Iodine-catalyzed and solvent-controlled selective electrophilic cyclization and oxidative esterification of ortho-alkynyl aldehydes

Article abstract of DOI:10.1039/b927185f

4-Iodo-pyrano[4,3-b]quinolines and ortho-alkynyl esters were synthesized selectively from ortho-alkynyl aldehydes by an iodine-catalyzed and solvent controlled reaction.

Full text of DOI:10.1039/b927185f

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Supporting Information
Iodine-catalyzed and solvent-controlled selective electrophilic
cyclization and oxidative esterification of ortho-alkynyl aldehydes
a
a
b
Akhilesh Kumar Verma,* Trapti Aggarwal , Vineeta Rustagi, and Richard C. Larock*
Synthetic Organic Chemistry Research Laboratory, Department of Chemistry, University of
Delhi, Delhi 110007, India and Department of Chemistry, Iowa State University of Science and
Technology, Ames, Iowa, USA
Page
1
2
3
4
5
. General………………………………………………………………………….. S2-S2
. Preparation of the 2-alkynylaldehydes (1a-i)………………………………….. S3-S5
. Synthesis of 4-iodo-1H-pyrano[4,3-b]quinolines (2a-b). ……………………… S6-S7
. synthesis of alkyl 2-(alkynyl)quinoline-3-carboxylates (3a-i)………………… S7-S10
. Synthesis of 4-iodo-3-aryl-1H-pyrano[4,3-b]quinolin-1-one (4a-i)…………..
S11-S13
1
13
6
. Copies of H and C NMRs……………………………………………………. S14-S63
S- 1

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Experimental Section
1
13
General. H and C NMR spectra were recorded at 300 and 75.5 MHz or 400 and 100 MHz
respectively. Thin-layer chromatography was performed using commercially prepared 100-mesh
silica gel plates, and visualization was effected with short wavelength UV light (254 nm) and a
4 4 2 3
basic KMnO solution [3 g of KMnO + 20 g of K CO + 5 mL of NaOH (5 %) + 300 mL of
H O]. All melting points are uncorrected. Mass spectra were recorded on a Finnigan TSQ700
2
triple quadrupole mass spectrometer (Finnigan MAT, San Jose, CA). High resolution mass
spectra were recorded on a Kratos MS50TC double focusing magnetic sector mass spectrometer
using EI at 70 eV.
Reagents. All reagents were used directly as obtained commercially unless otherwise noted.
2 2
Anhydrous forms of ethyl ether, hexanes, ethyl acetate, and CH Cl were purchased from Merk
Chemical Co. 2-Bromobenzaldehyde, terminal alkynes, Et N and The palladium salts were
3
purchased from Aldrich Chemical Co., Inc.
Preparation of starting materials:
1
1
(
1). 2-chloroquinoline-3-carbaldehydes : They were prepared by the reported procedure.
CHO
1
.POCl (9.0equiv)
O
3
N
CH3
N
Cl
2.DMF (3.0equiv)
H
2
(
2).2-(alkynyl)quinoline-3-carbaldehydes : They were prepared by the Sonogashira coupling
2
reaction of 2-chloroquinoline-3-carbaldehyde with various terminal alkynes. All commercially
available compounds were used as received.
S- 2

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2
-(phenylethynyl)quinoline-3-carbaldehyde (1a). The product was
1
obtained as a white solid- mp 122-124 °C : HNMR (300 MHz, CDCl
3
): δ = 10.8 (s, 1H), 8.75
(
s, 1H), 8.81 (d, J = 8.4Hz, 1H), 797 (d, J = 8.1Hz, 1H), 7.87 (td, J = 1.5Hz, 1H), 7.72-7.61 (m,
1
3
3
H), 7.48-7.42 (m, 3H) ; C NMR (CDCl ): δ 190.81, 150.18, 143.91, 137.17, 133.07, 132.33,
3
+
129.88, 129.68, 129.34, 128.84, 128.62, 128.26, 126.44, 121.35, 95.55, 85.55. MS (ESI) :[M]
Calcd for [C18H11NO] : 257.0841, found 257.0852.
