MAGNETIC RESONANCE IN CHEMISTRY
Magn. Reson. Chem. 2000; 38: 384–385
Reference Data
aniline (0.1 mol) and glacial acetic acid (83 ml). The contents of the reac-
tion vessel were then heated at 45–50 °C for 2 h, then cooled and poured
into a solution of aqueous sodium acetate (16.6 g in 340 ml of water).
The crystals obtained were filtered off, washed with cold water and
recrystallized from ethanol. The yields were 55–87%. Melting points
of the products were consistent with those reported earlier.2
a-Phenylsulfonyl-N-arylacetamides
1
(a-phenylsulfonylacetanilides): H,13C and 15N NMR
spectral characterization
1
2
∗
Erkki Kolehmainen, Henryk Janota,
˛-Phenylsulfonylacetanilides, RC6H4NHCOCH2SO2C6H5, where
R D H (1), 3-OCH3 (2), 4-NO2 (3), 3-NO2 (4), 4-CH3 (5), 4-Cl (6), 4-Br
(7), 4-I (8), 4-NHCOCH3 (9), 4-OCH3 (10) and 4-N(CH /2 (11), were
prepared according to the following procedure. A soluti3on of sodium
benzenesulfinate (0.011 mol), ˛-chloroacetanilide (0.01 mol) and tetra-
butylammonium bromide (0.5 mmol, catalyst) in 1,2-dimethoxyethane
(80 ml) was refluxed for 4 h. The cold reaction mixture was then poured
into cold water. The crystals obtained were filtered off, washed with
water and recrystallized from ethanol. The yields were 45–77%. Melt-
ing points of the known products [R D H (1), 4-NO2 (3) 4-Cl (6) and
4-OCH3 (10)] are consistent with those reported earlier.3 Melting points
are uncorrected. Satisfactory elemental analytical data (š0.3% for C,
H, N and S) were obtained for all new compounds. Melting points of
the new products were 3-OCH3 (2) 131–132 3-NO2 (4) 177–179, 4-
CH3 (5) 145–148, 4-Br (7) 164–166, 4-I (8) 170–173, 4-NHCOCH3
(9) 215–218 and 4-N(CH3/2 (11) 159–161 °C).
Ryszard Gawinecki,2 Katri Laihia1 and
Reijo Kauppinen1
1
Department of Chemistry, University of Jyva¨skyla¨, P.O. Box 35,
FIN-40351 Jyva¨skyla¨, Finland
2
Department of Chemistry, Technical and Agricultural
University, Seminaryjna 3, PL-85-326 Bydgoszcz, Poland
Received 15 November 1999; accepted 6 December 1999
ABSTRACT: 1H and 13C NMR chemical shift assignments for 11
˛-phenylsulfonylacetanilides and 15N NMR chemical shifts for four
representative congeners are reported. The 1H and 13C chemical shift
assignments are based on DQF COSY and PFG H,13C HMQC/HMBC
1
experiments. The 15N NMR chemical shifts were determined by PFG
1H,15N HMBC experiments. The correlation analyses with Hammett-
type substituent constants gave a significant result with υ(C-1) in the
aniline ring. Copyright 2000 John Wiley & Sons, Ltd.
Spectra
All NMR experiments were performed on 0.1 M CDCl3 solutions at
30 °C (unless stated otherwise) with a Bruker Avance DRX 500 spec-
trometer equipped with a 5 mm diameter inverse detection broadband
probe head and z-gradient accessory working at 500.132 MHz for 1H,
125.758 MHz for 13C and 50.688 MHz for 15N. In 1H NMR experiments
the spectral width was 5200 Hz, number of data points 65K and num-
ber of scans eight. The FIDs were exponentially windowed by a line
broadening factor of the digital resolution (0.08 Hz) prior to Fourier
KEYWORDS: NMR; 1H NMR; 13C NMR; 15N NMR; ˛-phenylsulfonyl-
acetanilides
INTRODUCTION
1
transformation (FT). The H NMR chemical shifts are referenced to the
signal of the internal 2% TMS .υ D 0.00 ppm/. In 13C NMR experi-
ments the spectral width was 32 700 Hz, number of data points 65K and
number of scans 400. The FIDs were exponentially windowed by a line
broadening factor of the digital resolution (0.5 Hz) prior to FT. The 13C
NMR chemical shifts are referenced to the signal of the internal 2%
TMS .υ D 0.00 ppm/.
