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ppm: 3.99 d.d.d (1H, OCH2, J = 5.6, 9.8, 1.4 Hz),
4.10 m (1H, CHOH, J = 2.6, 5.6 Hz), 4.16 d.d (1H,
OCH2, J = 2.6, 9.8 Hz), 4.47 br.s (2H, OH), 6.89–
6.92 m (3H, o-H, p-H), 7.23–7.28 m (2H, m-H).
13C NMR spectrum (DMSO-d6), δC, ppm: 70.9 (CHO),
71.9 (CH2O), 115.4 (Co), 121.3 (Cp), 130.3 (Cm), 159.6
(Ci), 174.3 (COOH). Found, %: C 59.58; H 5.32.
C9H10O4. Calculated, %: C 59.34; H 5.53.
ppm: 56.7 (CH3), 71.3 (CHO), 72.9 (CH2O), 114.0
(C3′), 116.1 (C6′), 122.3 (C4′), 123.2 (C5′), 149.6 (C1′),
151.1 (C2′), 175.0 (COOH). Found, %: C 56.73;
H 5.54. C10H12O5. Calculated, %: C 56.60; H 5.70.
(S)-2-Hydroxy-3-(2-methoxyphenoxy)propanoic
acid (S)-(Ic). Yield 74%, mp 70–72°C, Rf 0.19, [α]D20 =
+16.9 (c = 0.9, MeOH); ee 99.8% [methyl ester;
HPLC, Chiralcel OD, eluent A; tmaj 7.8, tmin 22.9 min].
IR spectrum, ν, cm–1: 3485, 3403, 3263 (OH), 2938–
2551 (COOH), 1739, 1715 (C=O), 1593 (C=Carom).
1H NMR spectrum (CDCl3), δ, ppm: 3.86 s (3H, CH3),
4.29 d.d (1H, OCH2, J = 4.0, 10.1 Hz), 4.36 d.d (1H,
OCH2, J = 4.8, 10.1 Hz), 4.54 d.d (1H, CHOH, J = 4.0,
4.8 Hz), 6.60 br.s (2H, OH), 6.88– 6.94 m (2H, Harom),
6.95–7.02 m (2H, Harom). Found, %: C 55.96; H 5.78.
C10H12O5. Calculated, %: C 56.60; H 5.70.
(S)-2-Hydroxy-3-phenoxypropanoic acid (S)-(Ia).
Yield 80%, mp 132–134°C, Rf 0.26, [α]D20 = +25.6 (c =
1.2, MeOH); ee 99.7% [methyl ester; HPLC, Chiralcel
OD, eluent A; tmaj 6.0, tmin 12.0 min]. IR spectrum, ν,
cm–1: 3524 (OH), 2964–2506 (COOH), 1737, 1707
1
(C=O), 1595 (C=Carom). H NMR spectrum (CD3OD),
δ, ppm: 4.16 d.d (1H, OCH2, J = 5.6, 9.8 Hz), 4.26 d.d
(1H, OCH2, J = 2.6, 9.8 Hz), 4.38 d.d (1H, CHOH, J =
2.6, 5.6 Hz), 6.86–6.98 m (3H, Harom), 7.26–7.29 m
(2H, Harom). Found, %: C 59.19; H 5.43. C9H10O4. Cal-
culated, %: C 59.34; H 5.53.
rac-3-(2-Chlorophenoxy)-2-hydroxypropanoic
acid (rac-Id). Yield 74%, mp 136–137°C (from
EtOAc), Rf 0.28. IR spectrum, ν, cm–1: 3385 (OH),
2968–2572 (COOH), 1763, 1721 (C=O), 1590
rac-2-Hydroxy-3-(2-methylphenoxy)propanoic
acid (rac-Ib). Yield 75%, mp 153–154°C (first from
H2O and then from CH2Cl2); published data [11]:
mp 146–146.5°C; Rf 0.33. IR spectrum, ν, cm–1: 3423
(OH), 2943–2645 (COOH), 1725 (C=O), 1602, 1590
1
(C=Carom). H NMR spectrum (CD3OD), δ, ppm:
4.30 d.d (1H, OCH2, J = 5.0, 10.0 Hz), 4.36 d.d (1H,
OCH2, J = 3.1, 10.0 Hz), 4.55 d.d (1H, CHOH, J = 3.1,
5.0 Hz), 6.95 d.d.d (1H, 4′-H, J = 1.3, 7.9, 9.0 Hz),
7.11 d.d (1H, 6′-H, J = 1.3, 8.2 Hz), 7.26 d.d.d (1H,
5′-H, J = 1.6, 8.2, 9.0 Hz), 7.36 d.d (1H, 3′-H, J = 1.6,
7.9 Hz). 13C NMR spectrum (CD3OD), δC, ppm: 70.7
(CHO), 72.0 (CH2O), 114.4 (C6′), 121.5 (C4′), 122.9
(C2′), 127.6 (C5′), 129.8 (C3′), 154.6 (C1′), 175.0
(COOH). Found, %: C 49.68; H 4.38. C9H9ClO4. Cal-
culated, %: C 49.90; H 4.19.