2
-((4-methoxyphenyl)ethynyl)quinoline-3-carbaldehyde (1b). The
1
product was obtained as a orange solid- mp 140-142 °C : HNMR (300 MHz, [D]CDCl
3
): δ =
1
6
1
0.80 (s, 1H), 8.73 (s, 1H), 8.16 (d, J = 8.4Hz, 1H), 7.96-7.83 (m, 2H), 7.66-7.59 (m, 3H), 6.95-
1
3
.83 (m, 2H), 3.86 (s, 3H); C(CDCl
3
): 190.95, 160.86, 150.20, 144.24, 137.05, 133.99, 132.94,
+
29.63, 129.23, 128.69, 127.98, 126.27, 114.27, 113.28, 96.12, 84.22, 55.37. MS (ESI) :[M]
Calcd for [C H NO ] : 287.0946, found 287.0951.
1
9
13
2
2
-(hex-1-ynyl)quinoline-3-carbaldehyde (1c). The product was obtained
1
as a yellow oil: HNMR (300 MHz, [D]CDCl ): δ = 10.68 (s, 1H), 8.68 (s, 1H), 8.11 (d, J =
3
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8
.4Hz, 1H), 7.93-7.80 (m, 2H), 7.61-7.56 (m, 2H), 2.59 (t, J = 7.2Hz, 2H), 1.73-1.66 (m, 2H),
1
3
1
1
.57-1.47 (m, 2H), 0.97 (t, J = 7.2Hz, 3H); C NMR (CDCl ): 191, 150.07, 144.47, 136.76,
3
31.81, 129.57, 129.16, 128.74, 127.88, 126.24, 98.14, 87.79, 30.24, 22.19, 19.35, 13.58. MS
+
(
ESI) :[M] Calcd for [C16
H15NO] : 237.1154, found 237.1162.
2-(m-tolylethynyl)quinoline-3-carbaldehyde (1d). The product was
1
obtained as a orange solid - mp 126-128 °C: HNMR (300MHz, [D]CHCl
3
) δ :10.81 (s, 1H),
8
.74 (s, 1H), 8.17 (d, J = 8.7Hz, 1H), 7.96 (d, J = 8.1Hz, 1H), 7.87 (t, J = 7.2Hz, 1H), 7.63 (t, J
1
3
=
3
7.2Hz, 1H), 7.51 (d, J = 7.8Hz, 2H), 7.33-7.24 (m, 2H); C NMR (CDCl ): 190.90, 150.19,
144.01, 138.37, 137.09, 133.02, 132.86, 130.80, 129.67, 129.41, 129.32, 128.82, 128.50,
+
1
28.19, 126.40, 121.13, 95.88, 85.25, 21.25. MS (ESI) :[M] Calcd for [C H NO]: 271.0997,
1
9
13
found 271.0970.
2
-(p-tolylethynyl)quinoline-3-carbaldehyde (1e). The product was
1
obtained as a white solid- mp 138-140 °C : HNMR (300 MHz, [D]CDCl
3
): δ = 10.78 (s, 1H),
8
7
1
8
.71 (s, 1H), 8.15 (d, J = 8.7Hz, 1H), 7.91 (d, J = 8.1Hz, 1H), 7.85-7.79 (d, J = 8.4Hz, 1H),
13
.60-7.53 (m, 3H), 7.19-7.15 (m, 2H), 2.34 (s, 3H); C NMR (CDCl ) : 190.94, 150.22, 144.14,
3
40.36, 137.07, 133.00, 132.26, 129.67, 129.39, 129.31, 128.80, 128.12, 126.38, 118.26, 96.03,
+
5.13, 21.70. MS (ESI) :[M] Calcd for [C19
H
13NO]: 271.0997, found : 271.0979.
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2
-(cyclohexylethynyl)quinoline-3-carbaldehyde (1f). The product was
1
obtained as a white solid- mp 130-132 °C : HNMR (300 MHz, [D]CDCl
3
): δ 8.6 (s, 1H), 8.12
(d, J = 8.7Hz, 1H), 7.93 (d, J = 8.1Hz, 1H), 7.86-7.80 (m, 1H), 7.58 (td, J = 0.9Hz, 7.9Hz, 1H),
1
3
2
1
2
3
.02-1.97 (m, 2H), 1.82-1.55 (m, 5H), 1.47-1.36 (m, 3H). C NMR (CDCl ): 191.40, 150.10,
44.61, 136.76, 132.83, 129.61, 129.20, 128.77, 127.88, 126.25, 102.02, 77.47, 32.12, 29.90,
+
5.75, 24.94. MS (ESI) :[M] Calcd for [C18
H
17NO]: 263.13, found : 263.11.
