIKey:VTVZUQKWCBSTIX-UHFFFAOYSA-N
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Compound 9d
Molecular Weight:242.336
Molecular Formula:C15H14OS
InChIKey:YHOCTMWVBSFOPY-UHFFFAOYSA-N
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Compound 9e
Molecular Weight:258.335
Molecular Formula:C15H14O2S
InChIKey:FCPGMIDFJVGKPQ-UHFFFAOYSA-N
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Compound 10a
Molecular Weight:273.307
Molecular Formula:C14H11NO3S
InChIKey:AKVORDXUPYCYEI-UHFFFAOYSA-N
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Compound 10b
Molecular Weight:352.203
Molecular Formula:C14H10BrNO3S
InChIKey:VBLFBEQFRQIPFC-UHFFFAOYSA-N
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Compound 10c
Molecular Weight:307.752
Molecular Formula:C14H10ClNO3S
InChIKey:OCIOJDSYTOOKLW-UHFFFAOYSA-N
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Compound 10d
Molecular Weight:287.334
Molecular Formula:C15H13NO3S
InChIKey:CYJUWQMBRWCKSR-UHFFFAOYSA-N
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Compound 10e
Molecular Weight:303.333
Molecular Formula:C15H13NO4S
InChIKey:DECJBXHUMIRWKG-UHFFFAOYSA-N
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Compound 11
Molecular Weight:287.334
Molecular Formula:C15H13NO3S
InChIKey:SFDYWEZHWWQUHM-UHFFFAOYSA-N
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Compound 12
Molecular Weight:307.752
Molecular Formula:C14H10ClNO3S
InChIKey:XGKRIFDHMNKIDD-UHFFFAOYSA-N
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Compound 6
Molecular Weight:110.177
Molecular Formula:C6H6S
InChIKey:RMVRSNDYEFQCLF-UHFFFAOYSA-N
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Compound 7
Molecular Weight:124.203
Molecular Formula:C7H8S
InChIKey:WLHCBQAPPJAULW-UHFFFAOYSA-N
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Compound 8
Molecular Weight:144.622
Molecular Formula:C6H5ClS
InChIKey:VZXOZSQDJJNBRC-UHFFFAOYSA-N
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