Synthesis of Unsaturated â-Hydroxy Acids
8.7 Hz, CHd), 5.03-4.94 (m, 3 H, CH2d, CHOH), 3.25 (dd, 1
H, J ) 8.7, 6.5 Hz, CH-COOH); 13C NMR (62.9 MHz, CDCl3)
δ 173.8, 145.9, 134.9, 127.6, 126.4, 122.4, 119.4, 71.7, 59.0.
An ti: white solid; mp 131 °C; 1H NMR (250 MHz, acetone-
d6) δ 7.33-7.05 (m, 3 H, Ar), 5.62 (ddd,1 H, J ) 17.2, 10.2, 8.8
Hz, CHd), 5.00-4.91 (m, 3 H, CH2d, CHOH), 3.33 (t, 1 H, J
) 8.8 Hz, CH-COOH); 13C NMR (62.9 MHz, CDCl3) δ 174.1,
145.6, 134.7, 127.6, 126.7, 123.1, 119.2, 72.1, 59.6; IR (KBr,
cm-1) 3500-2400 (OH), 1704 (CdO). MS (CI, NH3) m/z 217
(M + NH4+), 199 (M + H+). Anal. Calcd for C9H10O3S1: C,
54.53; H, 5.08. Found: C, 54.52; H, 5.09.
(m, 1 H, CH), 3.46-3.35 (m, 3 H, CH-COOH, CH2); 13C NMR
(62.9 MHz, acetone-d6) δ 199.0, 173.9, 143.8, 137.1, 134.1,
129.7, 129.1, 128.9, 127.7, 120.1, 58.4, 43.3; IR (KBr, cm-1
)
3500-2500 (OH), 1705 (CdO); MS (CI, NH3) m/z 312 (M +
NH4+), 295 (M + H+). Anal. Calcd for C19H18O3: C, 77.53; H,
6.16. Found: C, 77.49; H, 6.17.
2-(1-Hydr oxy-1-ph en ylm eth yl)-3-m eth ylbu t-3-en oic Acid
(2a ).8,23
1
Syn : white solid; mp 147 °C; H NMR (250 MHz, acetone-
d6) δ 7.47-7.25 (m, 5 H, Ph), 5.08 (d, 1 H, J ) 9.3 Hz, CHOH),
5.02-4.98 (m, 2 H, CH2d), 3.47 (d, 1 H, J ) 9.3 Hz,
CH-COOH), 1.94 (s, 3 H, Me); 13C NMR (62.9 MHz, acetone-
d6) δ 172.8, 144.3, 142.1, 128.7, 128.1, 127.8, 115.9, 73.6, 61.9,
20.9.
2-Vin yl-3-h yd r oxy-5-m eth ylh ex-4-en oic Acid (1g).
1
Syn : yellow solid; mp 87 °C; H NMR (250 MHz, CDCl3) δ
6.75 (s, 2 H, OH), 5.86 (dt, 1 H, J ) 17.1, 9.6 Hz, CHd), 5.28-
5.14 (m, 3 H, CH2d, CHdCMe2), 4.61 (dd, 1 H, J ) 8.9, 6.0
Hz, CHOH), 3.08 (dd 1 H, J ) 9.6, 6.0 Hz, CH-COOH), 1.67
(s, 3 H, Me), 1.63 (s, 3 H, Me); 13C NMR (62.9 MHz, CDCl3) δ
176.5, 136.9, 130.6, 122.3, 119.7, 68.2, 55.4, 24.9, 17.5.
An ti: yellow oil; 1H NMR (250 MHz, CDCl3) δ 5.75-5.61
(m, 1 H, CHd), 5.21-5.06 (m, 3 H, CH2d, CHdCMe2), 4.58 (t,
1 H, J ) 8.5 Hz, CHOH), 3.10 (t, 1 H, J ) 8.5 Hz, CH-COOH),
1.67 (s, 3 H, Me), 1.63 (s, 3 H, Me); 13C NMR (62.9 MHz, CDCl3)
δ 177.9, 138.1, 131.8, 124.2, 119.8, 69.4, 57.1, 25.9, 18.7; IR
(KBr, cm-1) 3500-2300 (OH), 1710 (CdO); MS (CI, NH3) m/z
188 (M + NH4+). Anal. Calcd for C9H14O3: C, 63.51; H, 8.29.
Found: C, 63.74; H, 8.27.