6
-methoxy-2-(phenylethynyl)quinoline-3-carbaldehyde
(1g).
1
The product was obtained as a yellow solid- mp 164-166 °C: HNMR (300MHz, [D]CHCl
3
) δ:
10.78 (s, 1H), 8.61 (s, 1H), 8.06 (d, J = 9.3Hz, 1H), 7.70-7.67 (m, 2H), 7.52-7.41 (m, 4H), 7.17
1
3
(
d, J = 2.7 Hz, 1H), 3.96 (s, 3H). C NMR (CDCl
3
): 191.04, 159.00, 146.59, 141.46, 135.33,
132.21, 130.77, 129.64, 129.07, 128.56, 127.75, 126.29, 121.58, 106.25, 94.73, 85.56, 55.77. MS
+
(
ESI) :[M] Calcd for [C19
H13NO
2
] : 287.09, found : 287.13.
2-(thiophen-3-ylethynyl)quinoline-3-carbaldehyde (1h). The product
1
was obtained as a white solid - mp 122-124 °C: HNMR (300MHz, [D]CHCl
3
) δ: 10.78 (s, 1H),
7
7
.97 (d, J = 8.4Hz, 1H), 7.88 (td, J = 1.5Hz, 1H), 7.79-7.78 (m, 1H), 7.63 (td, J = 0.9 Hz, 1H),
13
.39-7.33 (m, 2H); C NMR (CDCl ): 190.79, 150.21, 143.94, 137.17, 133.06, 131.60, 129.99,
3
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+
1
29.68, 129.32, 128.76, 128.21, 126.41, 125.98, 120.52, 90.84, 85.38. MS (ESI) :[M] Calcd for
[
C H NOS] : 263.0405, found : 263.0450.
1
6
9
2-(3,3-dimethylbut-1-ynyl)quinoline-3-carbaldehyde (1i). The product
1
was obtained as a dirty white solid- mp 118-120 °C: HNMR (300MHz, [D]CHCl ) δ: 8.7 (s,
3
1
0
1
H), 8.14 (d, J = 8.4Hz, 1H), 7.91 (td, J = 0.6Hz, 7.5Hz, 1H), 7.86-7.81 (m, 1H), 7.60 (td, J =
.6Hz, 7.5Hz, 1H) . 13C NMR (CDCl
3
): 191.40, 150.06, 144.58, 136.77, 132.83, 129.63, 128.75,
+
27.88, 126.25, 105.82, 76.08, 30.57, 28.40. MS (ESI): [M] Calcd for [C16
H15NO] : 237.12,
found: 237.20.
General procedure for the synthesis of 4-iodo-1H-pyrano[4,3-b]quinolines (2a-b). Into a
solution of the 2-(alkynyl)quinoline-3-carbaldehyde (0.25 mmol), K CO (2.5 equiv) and the
nucleophile (1.2 equiv) in CH Cl (2.0 mL), I (2.5 equiv) was added and the solution was stirred
2
3
2
2
2
at room temperature until the total disappearance of the starting material as determined by TLC
analysis. The reaction mixture was then quenched with satd aq Na (5.0 mL) and water (5.0
mL). The resulting solution was extracted using ethyl acetate. The combined organic extracts
were dried over anhydrous Na SO and concentrated under vacuum. The crude product was
2 2 3
S O
2
4
purified by flash column chromatography (neutral aluminum oxide, hexane/EtOAc) to afford
pure compounds.
4
-iodo-1-methoxy-3-phenyl-1H-pyrano[4,3-b]quinoline(2a).
