Nafion-H Catalyzed Synthesis of Polyhydroquinolines Via the Hantzsch Multi-Component Reaction
Supplementary Material
Nafion-H® catalyzed synthesis of Polyhydroquinolines via the Hantzsch Multi-component Reaction
Mazaahir Kidwai ● Ritika Chauhan ● Divya Bhatnagar ● Abhay K. Singh ● Biswajit Mishra ● Sharmistha Dey
Table 1. Crystal data and structure refinement for du_phq12.
CCDC Number796332
Identification code du_phq12
Empirical formula C23 H23 N O3
Formula weight 361.42
Temperature 293(2) K
Wavelength 1.54178 Å
Crystal system Triclinic
Space group P -1
Unit cell dimensionsa = 9.8640(10) Å= 116.36°.
b = 15.1480(10) Å= 92.87°.
c = 16.0630(10) Å = 103.32°.
Volume2060.5(3) Å3
Z2
Density (calculated)0.583 Mg/m3
Absorption coefficient0.307 mm-1
F(000)384
Crystal size0.2 x 0.4 x 0.2 mm3
Theta range for data collection3.12 to 69.94°.
Index ranges-12<=h<=11, -18<=k<=16, 0<=l<=19
Reflections collected7518
Independent reflections7518 [R(int) = 0.0000]
Completeness to theta = 69.94°96.4 %
Absorption correctionNone
Refinement methodFull-matrix least-squares on F2
Data / restraints / parameters7518 / 0 / 488
Goodness-of-fit on F21.577
Final R indices [I>2sigma(I)]R1 = 0.1824, wR2 = 0.4724
R indices (all data)R1 = 0.2677, wR2 = 0.5058
Extinction coefficient0.0005(8)
Largest diff. peak and hole4.210 and -0.508 e.Å-3
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for du_phq12. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
______
xyzU(eq)
______
N(01B) 3182(8) 3200(5) 4300(5) 50(2)
O(03A) -983(7) -1829(5) 1361(5) 70(2)
C(23B) 5874(18) 4752(14) 8947(10) 142(6)
C(15B) 2884(8) 4769(6) 5416(5) 38(2)
O(01A) 2263(8) 1600(4) 2455(4) 65(2)
C(11B) 3324(8) 4544(6) 6223(5) 36(2)
C(12B) 4134(8) 3767(6) 5885(6) 44(2)
C(14B) 2731(8) 4102(6) 4517(5) 39(2)
C(15A) 2170(10) 235(6) 978(6) 48(2)
C(16B) 2561(9) 5720(7) 5654(6) 45(2)
N(01A) 1854(9) -1029(6) -592(5) 61(2)
C(13B) 3978(9) 3079(6) 4948(6) 44(2)
C(12A) 377(9) -1445(6) 361(6) 46(2)
C(06A) 2153(9) -533(6) 2777(6) 44(2)
C(01B) 2046(9) 4209(6) 6604(5) 42(2)
C(06B) 1839(9) 4745(7) 7550(6) 44(2)
C(11A) 1244(9) -510(6) 1235(6) 46(2)
O(03B) 5265(8) 4504(6) 7405(4) 88(3)
C(01A) 2197(9) -794(6) 1835(5) 43(2)
C(19B) 2189(10) 4207(7) 3722(5) 52(2)