˛-Phenylsulfonylacetanilides, RC6H4NHCOCH2SO2C6H5 are used as
herbicides and have antibacterial and fungicidal properties.1 With regard
to their structural and electronic properties, there are two basic questions
to be answered: (i) how easily the ring substituent effects from the
aniline moiety are transmitted to the other parts of the molecule
and (ii) whether there are any keto–enol or amino–imino tautomeric
equilibria present, which both in principle are possible. Therefore, a
systematic NMR investigation of ˛-phenylsulfonylacetanilides and the
determination of their spectral parameters are of great importance. To
our knowledge, these data have not been reported previously.
In DQF 1H,1H COSY4 experiments, the spectral range was limited
only in the aromatic part with 550 Hz/128 points (along the t1 axis)
and 550 Hz/256 points (along the t2 axis). The time domain along the t1
axis was zero filled to 256 points and shifted sine-bell window functions
along both axes were used prior to FT.
In PFG 1H,13C HMQC5 experiments, the spectral ranges were
1
2600 Hz/1024 points (along the t2 D H axis) and 13 125 Hz/512 points
(along the t1
D
13C axis). Eight scans were accumulated for every t1
increment and GARP composite pulse decoupling was used to remove
nJ(H,C)s. The time domain along the t1 axis was zero filled to 1024
points and sine-bell weighting functions along both axes were used prior
to FT. In PFG H,13C HMBC experiments, the acquisition and process-
1
ing parameters were the same as in HMQC but the number of scans
was 64 and a 50 ms delay was implemented in the pulse sequence for
evolution of the long-range couplings. A low-pass filter was used to
remove the correlations transmitted by 1J(1H,13C)s.
EXPERIMENTAL
Compounds
In PFG 1H,15N HMBC6 experiments, the spectral range and the
1
number of data points along the t2 D H axis were the same as above.
Along the t1 D 15N axis the spectral range was 22 500 Hz (450 ppm)/512
points which was zero filled to 1024 prior to FT. Again 64 scans were
accumulated for every t1 increment and a 50 ms delay was used for
evolution of nJ(1H,15N/ couplings. Shifted sine-bell window functions
were used along both axes prior to FT. The 15N NMR chemical shifts
were referenced to the signal of an external neat CH3NO2 sample
in a 1 mm diameter capillary tube inserted coaxially inside the 5 mm
diameter NMR tube.
There are three known methods for synthesizing ˛-phenylsulfonylacet-
anilides: (i) condensation of arylsulfonylacetyl chlorides with aromatic
amines,1a (ii) condensation of sodium arenesulfinates with ˛-chloroace-
tanilides1b and (iii) condensation of arenesulfinic acids with ˛-chloroace-
tylacetanilides.1c A modification of method (ii) was used in this
work. The ˛-chloroacetanilides, RC6H4NHCOCH2Cl [R
D
H, 3-
OCH3, 4-NO2, 3-NO2, 4-CH3, 4-Cl, 4-Br, 4-I, 4-NHCOCH3, 4-OCH3,
4-N.CH3/2] used as starting materials were obtained by addition of
chloroacetyl chloride (8 ml, 11.3 g, 0.1 mol) to the stirred mixture of
RESULTS AND DISCUSSION
* Correspondence to: E. Kolehmainen, Department of Chemistry, University of
The 1H,13C and 15N NMR chemical shifts of the ˛-(phenylsulfonyl)ace-
Jyva¨skyla¨, P.O. Box 35, FIN-40351 Jyva¨skyla¨, Finland; e-mail: ekolehma@cc.jyu.fi
tanilides are given in Tables 1–3. The correlation analyses of the
Copyright 2000 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2000; 38: 384–385
Kolehmainen, Erkki