The
1
product was obtained as a yellow solid- mp 116-118 °C: HNMR (300MHz, [D]CHCl
3
) δ : 8.20
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(
d, J = 8.7Hz, 1H), 7.97 (s, 1H), 7.82 (d, J = 8.1Hz, 1H), 7.75-7.70 (m, 3H), 7.53-7.45 (m, 4H),
1
3
6
1
.22 (s, 1H), 3.71 (s, 3H); C NMR (CDCl ) :157.69, 148.85, 147.82, 136.98, 133.12, 130.28,
3
+
29.92, 129.84, 129.53, 127.50, 126.39, 121.83, 100.45, 78.01, 77.23, 56.47. HRMS (ESI) :[M]
2
Calcd for [C19H14INO ] : 415.0069, found : 415.0073.
4
-iodo-1-methoxy-3-(4-methoxyphenyl)-1H-pyrano[4,3-b]quinoline
1
(
2b). The product was obtained as yellow solid - mp 130-132 °C : HNMR (300MHz, [D]CHCl
3
)
δ: 8.19 (d, J = 8.4Hz, 1H), 7.95 (s, 1H), 7.81 (d, J = 8.1Hz, 1H), 7.74-7.69 (m, 3H), 7.49 (td, J =
1
3
0
1
1
4
.9, 6.9 Hz, 1H), 6.99-6.95 (m, 2H) 6.21 (s, 1H), 3.85 (s, 3H), 3.69 (s, 3H); C NMR (CDCl ):
3
59.70, 156.35, 147.83, 147.19, 131.93, 130.69, 129.20, 128.44, 128.10, 126.47, 126.38, 125.24,
+
20.91, 112.21, 99.41, 76.21, 55.45, 54.35. HRMS (ESI): [M] Calcd for [C20
3
H16INO ] :
45.0175, found : 445.034.
General procedure for the synthesis of alkyl 2-(alkynyl)quinoline-3-carboxylates (3a-i): To
a solution of I (2.5 equiv) in 30 equiv nucleophile were added 2-(alkynyl)quinoline-3-
2
2 3
carbaldehyde (0.25 mmol), K CO (2.5 equiv) . The resulting reaction mixture was heated under
0
an Ar atmosphere at 70 C until the total disappearance of the starting material as determined by
TLC analysis. The reaction mixture was then quenched with satd aq Na
5.0 mL). The resulting solution was extracted using ethyl acetate. The combined organic
extracts were dried over anhydrous Na SO and concentrated under vacuum. The crude product
2 2 3
S O (5.0 mL) and water
(
2
4
was purified by flash column chromatography (neutral aluminum oxide, hexane/EtOAc) to
afford pure compounds.
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Methyl 2-(phenylethynyl)quinoline-3-carboxylate (3a). The product
°
1
was obtained as orange solid- mp 96-98 C: HNMR (300MHz, [D]CHCl
3
) δ: 8.8 (s, 1H), 8.16
(d, J = 8.1Hz, 1H), 7.89 (d, J = 8.1Hz, 1H), 7.83 (td, J = 1.2, 7.2 Hz,,1H), 7.73-7.70 (m, 2H),
1
3
7
1
9
3
.60 (t, J =7.8Hz, 1H), 7.4-7.38 (m, 3H), 4.04 (s, 3H); C NMR (CDCl ) : 165.65, 149.05,
41.62, 139.77, 132.40, 132.24, 129.30, 129.18, 128.55, 128.40, 127.93, 125.83, 125.56, 122.39,
+
3.46, 88.47, 52.64. HRMS (ESI): [M] Calcd for [C H NO ] : 287.0946, found : 287.0949.
1
9
13
2
Methyl 2-(hex-1-ynyl)quinoline-3-carboxylate (3b). The product was
1
obtained as orange oil: HNMR (300MHz, [D]CHCl
3
) δ: 8.70 (s, 1H), 8.10 (d, J = 8.4Hz, 1H),
7
2
1
1
.85-7.75 (m, 2H), 7.55 (t, J = 6.9Hz, 1H), 3.99 (s, 3H), 2.57 (t, J = 7.2Hz, 2H), 1.75-1.65 (m,
1
3
H), 1.60-1.50 (m, 2H), 0.97 (t, J = 7.2Hz, 3H); C NMR (CDCl ): δ 164.88, 147.86, 140.88,
3
38.39, 130.95, 127.96, 127.37, 126.55, 124.58, 124.53, 94.90, 78.90, 51.43, 29.35, 21.09, 18.54,
+
2.62. HRMS (ESI): [M] Calcd for [C17
H
17NO
2
] : 267.1259, found : 267.1261.