C(17B) 1970(10) 5881(7) 4872(6) 55(2)
C(21A) -816(10) -2160(7) 464(7) 62(3)
C(05A) 3096(11) -830(7) 3259(7) 58(3)
C(21B) 5086(10) 3719(7) 6587(6) 49(2)
C(05B) 596(11) 4351(9) 7827(7) 62(3)
C(02B) 1000(10) 3334(7) 6013(7) 57(2)
C(20B) 4573(10) 2199(6) 4513(6) 56(2)
C(16A) 2670(10) 1306(7) 1708(7) 54(2)
C(07B) 2880(12) 5667(7) 8237(6) 62(3)
O(02B) 5686(9) 3089(6) 6462(6) 97(3)
C(14A) 2447(10) -54(7) 108(6) 49(2)
C(02A) 3116(10) -1343(7) 1369(6) 56(2)
C(13A) 761(10) -1698(6) -488(6) 52(2)
C(07A) 1319(11) 40(7) 3322(6) 61(3)
O(02A) -1609(10) -2923(8) -135(6) 133(4)
C(03B) -225(11) 2966(8) 6323(10) 80(4)
C(04B) -421(12) 3478(8) 7227(9) 69(3)
C(10A) 3077(14) -551(9) 4197(8) 78(3)
C(04A) 3994(12) -1378(8) 2770(8) 72(3)
C(03A) 4005(12) -1624(8) 1859(8) 77(3)
C(20A) 156(12) -2651(8) -1450(6) 79(3)
C(17A) 3659(13) 2039(7) 1435(7) 76(3)
C(18B) 1273(11) 4871(7) 3974(7) 65(3)
C(09A) 2245(15) -36(11) 4677(8) 92(4)
C(08A) 1322(14) 297(9) 4254(7) 87(4)
C(22A) -2096(12) -2498(9) 1525(9) 92(4)
C(19A) 3404(13) 678(7) -148(7) 73(3)
C(08B) 2625(15) 6135(11) 9135(8) 94(4)
C(10B) 410(15) 4903(10) 8797(9) 85(4)
C(09B) 1430(17) 5792(11) 9414(8) 94(4)
C(18A) 4387(14) 1560(9) 703(8) 94(4)
C(23A) -2223(14) -1976(11) 2556(10) 114(5)
C(22B) 6338(16) 4661(13) 8182(8) 117(6)
O(01B) 2834(8) 6429(5) 6480(4) 67(2)
______
Table 3. Bond lengths [Å] and angles [°] for du_phq12.
______
N(01B)-C(13B) 1.373(10)
N(01B)-C(14B) 1.436(10)
N(01B)-H(01A) 0.8999
O(03A)-C(21A) 1.331(11)
O(03A)-C(22A) 1.435(12)
C(23B)-C(22B) 1.294(16)
C(23B)-H(23A) 0.9600
C(23B)-H(23B) 0.9600
C(23B)-H(23C) 0.9600
C(15B)-C(14B) 1.319(10)
C(15B)-C(16B) 1.435(11)
C(15B)-C(11B) 1.546(10)
O(01A)-C(16A) 1.206(10)
C(11B)-C(12B) 1.493(11)
C(11B)-C(01B) 1.510(11)
C(11B)-H(11A) 0.9600
C(12B)-C(13B) 1.372(11)
C(12B)-C(21B) 1.469(12)
C(14B)-C(19B) 1.446(11)
C(15A)-C(14A) 1.329(11)
C(15A)-C(16A) 1.461(12)
C(15A)-C(11A) 1.503(12)
C(16B)-O(01B) 1.246(9)
C(16B)-C(17B) 1.496(11)
N(01A)-C(14A) 1.360(11)
N(01A)-C(13A) 1.373(11)
N(01A)-H(01B) 0.9000
C(13B)-C(20B) 1.479(11)
C(12A)-C(13A) 1.343(11)
C(12A)-C(21A) 1.476(13)
C(12A)-C(11A) 1.504(11)
C(06A)-C(07A) 1.387(12)
C(06A)-C(01A) 1.389(11)
C(06A)-C(05A) 1.449(12)
C(01B)-C(02B) 1.370(11)
C(01B)-C(06B) 1.423(11)