1
An ti: white solid; mp 132 °C; H NMR (250 MHz, acetone-
d6) δ 7.44-7.27 (m, 5 H, Ph), 5.07 (d, 1 H, J ) 9.9 Hz, CHOH),
4.88 (s, 1 H, CH2d), 4.76 (s, 1 H, CH2)), 3.44 (d, 1 H, J ) 9.9
Hz, CH-COOH), 1.56 (s, 3 H, Me); 13C NMR (62.9 MHz,
acetone-d6) δ 175.2, 144.0, 141.8, 129.1, 128.5, 128.2, 116.1,
75.6, 62.4, 22.4; IR (KBr, cm-1) 3500-2500 (OH), 1725 (Cd
O); MS (CI, NH3) m/z 224 (M + NH4+), 207 (M + H+). Anal.
Calcd for C12H14O3: C, 69.89; H, 6.84. Found: C, 69.88; H,
6.84.
2-(1-Hyd r oxy-2,2-d im eth ylp r op yl)-3-m eth ylbu t-3-en o-
ic Acid (2c).
1
Syn : white solid; mp 137 °C; H NMR (250 MHz, acetone-
2-(1-Hyd r oxy-2,2-d im eth ylp r op yl)bu t-3-en oic Acid (1i).
Syn : white solid; mp 99 °C; 1H NMR (250 MHz, acetone-d6)
δ 6.19 (ddd, 1H, J ) 17.2, 10.1, 8.7 Hz, CHd), 5.43 (d, 1 H, J
) 17.2 Hz, CH2d), 5.31 (d, 1 H, J ) 10.1 Hz, CH2d), 3.66 (d,
1 H, J ) 4.9 Hz, CHOH), 3.49 (dd, 1 H, J ) 8.7, 4.9 Hz, CH-
COOH), 1.13 (s, 9 H, Me); 13C NMR (62.9 MHz, acetone-d6) δ
175.1, 137.8, 117.9, 81.1, 53.4, 37.1, 27.1.
d6) δ 4.96-4.94 (m, 2 H, CH2d), 3.85 (d, 1 H, J ) 8.6 Hz,
CHOH), 3.29 (d, 1 H, J ) 8.6 Hz, CH-COOH), 1.88 (s, 3 H,
Me), 0.97 (s, 9 H, Me3C); 13C NMR (62.9 MHz, acetone-d6) δ
173.5, 142.8, 115.0, 76.4, 55.2, 35.6, 25.5, 20.4.
An ti: white solid; mp 124 °C; 1H NMR (250 MHz, acetone-
d6) δ 4.96-4.85 (m, 2 H, CH2d), 3.48 (d, 1 H, J ) 3.9 Hz,
CHOH), 3.23 (d, 1 H, J ) 3.9 Hz, CH-COOH), 1.79 (s, 3 H,
Me), 0.87 (s, 9 H, Me3C); 13C NMR (62.9 MHz, acetone-d6) δ
1
An ti: white solid; mp 86 °C; H NMR (250 MHz, acetone-
175.4, 144.0, 114.9, 79.6, 54.1, 37.2, 26.9, 22.2; IR (KBr, cm-1
)
d6) δ 6.06 (ddd, 1H, J ) 17.2, 10.1, 8.7 Hz, CHd), 5.33-5.15
(m, 2 H, CH2d), 3.78 (d, 1 H, J ) 4.9 Hz, CHOH), 3.35 (dd, 1
H, J ) 8.7, 4.9 Hz, CH-COOH), 0.98 (s, 9 H, Me); 13C NMR
(62.9 MHz, acetone-d6) δ 175.6, 136.2, 118.6, 78.8, 54.0, 36.9,
27.2. IR (KBr, cm-1) 3500-2400 (OH), 1705 (CdO); MS (CI,
NH3) m/z 190 (M + NH4+), 173 (M + H+). Anal. Calcd for
C9H16O3: C, 62.77; H, 9.36. Found: C, 62.81; H, 9.35.
3500-2500 (OH), 1725 (CdO); MS (CI, NH3) m/z 204 (M +
NH4+), 187 (M + H+). Anal. Calcd for C10H18O3: C, 64.49; H,
9.74. Found: C, 64.41; H, 9.77.
2-(1-Hyd r oxy-1,1-d ip h en ylm eth yl)-3-m eth ylbu t-3-en o-
ic a cid (2e): white solid; mp 190 °C; 1H NMR (250 MHz,
acetone-d6) δ 7.72-7.14 (m, 10 H, Ph), 5.03 (s, 1 H, CH2d),
4.89 (s, 1 H, CH2d), 4.53 (s, 1 H, CH-COOH), 1.62 (s, 3 H,
Me); 13C NMR (62.9 MHz, acetone-d6) δ 176.9, 149.9, 145.9,
140.6, 129.4, 128.8, 128.0, 127.5, 127.1, 126.9, 118.6, 79.6, 59.3,
24.0; IR (KBr, cm-1) 3500-2500 (OH), 1725 (CdO); MS (CI,
NH3) m/z 300 (M + NH4+). Anal. Calcd for C18H18O3: C, 76.57;
H, 6.43. Found: C, 76.55; H, 6.41.