Methyl 2-(m-tolylethynyl)quinoline-3-carboxylate (3c). The product
°
1
was obtained as orange solid- mp 104-106 C: HNMR (300MHz, [D]CHCl
3
) δ : 8.79 (s, 1H),
8
2
.16 (d, J = 8.7Hz, 1H), 7.89-7.79 (m, 2H), 7.62-7.51 (m, 3H), 7.30-7.19 (m, 2H), 4.04 (s, 3H),
1
3
.37 (s, 3H);
3
C NMR (CDCl ): 165.66, 149.05, 141.69, 139.73, 138.07, 132.91, 132.20,
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130.23, 129.51, 129.16, 128.53, 128.34, 127.87, 125.78, 125.52, 122.17, 93.73, 88.16, 52.63,
+
2
1.27. HRMS (ESI): [M] Calcd for [C H NO ] : 301.1103, found : 301.1110.
2
0
15
2
Ethyl 2-(p-tolylethynyl)quinoline-3-carboxylate (3d). The product was
1
obtained as orange solid - mp 94-96 °C: HNMR (300MHz, [D]CHCl ) δ: 8.78 (s, 1H), 8.16 (d,
3
J = 8.4Hz, 1H), 7.91-7.79 (m, 2H), 7.62-7.57 (m, 3H), 7.27-7.18 (m, 2H), 4.50 (q, J = 6.9Hz,
1
3
2
1
8
3
3
H), 2.41 (s, 3H), 1.41 (t, J = 7.2Hz, 3H); C NMR (CDCl ): δ 165.38, 149.00, 141.76,
39.55,132.95, 132.26, 132.10, 129.18, 129.14, 128.51, 127.79, 125.92, 125.81, 119.34, 93.76,
+
8.04, 61.74, 21.68, 14.40. HRMS (ESI): [M] Calcd for [C21
2
H17NO ] : 315.1259, found :
15.1261.
Methyl 2-(cyclohexylethynyl)quinoline-3-carboxylate (3e). The product
1
was obtained as orange solid - mp 70-74 °C: HNMR (300MHz, [D]CHCl
3
) δ: 8.71 (s, 1H), 8.11
(
d, J = 8.4Hz, 1H), 7.85 (d, J = 8.1Hz, 1H), 7.78 (td, J = 8.4Hz, 1.5Hz, 1H), 7.56 (t, J = 6.9Hz,
1H), 3.99 (s, 1H), 2.79-2.70 (m, 1H), 2.00-1.84 (m, 2H), 1.82-1.54 (m, 5H), 1.45-1.31 (m, 3H).
1
3
C NMR (CDCl
3
): 166.11, 148.87, 141.93, 139.41, 131.95, 129.03, 128.40, 127.55, 125.87,
+
1
25.62, 99.65, 79.90, 52.48, 32.17, 30.03, 29.70, 25.88, 24.93. HRMS (ESI): [M] Calcd for
19 2
[C H19NO ] : 293.14, found: 293.22.
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Methyl 6-methoxy-2-(phenylethynyl)quinoline-3-carboxylate
1
(
3f). The product was obtained as yellow solid - mp 152-154 °C: HNMR (300MHz, [D]CHCl
3
)
δ: 8.68 (s, 1H), 8.05 (d, J = 9.3Hz, 1H), 7.71-7.69 (m, 2H), 7.469 (dd, J = 9.3Hz, 2.1Hz, 1H),
1
3
7
1
1
3
.39-7.37 (m, 3H), 7.12 (d, J = 2.4Hz, 1H), 4.03 (s, 1H), 3.94 (m, 1H) . C NMR (CDCl ):
65.83, 158.82, 145.33, 139.00, 138.18, 132.25, 130.63, 129.04, 128.34, 127.07, 125.84, 125.23,
+
22.59, 105.50, 92.54, 88.49, 55.68, 52.55. HRMS (ESI): [M] Calcd for [C20
H
15NO
3
] : 317.11,
found: 317.15.