C(06B)-C(05B) 1.417(13)
C(06B)-C(07B) 1.442(12)
C(11A)-C(01A) 1.568(11)
C(11A)-H(11B) 0.9600
O(03B)-C(21B) 1.290(10)
O(03B)-C(22B) 1.491(12)
C(01A)-C(02A) 1.391(12)
C(19B)-C(18B) 1.445(12)
C(19B)-H(19A) 0.9600
C(19B)-H(19B) 0.9599
C(17B)-C(18B) 1.533(12)
C(17B)-H(17A) 0.9600
C(17B)-H(17B) 0.9600
C(21A)-O(02A) 1.180(11)
C(05A)-C(10A) 1.375(13)
C(05A)-C(04A) 1.386(14)
C(21B)-O(02B) 1.185(10)
C(05B)-C(04B) 1.358(14)
C(05B)-C(10B) 1.450(14)
C(02B)-C(03B) 1.419(14)
C(02B)-H(02A) 0.9600
C(20B)-H(20A) 0.9600
C(20B)-H(20B) 0.9601
C(20B)-H(20C) 0.9600
C(16A)-C(17A) 1.534(13)
C(07B)-C(08B) 1.363(13)
C(07B)-H(07A) 0.9599
C(14A)-C(19A) 1.501(12)
C(02A)-C(03A) 1.404(13)
C(02A)-H(02B) 0.9600
C(13A)-C(20A) 1.535(11)
C(07A)-C(08A) 1.369(12)
C(07A)-H(07B) 0.9600
C(03B)-C(04B) 1.358(14)
C(03B)-H(03A) 0.9600
C(04B)-H(04A) 0.9601
C(10A)-C(09A) 1.304(16)
C(10A)-H(10A) 0.9599
C(04A)-C(03A) 1.340(14)
C(04A)-H(04B) 0.9601
C(03A)-H(03B) 0.9599
C(20A)-H(20D) 0.9599
C(20A)-H(20E) 0.9601
C(20A)-H(20F) 0.9600
C(17A)-C(18A) 1.411(13)
C(17A)-H(17C) 0.9600
C(17A)-H(17D) 0.9600
C(18B)-H(18A) 0.9601
C(18B)-H(18B) 0.9600
C(09A)-C(08A) 1.413(18)
C(09A)-H(09A) 0.9600
C(08A)-H(08A) 0.9600
C(22A)-C(23A) 1.512(15)
C(22A)-H(22A) 0.9600
C(22A)-H(22B) 0.9600
C(19A)-C(18A) 1.497(14)
C(19A)-H(19C) 0.9601
C(19A)-H(19D) 0.9600
C(08B)-C(09B) 1.356(17)
C(08B)-H(08B) 0.9600
C(10B)-C(09B) 1.378(17)
C(10B)-H(10B) 0.9600
C(09B)-H(09B) 0.9600
C(18A)-H(18C) 0.9599
C(18A)-H(18D) 0.9599
C(23A)-H(23D) 0.9600
C(23A)-H(23E) 0.9599
C(23A)-H(23F) 0.9601
C(22B)-H(22C) 0.9600
C(22B)-H(22D) 0.9600
C(13B)-N(01B)-C(14B) 123.8(6)
C(13B)-N(01B)-H(01A) 118.0
C(14B)-N(01B)-H(01A) 118.1
C(21A)-O(03A)-C(22A) 115.2(8)
C(22B)-C(23B)-H(23A) 115.1
C(22B)-C(23B)-H(23B) 112.1
H(23A)-C(23B)-H(23B) 109.5
C(22B)-C(23B)-H(23C) 100.8
H(23A)-C(23B)-H(23C) 109.5
H(23B)-C(23B)-H(23C) 109.5
C(14B)-C(15B)-C(16B) 118.7(7)
C(14B)-C(15B)-C(11B) 122.7(7)
C(16B)-C(15B)-C(11B) 118.6(7)
C(12B)-C(11B)-C(01B) 112.2(6)
C(12B)-C(11B)-C(15B) 109.7(6)
C(01B)-C(11B)-C(15B) 110.7(6)
C(12B)-C(11B)-H(11A) 107.7
C(01B)-C(11B)-H(11A) 108.5
C(15B)-C(11B)-H(11A) 107.9
C(13B)-C(12B)-C(21B) 119.4(8)
C(13B)-C(12B)-C(11B) 122.1(8)
C(21B)-C(12B)-C(11B) 118.4(7)
C(15B)-C(14B)-N(01B) 117.3(7)