2-(1-Hyd r oxy-1,1-d ip h en ylm eth yl)bu t-3-en oic a cid (1j):
white solid; mp 175 °C; 1H NMR (250 MHz, acetone-d6) δ 7.74-
7.24 (m, 10 H, Ph), 5.94 (ddd, 1 H, J ) 17.3, 10.3, 8.0 Hz, CHd
), 5.24 (d, 1 H, J ) 17.3 Hz, CH2d), 5.12 (d, 1 H, J ) 10.3 Hz,
CH2d), 4.56 (d, 1 H, J ) 8.0 Hz, CH-COOH); 13C NMR (62.9
MHz, acetone-d6) δ 176.0, 148.2, 145.0, 132.8, 128.6, 128.2,
127.2, 126.7, 126.0, 125.9, 119.8, 78.5, 56.8; IR (KBr, cm-1
)
2-(1-Hyd r oxycycloh exyl)-3-m eth ylbu t-3-en oic
a cid
(2g): white solid; mp 97 °C; 1H NMR (250 MHz, acetone-d6) δ
4.95 (s, 2 H, CH2d), 3.12 (s, 1H, CH-COOH), 1.83 (s, 3H, Me),
1.61-1.24 (m, 10 H, CH2); 13C NMR (62.9 MHz, acetone-d6) δ
175.9, 141.6, 117.5, 72.7, 61.8, 38.7, 35.9, 26.8, 23.0, 22.9, 22.7;
IR (KBr, cm-1) 3500-2500 (OH), 1725 (CdO); MS (CI, NH3)
m/z 216 (M + NH4+), 199 (M + H+). Anal. Calcd for C11H18O3:
C, 66.64; H, 9.15. Found: C, 66.63; H, 9.15.
3500-2500 (OH), 1705 (CdO); MS (CI, NH3) m/z 286 (M +
NH4+). Anal. Calcd for C17H16O3: C, 76.10; H, 6.01. Found:
C, 76.07; H, 5.99.
2-(1-Hyd r oxycycloh exyl)bu t-3-en oic a cid (1n ): white
solid; mp 96 °C; 1H NMR (250 MHz, CDCl3) δ 7.19 (s, 2 H,
OH), 5.91 (dt, 1 H, J ) 17.0, 9.7, Hz, CHd), 5.21 (m, 2 H, CH2d
), 3.05 (d, 1 H, J ) 9.7 Hz, CH-COOH), 1.63-1.20 (m, 10 H,
CH2); 13C NMR (62.9 MHz, CDCl3) δ 178.6, 132.0, 121.1, 72.7,
59.8, 37.0, 34.8, 25.8, 22.2, 21.8; IR (KBr, cm-1) 3500-2400
(OH), 1710 (CdO); MS (CI, NH3) m/z 202 (M + NH4+), 185 (M
+ H+). Anal. Calcd for C10H16O3: C, 65.19; H, 8.75. Found: C,
65.26; H, 8.74.
2-(3-Oxo-1,3-diph en ylpr opyl)bu t-3-en oic acid (1o): white
solid; mp 148 °C; 1H NMR (250 MHz, acetone-d6) δ 10.50 (s, 2
H, OH), 7.87-7.83 (m, 2 H, Ph), 7.53-7.02 (m, 8 H, Ph), 5.89
(dt, 1 H, J ) 17.1, 9.9 Hz, CHd), 5.28 (dd, 1 H, J ) 17.1, 1.5
Hz, CH2d), 5.16 (dd, 1 H, J ) 9.9, 1.5 Hz, CH2d), 3.82-3.72
Su p p or tin g In for m a tion Ava ila ble: Spectral and ana-
lytical data for all the other prepared compounds. This
material is available free of charge via the Internet at
http://pubs.acs.org.
J O020128U
(23) Su, H.; Shirai, K.; Kumamoto, T. Bull. Chem. Soc. J pn. 1992,
65, 2794.
J . Org. Chem, Vol. 67, No. 16, 2002 5615