Methyl 2-(thiophen-3-ylethynyl)quinoline-3-carboxylate (3g). The
1
product was obtained as orange solid- mp 86-88 °C: HNMR (300MHz, [D]CHCl
3
) δ: 8.79 (s,
1
H), 8.14 (d, J = 8.4Hz, 1H), 7.89-7.76 (m, 3H), 7.59 (t, J = 7.2Hz, 1H), 7.36-7.31 (m, 2H), 4.03
1
3
(
s, 3H); C NMR (CDCl ): δ 165.48, 148.96, 141.56, 149.73, 132.19, 130.99, 130.12, 129.04,
3
+
1
28.49, 127.81, 125.68, 125.46, 125.25, 121.47, 88.72, 88.12, 52.53. HRMS (ESI): [M] Calcd
for [C17
H
11NO
2
S] : 293.0510, found : 293.0570.
Methyl 2-(3,3-dimethylbut-1-ynyl)quinoline-3-carboxylate (3h). The
1
product was obtained as yellow solid - mp 50-54 °C: HNMR (300MHz, [D] CHCl ) δ: 8.70
3
(
(
s,1H), 8.125 (d, J = 8.4Hz, 1H), 7.86-7.76 (m, 2H), 7.56 (t, J = 7.2Hz, 1H), 3.05 (s, 1H), 1.42
13
s, 9H). C NMR (CDCl
3
): 166.23, 148.81, 141.84, 139.42, 131.91, 129.07, 128.40, 127.56,
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+
1
26.13, 125.63, 103.28, 78.63, 52.46, 30.59, 28.30. HRMS (ESI): [M] Calcd for [C17
2
H17NO ]:
267.13, found: 267.18.
Ethyl 2-(phenylethynyl)quinoline-3-carboxylate (3i). The product was
1
obtained as yellow solid- mp 90-92 °C: HNMR (300MHz, [D]CHCl
3
) δ: 8.80 (s, 1H), 8.17( d, J
=
8.7Hz, 1H), 7.99-7.81 (m, 2H), 7.72-7.59 (m, 3H), 7.40-7.38 (m, 3H), 4.50 (q, J = 7.2Hz, 2H),
1
3
1
1
.45 (t, J = 7.2Hz, 3H) ; C NMR (CDCl
3
): δ 165.29, 148.99, 139.60, 132.32, 132.15, 129.23,
+
29.17, 128.52, 128.38, 127.90, 125.91, 122.41, 93.46, 88.47, 61.76, 14.38. HRMS (ESI): [M]
Calcd for [C H NO ] : 301.1103, found : 301.1119.
2
0
15
2
General procedure for the synthesis of 4-iodo-3-aryl-1H-pyrano[4,3-b]quinolin-1-one (4a-
e): To a solution of I (2.5 equiv) in CH Cl (2.0 mL) were added 2-(alkynyl) quinoline-3-
2
2
2
carbaldehyde (0.25 mmol). The resulting reaction mixture was stirred under an Ar atmosphere at
room temperature until the total disappearance of the starting material as determined by TLC
analysis. The reaction mixture was then quenched with satd aq Na S O (5.0 mL) and water (5.0
2
2
3
mL). The resulting solution was extracted using ethyl acetate. The combined organic extracts
2 4
were dried over anhydrous Na SO and concentrated under vacuum. The crude product was
purified by recrystallization.
4
-iodo-3-phenyl-1H-pyrano[4,3-b]quinolin-1-one (4a). The product was
1
obtained as orange solid – mp 224-226 °C : HNMR (300MHz, [D] CHCl ) δ: 9.12 (s, 1H), 8.29
3
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(
d, J = 8.7Hz, 1H), 8.04 (d, J = 8.4Hz, 1H), 7.94 (t, J = 7.5Hz, 1H), 7.83-7.82 (m, 2H) , 7.67 (t, J
13
=
7.5Hz, 1H), 7.52-7.50 (m, 3H); C NMR (CDCl ): δ 161.64, 157.66, 151.64, 150.54, 140.73,
3
134.78, 133.64, 130.56, 130.03, 129.66, 129.09, 128.09, 127.79, 127.41, 114.23, 81.67. HRMS
+
(
ESI): [M] Calcd for [C18
H10INO
2
] : 398.9756, found : 399.9750.