C(15B)-C(14B)-C(19B) 126.2(8)
N(01B)-C(14B)-C(19B) 116.5(7)
C(14A)-C(15A)-C(16A) 121.5(9)
C(14A)-C(15A)-C(11A) 121.5(8)
C(16A)-C(15A)-C(11A) 116.9(8)
O(01B)-C(16B)-C(15B) 121.9(7)
O(01B)-C(16B)-C(17B) 119.6(8)
C(15B)-C(16B)-C(17B) 118.4(7)
C(14A)-N(01A)-C(13A) 121.8(7)
C(14A)-N(01A)-H(01B) 119.0
C(13A)-N(01A)-H(01B) 119.2
C(12B)-C(13B)-N(01B) 118.1(8)
C(12B)-C(13B)-C(20B) 128.7(8)
N(01B)-C(13B)-C(20B) 113.2(7)
C(13A)-C(12A)-C(21A) 119.5(8)
C(13A)-C(12A)-C(11A) 121.5(8)
C(21A)-C(12A)-C(11A) 118.6(8)
C(07A)-C(06A)-C(01A) 125.4(9)
C(07A)-C(06A)-C(05A) 116.0(9)
C(01A)-C(06A)-C(05A) 118.6(8)
C(02B)-C(01B)-C(06B) 116.5(8)
C(02B)-C(01B)-C(11B) 119.1(8)
C(06B)-C(01B)-C(11B) 124.3(7)
C(05B)-C(06B)-C(01B) 119.2(9)
C(05B)-C(06B)-C(07B) 119.5(8)
C(01B)-C(06B)-C(07B) 121.3(8)
C(15A)-C(11A)-C(12A) 110.4(7)
C(15A)-C(11A)-C(01A) 109.0(7)
C(12A)-C(11A)-C(01A) 111.9(6)
C(15A)-C(11A)-H(11B) 109.3
C(12A)-C(11A)-H(11B) 108.4
C(01A)-C(11A)-H(11B) 107.8
C(21B)-O(03B)-C(22B) 119.0(9)
C(02A)-C(01A)-C(06A) 120.1(8)
C(02A)-C(01A)-C(11A) 116.2(7)
C(06A)-C(01A)-C(11A) 123.7(8)
C(18B)-C(19B)-C(14B) 111.8(7)
C(18B)-C(19B)-H(19A) 109.7
C(14B)-C(19B)-H(19A) 109.4
C(18B)-C(19B)-H(19B) 109.1
C(14B)-C(19B)-H(19B) 108.5
H(19A)-C(19B)-H(19B) 108.2
C(16B)-C(17B)-C(18B) 112.9(7)
C(16B)-C(17B)-H(17A) 107.7
C(18B)-C(17B)-H(17A) 107.2
C(16B)-C(17B)-H(17B) 109.7
C(18B)-C(17B)-H(17B) 111.4
H(17A)-C(17B)-H(17B) 107.7
O(02A)-C(21A)-O(03A) 120.1(10)
O(02A)-C(21A)-C(12A) 128.2(10)
O(03A)-C(21A)-C(12A) 111.7(8)
C(10A)-C(05A)-C(04A) 121.9(10)
C(10A)-C(05A)-C(06A) 118.6(11)
C(04A)-C(05A)-C(06A) 119.5(9)
O(02B)-C(21B)-O(03B) 121.2(9)
O(02B)-C(21B)-C(12B) 127.6(9)
O(03B)-C(21B)-C(12B) 111.1(8)
C(04B)-C(05B)-C(06B) 123.0(10)
C(04B)-C(05B)-C(10B) 118.6(10)
C(06B)-C(05B)-C(10B) 118.4(10)
C(01B)-C(02B)-C(03B) 122.3(10)
C(01B)-C(02B)-H(02A) 117.6
C(03B)-C(02B)-H(02A) 120.0
C(13B)-C(20B)-H(20A) 108.9
C(13B)-C(20B)-H(20B) 109.7
H(20A)-C(20B)-H(20B) 109.5
C(13B)-C(20B)-H(20C) 109.8
H(20A)-C(20B)-H(20C) 109.5
H(20B)-C(20B)-H(20C) 109.5
O(01A)-C(16A)-C(15A) 121.8(9)
O(01A)-C(16A)-C(17A) 122.5(8)
C(15A)-C(16A)-C(17A) 115.5(9)
C(08B)-C(07B)-C(06B) 118.4(10)
C(08B)-C(07B)-H(07A) 121.0
C(06B)-C(07B)-H(07A) 120.6
