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DOI: 10.1055/s-2008-1078277
K-10 Clay-Catalyzed Enol-Driven Decarboxylative Ring-Transformation Approach to Dihydro- and Tetrahydroquinolines from Carbohydrates
Publication History
Publication Date:
21 August 2008 (online)
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Abstract
An original synthetic approach to 4-polyhydroxyalkylquinolines using unprotected d-glucose/d-xylose as biorenewable resources is reported. The synthetic protocol involves enol-driven Michael-type addition of cyclic ketones to aldose-derived 1,3-oxazin-2-ones followed by decarboxylative ring transformation to yield various novel 5,6-dihydro-/5,6,7,8-tetrahydro-4-polyhydroxyalkylquinolines and their 5-, 6-, or 8-one analogues. This is a one-pot montmorillonite K-10 clay-catalyzed process proceeding under solvent-free microwave irradiation conditions.
Key words
carbohydrates - mineral-catalyzed - microwaves - solvent-free - 1,3-oxazin-2-ones(thiones) - quinolines
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References and Notes
General Procedure
for the Synthesis of 1,3-Oxazin-2-ones(thiones)
4: Thoroughly mixed d-xylose/d-glucose 1 (1 mmol),
semicarbazide hydrochloride/thiosemicarbazide 2 (1 mmol), sodium acetate (1 mmol) and
montmorillonite K-10 clay (0.10 g) in a 20-mL vial were subjected
to microwave irradiation in a CEM Discover Focused Microwave Synthesis
System for 10 min at 90 ˚C. After completion of the reaction
as indicated by TLC, H2O (10 mL) was added to precipitate
the crude product, which was recrystallized from EtOH to afford
analytically pure sample of 4.
Characterization Data of Representative Compounds: Compound 4a: white solid; yield: 82%;
mp 145-148 ˚C. IR (KBr): 3392, 3386, 3011, 1692
cm-¹. ¹H NMR (400
MHz, DMSO-d
6): δ = 4.11
(dd, J
2
′
Ha,2
′
Hb = 10.1
Hz, J
1
′
H,2
′
Ha = 5.4 Hz,
1 H, 2′Ha), 4.30 (dd, J
1
′
H,2
′
Ha = 5.4
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 1′H), 4.63 (dd, J
2
′
Ha,2
′
Hb = 10.1
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 2′Hb), 4.93-5.21 (br s, 2
H, 2 × OH, exch. D2O), 7.48 (d, J
5H,6H = 8.1 Hz,
1 H, 5-H), 7.89 (d, J
5H,6H = 8.1
Hz, 1 H, 4-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 64.5,
65.3, 73.7, 86.2, 105.9, 174.5. MS (FAB): m/z = 158 [M + H+].
Anal. Calcd for C6H7NO4: C, 45.86;
H, 4.49; N, 8.91. Found: C, 46.17; H, 4.58; N, 8.79.
Compound 4b: white solid; yield: 80%;
mp 159-161 ˚C. IR (KBr): 3391, 3386, 3009, 1051
cm-¹. ¹H NMR (400
MHz, DMSO-d
6): δ = 4.13
(dd, J
2
′
Ha,2
′
Hb = 10.1
Hz, J
1
′
H,2
′
Ha = 5.3 Hz,
1 H, 2′Ha), 4.29 (dd, J
1
′
H,2
′
Ha = 5.3
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 1′H), 4.66 (dd, J
2
′
Ha,2
′
Hb = 10.1
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 2′Hb), 4.93-5.25 (br s, 2
H, 2× OH, exch. D2O), 7.47 (d, J
5H,6H = 8.2
Hz, 1 H, 5-H), 7.91 (d, J
5H,6H = 8.2
Hz, 1 H, 4-H). ¹³C NMR (100 MHz, DMSO-d
6): δ= 64.2,
65.4, 73.3, 86.5, 105.7, 192.3. MS (FAB): m/z = 174 [M + H+].
Anal. Calcd for C6H7NO3S: C, 41.61;
H, 4.07; N, 8.09. Found: C, 41.86; H, 4.21; N, 7.88.