1
(C=Carom). H NMR spectrum (DMSO-d6), δ, ppm:
2.13 s (3H, CH3), 4.04 d.d (1H, OCH2, J = 5.4,
9.9 Hz), 4.16 d.d (1H, OCH2, J = 3.2, 9.9 Hz), 4.21 d.d
(1H, CHOH, J = 3.2, 5.4 Hz), 5.35 br.s (2H, OH),
6.82 t (1H, 5′-H, J = 7.3 Hz), 6.89 d (1H, 6′-H, J =
8.2 Hz), 7.09–7.13 m (2H, 3′-H, 4′-H). 13C NMR spec-
trum (DMSO-d6), δC, ppm: 15.8 (CH3), 69.8 (CHO),
70.9 (CH2O), 111.6 (C6′), 120.2 (C4′), 126.0 (C2′),
126.8 (C5′), 130.3 (C3′), 156.7 (C1′), 173.5 (COOH).
Found, %: C 60.91; H 5.96. C10H12O4. Calculated, %:
C 61.22; H 6.16.
(S)-3-(2-Chlorophenoxy)-2-hydroxypropanoic
acid (S)-(Id). Yield 75%, mp 135–137°C, Rf 0.29,
[α]D20 = +14.6 (c = 1, MeOH); ee 99.8% [methyl ester;
HPLC, Chiralcel OD, eluent A; tmaj 6.5, tmin 9.0 min].
IR spectrum, ν, cm–1: 3363 (OH), 2984–2553 (COOH),
1705 (C=O), 1588 (C=Carom). The NMR spectra
were identical to those given above for rac-Id. Found,
%: C 49.61; H 3.71. C9H9ClO4. Calculated, %:
C 49.90; H 4.19.
(S)-2-Hydroxy-3-(2-methylphenoxy)propanoic
acid (S)-(Ib). Yield 74%, mp 122–124°C, Rf 0.34,
[α]D20 = +26.8 (c = 0.7, MeOH); ee 99.8% [methyl
ester; HPLC, Chiralcel OD, eluent A; tmaj 6.9,
tmin 11.2 min]. IR spectrum, ν, cm–1: 3566, 3478, 3333
(OH), 2926–2592 (COOH), 1735, 1715 (C=O), 1602,
1590 (C=Carom). The NMR spectra were identical to
those given above for acid rac-Ib. Found, %: C 61.15;
H 6.10. C10H12O4. Calculated, %: C 61.22; H 6.16.
rac-3-(2-Bromophenoxy)-2-hydroxypropanoic
acid (rac-Ie). Yield 76%, mp 147–149°C (from
hexane–EtOAc), Rf 0.32. IR spectrum, ν, cm–1: 3422
(OH), 2963–2583 (COOH), 1726 (C=O), 1584
rac-2-Hydroxy-3-(2-methoxyphenoxy)propanoic
acid (rac-Ic). Yield 74%, mp 98–100°C, Rf 0.19.
IR spectrum, ν, cm–1: 3419 (OH), 2933–2551 (COOH),
1
(C=Carom). H NMR spectrum (CD3OD), δ, ppm:
4.27 d.d (1H, OCH2, J = 4.7, 9.9 Hz), 4.32 d.d (1H,
OCH2, J = 3.6, 9.9 Hz), 4.56 d.d (1H, CHOH, J = 3.6,
4.7 Hz), 6.86 d.d.d (1H, 4′-H, J = 1.1, 7.9, 8.1 Hz),
7.03 d.d (1H, 6′-H, J = 1.1, 8.2 Hz), 7.28 d.d.d (1H,
5′-H, J = 1.4, 8.1, 8.2 Hz), 7.50 d.d (1H, 3′-H, J = 1.4,
1
1723 (C=O), 1588 (C=Carom). H NMR spectrum
(CD3OD), δ, ppm: 3.85 s (3H, CH3), 4.11–4.17 m (1H,
CH2O), 4.24–4.31 m (2H, CHOH, CH2O), 6.85–
7.02 m (4H, Harom). 13C NMR spectrum (CD3OD), δC,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014