3
-butyl-4-iodo-1H-pyrano[4,3-b]quinolin-1-one (4b). The product was
1
obtained as yellow solid – mp 198-200 °C: HNMR (300MHz, [D]CHCl
3
) δ: 9.07 (s, 1H), 8.26
(
d, J = 8.7Hz, 1H), 8.01 (d, J = 8.1Hz, 1H), 7.92 (td, J = 1.2, 6.9Hz, 1H), 7.637 (td, J = 0.9,
8
3
1
.1Hz, 1H), 3.05 (t, J = 7.5Hz, 2H), 1.84-1.75 (m, 2H), 1.55-143 (m, 2H), 0.99 (t, J = 7.2Hz,
1
3
H); C NMR (CDCl ): δ 161.92, 161.80, 151.59, 150.24, 140.70, 133.53, 129.59, 1129.07,
3
+
27.48, 127.17, 114.03, 81.21, 37.45, 29.21, 22.29, 13.80. HRMS (ESI): [M] Calcd for
16 2
[C H14INO ] : 379.0069, found : 379.0062.
4
-iodo-3-p-tolyl-1H-pyrano[4,3-b]quinolin-1-one (4c). The product was
1
obtained as orange solid- mp 228-230 °C: HNMR (300MHz, [D]CHCl ) δ: 9.13 (s, 1H), 8.29
3
(
d, J = 8.4Hz, 1H), 8.05 (d, J = 7.8Hz, 1H), 7.94 (td, J = 1.5, 6.9Hz, 1H), 7.75 (d, J = 8.1Hz,
1
3
2
1
1
4
3
H), 7.68-7.64 (m, 1H), 7.31 (d, J = 7.8Hz, 2H), 2.45 (s, 3H) ; C NMR (CDCl ): δ 161.77,
57.82, 151.70, 150.71, 140.99, 140.71, 133.61, 131.90, 130.01, 129.68, 129.10, 128.78, 127.73,
+
27.41, 114.25, 81.23, 21.60. HRMS (ESI): [M] Calcd for [C19
2
H12INO ] : 412.9913, found :
13.9925.
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This journal is (c) The Royal Society of Chemistry 2010
3
-cyclohexyl-1H-pyrano[4,3-b]quinolin-1-one (4d). The product was
1
obtained as orange solid – mp 180-182 °C : HNMR (300MHz, [D]CHCl
3
) δ: 9.05 (s, 1H), 8.25
(
d, J = 8.4Hz, 1H), 8.00 (d, J = 8.1Hz, 1H), 7.93-7.88 (m, 1H), 7.62 (td, J = 0.9Hz, 8.1 Hz, 1H),
1
3
1
1
2
.95-1.88 (m, 4H), 1.79-1.60 (m, 3H), 1.50-1.28 (m, 3H) . C NMR (CDCl ): 164.15, 162.00,
3
51.59, 150.41, 140.67, 133.50, 129.56, 129.06, 127.43, 127.19, 114.33, 80.42, 46.61, 29.39,
+
5.93, 25.58. HRMS (ESI): [M] Calcd for [C18
H17NO
2
]: 279.13, found : 279.22.
4
-iodo-3-phenyl-1H-isochromen-1-one (4e). The product was obtained
1
as white solid – mp 136-138 °C : HNMR (300MHz, [D]CHCl
3
) δ: 8.31 (dd, J = 8.1Hz, 1H),
7
7
1
.91-7.80 (m, 1H), 7.83 (td, J = 1.2, 6.0Hz, 1H), 7.72-7.66 (m, 2H), 7.62-7.56 (m, 1H), 7.49-
13
.47 (m, 3H); C NMR (CDCl
3
): δ 161.57, 154.82, 138.19, 135.73, 135.26, 131.51, 130.21,
+
30.00, 129.76, 129.27, 128.10, 120.29, 77.44. MS (ESI): [M] Calcd for [C15
H
9
IO
2
] : 347.9647,
found : 348.9649.
REFERENCES:
1
2
.
.
O. Meth-Cohn, B. Narine and B. Tarnowski, Tetrahedron Lett., 1979, 33, 3111.
A. Chandra, B. Singh, S. Upadhaya and R. M. Singh, Tetrahedron, 2008, 64, 11680.
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H
N
CH3
1d
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H
N
CH3
1d
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O
H
N
1i
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