Compound 4c: white solid; yield: 79%;
mp 153-155 ˚C. IR (KBr): 3399-3382, 3008,
1689 cm-¹. ¹H NMR
(400 MHz, DMSO-d
6): δ = 3.88
(ddd, J
2
′
H,3
′
Ha = 5.4
Hz, J
1
′
H,2
′
H = 4.6
Hz, J
2
′
H,3
′
Hb = 2.7
Hz, 1 H, 2′H), 4.03 (dd, J
3
′
Ha,3
′
Hb = 10.5
Hz, J
2
′
H,3
′
Ha = 5.4
Hz, 1 H, 3′Ha), 4.37 (d, J
1
′
H,2
′
H = 4.6
Hz, 1 H, 1′H), 4.59 (dd, J
3
′
Ha,3
′
Hb = 10.5
Hz, J
2
′
H,3
′
Hb = 2.7
Hz, 1 H, 3′Hb), 5.01-5.37 (br s, 3
H, 3 × OH, exch. D2O), 7.51 (d, J
4H,5H = 8.1 Hz,
1 H, 5-H), 7.85 (d, J
4H,5H = 8.1
Hz, 1 H, 4-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 64.3,
65.9, 71.7, 73.5, 86.5, 106.3, 174.8. MS (FAB): m/z = 188 [M + H+]. Anal.
Calcd for C7H9NO5: C, 44.92; H,
4.85; N, 7.48. Found: C, 44.69; H, 4.73; N, 7.73.
Compound 4d: white solid; yield: 85%;
mp 141-142 ˚C. IR (KBr): 3398-3382, 3011,
1055 cm-¹. ¹H NMR
(400 MHz, DMSO-d
6): δ = 3.89
(ddd, J
2
′
H,3
′
Ha = 5.4
Hz, J
1
′
H,2
′
H = 4.7
Hz, J
2
′
H,3
′
Hb = 2.7
Hz, 1 H, 2′H), 4.06 (dd, J
3
′
Ha,3
′
Hb = 10.5
Hz, J
2
′
H,3
′
Ha = 5.4
Hz, 1 H, 3′Ha), 4.34 (d, J
1
′
H,2
′
H = 4.7
Hz, 1 H, 1′H), 4.63 (dd, J
3
′
Ha,3
′
Hb = 10.5
Hz, J
2
′
H,3
′
Hb = 2.7
Hz, 1 H, 3′Hb), 5.06-5.38 (br s, 3
H, 3 × OH, exch. D2O), 7.54 (d, J
4H,5H = 8.1 Hz,
1 H, 5-H), 7.81 (d, J
4H,5H = 8.1
Hz, 1 H, 4-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 64.7,
65.5, 71.5, 73.8, 86.7, 106.1, 192.7. MS (FAB): m/z = 204 [M + H+]. Anal.
Calcd for C7H9NO4S: C, 41.37; H,
4.46; N, 6.89. Found: C, 41.68; H, 4.31; N, 7.08.
General Procedure
for the Synthesis of 4-Poly-hydroxyalkylquinolines 6: An intimate,
solvent-free mixture of 1,3-oxazin-2-one(thione) 4 (2.4
mmol), cyclic ketone 5 (2.4 mmol) and montmorillonite
K-10 clay (0.25 g) in a 20-mL vial was subjected to MW irradiation
in a CEM Discover Focused Microwave Synthesis System at 90 ˚C
for 9-14 min. After completion of the reaction as indicated
by TLC, H2O (10 mL) was added to precipitate the crude product,
which was recrystallized from EtOH to give an analytically pure
sample of 6 as a white solid.
Characterization Data of Representative Compounds: Compound 6a: white solid; yield: 91%; mp
187-189 ˚C. IR (KBr): 3393, 3003, 1598, 1579,
1457 cm-¹. ¹H NMR
(400 MHz, DMSO-d
6): δ = 2.13-2.32
(m, 4 H, 5-CH2, 6-CH2), 3.74 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Ha = 5.5
Hz, 1 H, 2′Ha), 4.18 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 2′Hb), 4.29 (dd, J
1
′
H,2
′
Ha = 5.5
Hz, J
1
′
H,2
′
Hb = 2.9
Hz, 1 H, 1′H), 4.99-5.13 (br s, 2 H, 2 × OH,
exch. D2O), 5.76 (m, 1 H, 7-H), 6.89 (d, J
7H,8H = 6.1 Hz,
1 H, 8-H), 7.92 (d, J
2H,3H = 7.7
Hz, 1 H, 2-H), 8.07 (d, J
2H,3H = 7.7
Hz, 1 H, 3-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 23.9,
28.8, 64.1, 70.3, 121.9, 123.5, 130.5, 135.5, 144.8, 147.9, 153.1.
MS (FAB): m/z = 192 [M + H+].
Anal. Calcd for C11H13NO2: C, 69.09;
H, 6.85; N, 7.32. Found: C, 69.45; H, 6.71; N, 7.65.
