6
Tetrahedron
Correlations between the initial reaction rate and the
GC/MS (m/z (%)): 122 ([M]+, 30), 107 (85), 79 (100), 78 (23),
77 (57), 51 (23), 50 (11), 44 (17),43 (39), 39 (10).
substituent constant (σ+) in the aromatic ring characterizing its
nature were established. We compared the ρ constants of
bioreduction catalyzed by D. carota and P. crispum and found
that the sensitivity of the reduction to the nature of the
substituents is more significant in the case of D. carota
biocatalyst.
4.2.2. S-1-(4-chlorophenyl)ethanol (2b)
1H NMR (300 MHz, CDCl3, ppm): δ=1.29 d (3H, CH3), 5.35 q
(1H, CH-O), 7.34 m (4H, 4СHAr). 13C NMR (75 MHz, CDCl3,
ppm): δ=26.14 (СH3), 67.86 (CH-OH), 127.59 (2СHAr), 128.33
(2СHAr), 131.35 (CAr-Cl), 146.63 (CAr). GC/MS (m/z (%)): 155
([M]+, 20), 143 (25), 141 (93), 139 (38), 113 ( 40), 77 (100), 75
(22), 51 (23), 44 (58), 43 (59).
Comparison of ρ constants for D. сarota and P. crispum in
water and isooctane shows that the sensitivity of bioreduction to
the nature of the substituent tends to increase from water to
isooctane.
4.2.3. S-1-(4-bromophenyl)ethanol (3b)
1H NMR (300 MHz, CDCl3, ppm): δ=1.29 d (3H, CH3), 4.69 q
(1H, CH-OH), 7.28 d (2H, 2CHAr), 7.46 d (2H, CHAr). 13C NMR
(75 MHz, CDCl3, ppm): δ=26.04 (CH3), 67.96 (CH-OH), 119.85
(2CHAr), 127.98 (2CHAr), 131.25 (CAr-Br), 146.98 (CAr). GC/MS
(m/z (%)): 202 ([M]+, 12), 186 (39), 184 (43), 156 (21), 121
(26), 78 (45), 77 (100), 51 (26), 50 (19), 43 (69).
4. Experimental
4.1. General information
Acetophenone,
para-nitro-,
methoxy-,
chloro-
and
4.2.4. S-1-(4-nitrophenyl)ethanol (4b)
bromoacetophenones were purchased from commercial sources.
1H NMR (300 MHz, CDCl3, ppm): δ=1.45 d (3H, CH3), 4.85 q
(1H, CH-OH), 7.6 d (2H, 2СHAr), 8.16 d (2H, 2СHAr). 13C NMR
(75 MHz, CDCl3, ppm): δ=25.96 (1C, СH3), 67.88 (1C, CH-OH),
123.67 (2СHAr), 126.81 (2СHAr), 146.6 (1C, CAr), 155.62 (CAr-
NO2). GC/MS (m/z (%)): 244 ([M+], 7), 150 (100), 134 (5), 120
(10), 104 (29), 92 (15), 89(9), 76 (18), 50 (16), 42 (8).
Racemic alcohols were prepared from the corresponding
ketones by reduction with NaBH4.
Fresh carrots (D. carota) and parsley (P. crispum) were
purchased from a local market.
Gas chromatographic analyses were performed on
Khromatek-crystall-5000.2 with flame-ionization detector.
Enantioselective
column
Astec
CHIRALDEXB-PM
4.2.5. S-1-(4-methoxyphenyl)ethanol (5b)
(30m×0.25mm×0.12ꢀm); column temperature 100°C (1b), 120°C
(2b, 5b), 130°C (3b),150°C (4b); oven temperature 250 °C,
detector temperature 250 °C; helium as a carrier gas, flow rate
14.2 mL/min. For more efficient chromatographic separation of
enantiomeric alcohols, its acetyl derivatives were obtained.
1H and 13C NMR spectra were measured on Bruker AM-300
and AMX-300 spectrometeres. As internal δ (0.00) for standards
served TMS 1H NMR and CDCl3 δ (77.0) for 13C NMR
spectroscopy.
1H NMR (300 MHz, CDCl3, ppm): δ=1.28 d (3H, CH3), 3.7 s
(3H, CH3-O), 4.65 q (1H, CH-OH), 6.85 d (2H, 2CHAr), 7.23 d
(2H, CHAr). 13C NMR (75 MHz, CDCl3, ppm): δ=26.27 (СH3),
55.37 (CH3-O), 68.11 (CH-OH), 113.73 (2СHAr), 126.86
(2СHAr), 139.69 (CAr), 158.36 (CAr-O). GC/MS (m/z (%)): 152
([M]+, 25), 137 (100), 134 (18), 109 (53), 94 (30), 91 (15), 77
(30), 65 (14), 44 (16), 43 (29).
Acknowledgement
GC-MS analyses were performed using GCMS-QP2010S
Shimadzu. A mass spectrometer with an ion trap detector in full
scan mode under electron impact ionization (70 eV) in the 35-
500 amu range was used. The chromatographic column used for
the analysis was an HP-1MS capillary column (30 m×0.25
mm×0.25 ꢀm). The vaporizer temperature was 280°C, the
ionization chamber temperature was 200°C. Helium was used as
carrier gas, at a flow rate of 1.1 mL/min. The injections were
performed in mode at 100 -230 °C at a heating rate of 20°C/min.
This study was funded by the Ministry of Education and
Science of Russian Federation (grant no. 4.6451.2017/8.9).
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4.2.1. S-1-phenylethanol (1b)
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1H NMR (300 MHz, CDCl3, ppm): δ=1.40 d (3H, CH3), 4.74 q
(1Н, СН), 7.20-7.28 m (5Н, СНАr). 13C NMR (75 MHz, CDCl3,
ppm): δ=25.18 (1C, CH3), 70.05 (1C, CH), 125.34 (2C, СНАr),
127.18 (1C, СНАr), 128.28 (2C, СНАr), 145.92 (1C, СНАr).