Compound 6b: white solid; yield: 83%; mp
176-178 ˚C. IR (KBr): 3380-3398, 3009,
1603, 1582, 1455 cm-¹. ¹H
NMR (400 MHz, DMSO-d
6): δ = 2.13-2.32
(m, 4 H, 5-CH2, 6-CH2), 3.85 (ddd, J
2
′
H,3
′
Ha = 5.3
Hz, J
1
′
H,2
′
H = 4.6
Hz, J
2
′
H,3
′
Hb = 2.8
Hz, 1 H, 2′H), 4.05 (dd, J
3
′
Ha,3
′
Hb = 10.3
Hz, J
2
′
H,3
′
Ha = 5.3 Hz,
1 H, 3′Ha), 4.29 (d, J
1
′
H,2
′
H = 4.7
Hz, 1 H, 1′H), 4.56 (dd, J
3
′
Ha,3
′
Hb = 10.3
Hz, J
2
′
H,3
′
Hb = 2.8
Hz, 1 H, 3′Hb), 4.99-5.16 (br s, 3
H, 3 × OH, exch. D2O), 5.78 (m, 1 H, 7-H), 6.85
(d, J
7H,8H = 6.2
Hz, 1 H, 8-H), 7.95 (d, J
2H,3H = 7.7
Hz, 1 H, 2-H), 8.08 (d, J
2H,3H = 7.7
Hz, 1 H, 3-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 23.8,
28.9, 64.5, 70.1, 73.5, 121.7, 123.8, 130.1, 135.5, 144.9, 147.6,
153.2. MS (FAB): m/z = 222 [M + H+].
Anal. Calcd for C12H15NO3: C, 65.14;
H, 6.83; N, 6.33. Found: C, 64.86; H, 6.61; N, 6.55.
Compound 6e: white solid; yield: 89%; mp
203-205 ˚C. IR (KBr): 3395, 2998, 1693, 1601,
1585, 1451 cm-¹. ¹H
NMR (400 MHz, DMSO-d
6): δ = 2.18
(m, 2 H, 6-CH2), 2.67 (t, J
5H,6H = 6.3
Hz, 2 H, 5-CH2), 2.91 (t, J
6H,7H = 5.8
Hz, 2 H,
7-CH2), 3.71 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Ha = 5.5
Hz, 1 H, 2′Ha), 4.12 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Hb = 2.7
Hz, 1 H, 2′Hb), 4.23 (dd, J
1
′
H,2
′
Ha = 5.5
Hz, J
1
′
H,2
′
Hb = 2.7
Hz, 1 H, 1′H), 5.03-5.19 (br s, 2 H, 2 × OH,
exch. D2O), 7.89 (d, J
2H,3H = 7.6
Hz, 1 H, 2-H), 8.03 (d, J
2H,3H = 7.6
Hz, 1 H, 3-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 23.7,
25.2, 44.1, 63.5, 70.5, 129.5, 131.7, 145.9, 148.3, 155.1, 192.5.
MS (FAB): m/z = 208 [M + H+].
Anal. Calcd for C11H13NO3: C, 63.76; H,
6.32; N, 6.76. Found: C, 63.49; H, 6.61; N, 6.93.
Compound 6g: white solid; yield: 91%; mp
196-198 ˚C. IR (KBr): 3393, 2998, 1695, 1605,
1581, 1458 cm-¹. ¹H
NMR (400 MHz, DMSO-d
6): δ = 2.21
(m, 2 H, 7-CH2), 2.66 (t, J
7H,8H =
6.3 Hz, 2 H, 8-CH2), 2.92 (t, J
6H,7H = 5.7
Hz, 2 H, 6-CH2), 3.74 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Ha = 5.3
Hz, 1 H, 2′Ha), 4.11 (dd, J
2
′
Ha,2
′
Hb = 10.5
Hz, J
1
′
H,2
′
Hb = 2.7
Hz, 1 H, 2′Hb), 4.28 (dd, J
1
′
H,2
′
Ha = 5.3
Hz, J
1
′
H,2
′
Hb = 2.7
Hz, 1 H, 1′H), 5.07-5.18 (br s, 2 H, 2 × OH,
exch. D2O), 7.85 (d, J
2H,3H = 7.5
Hz, 1 H, 2-H), 8.04 (d, J
2H,3H = 7.5
Hz, 1 H, 3-H). ¹³C NMR (100 MHz, DMSO-d
6): δ = 23.9,
25.1, 44.6, 63.1, 70.8, 129.3, 131.7, 145.5, 148.3, 155.2, 192.3.
MS (FAB): m/z = 208 [M + H+].
Anal. Calcd for C11H13NO3: C, 63.76; H,
6.32; N, 6.76. Found: C, 63.93; H, 6.51; N, 6.59.