C(15A)-C(14A)-N(01A) 121.0(8)
C(15A)-C(14A)-C(19A) 121.9(8)
N(01A)-C(14A)-C(19A) 117.1(7)
C(01A)-C(02A)-C(03A) 119.6(9)
C(01A)-C(02A)-H(02B) 119.5
C(03A)-C(02A)-H(02B) 120.9
C(12A)-C(13A)-N(01A) 119.8(8)
C(12A)-C(13A)-C(20A) 131.3(9)
N(01A)-C(13A)-C(20A) 109.0(8)
C(08A)-C(07A)-C(06A) 123.8(11)
C(08A)-C(07A)-H(07B) 118.6
C(06A)-C(07A)-H(07B) 117.6
C(04B)-C(03B)-C(02B) 121.1(10)
C(04B)-C(03B)-H(03A) 119.4
C(02B)-C(03B)-H(03A) 119.4
C(03B)-C(04B)-C(05B) 117.8(10)
C(03B)-C(04B)-H(04A) 121.4
C(05B)-C(04B)-H(04A) 120.7
C(09A)-C(10A)-C(05A) 123.3(12)
C(09A)-C(10A)-H(10A) 118.0
C(05A)-C(10A)-H(10A) 118.6
C(03A)-C(04A)-C(05A) 120.5(10)
C(03A)-C(04A)-H(04B) 119.5
C(05A)-C(04A)-H(04B) 119.9
C(04A)-C(03A)-C(02A) 121.7(10)
C(04A)-C(03A)-H(03B) 120.3
C(02A)-C(03A)-H(03B) 117.9
C(13A)-C(20A)-H(20D) 108.8
C(13A)-C(20A)-H(20E) 109.9
H(20D)-C(20A)-H(20E) 109.5
C(13A)-C(20A)-H(20F) 109.7
H(20D)-C(20A)-H(20F) 109.5
H(20E)-C(20A)-H(20F) 109.5
C(18A)-C(17A)-C(16A) 114.7(9)
C(18A)-C(17A)-H(17C) 110.6
C(16A)-C(17A)-H(17C) 107.7
C(18A)-C(17A)-H(17D) 106.5
C(16A)-C(17A)-H(17D) 109.1
H(17C)-C(17A)-H(17D) 108.0
C(19B)-C(18B)-C(17B) 110.9(8)
C(19B)-C(18B)-H(18A) 109.5
C(17B)-C(18B)-H(18A) 107.9
C(19B)-C(18B)-H(18B) 110.4
C(17B)-C(18B)-H(18B) 109.6
H(18A)-C(18B)-H(18B) 108.4
C(10A)-C(09A)-C(08A) 120.9(11)
C(10A)-C(09A)-H(09A) 120.2
C(08A)-C(09A)-H(09A) 118.9
C(07A)-C(08A)-C(09A) 117.3(12)
C(07A)-C(08A)-H(08A) 121.1
C(09A)-C(08A)-H(08A) 121.5
O(03A)-C(22A)-C(23A) 108.5(10)
O(03A)-C(22A)-H(22A) 109.6
C(23A)-C(22A)-H(22A) 108.5
O(03A)-C(22A)-H(22B) 110.1
C(23A)-C(22A)-H(22B) 111.1
H(22A)-C(22A)-H(22B) 108.9
C(18A)-C(19A)-C(14A) 111.4(8)
C(18A)-C(19A)-H(19C) 107.5
C(14A)-C(19A)-H(19C) 110.4
C(18A)-C(19A)-H(19D) 110.5
C(14A)-C(19A)-H(19D) 108.5
H(19C)-C(19A)-H(19D) 108.4
C(07B)-C(08B)-C(09B) 123.5(13)
C(07B)-C(08B)-H(08B) 118.4
C(09B)-C(08B)-H(08B) 118.1
C(09B)-C(10B)-C(05B) 119.4(11)
C(09B)-C(10B)-H(10B) 121.1
C(05B)-C(10B)-H(10B) 119.5
C(08B)-C(09B)-C(10B) 120.9(11)
C(08B)-C(09B)-H(09B) 120.2
C(10B)-C(09B)-H(09B) 118.9
C(17A)-C(18A)-C(19A) 112.1(11)
C(17A)-C(18A)-H(18C) 106.6
C(19A)-C(18A)-H(18C) 107.0
C(17A)-C(18A)-H(18D) 111.2
C(19A)-C(18A)-H(18D) 111.6
H(18C)-C(18A)-H(18D) 108.0
C(22A)-C(23A)-H(23D) 111.6
C(22A)-C(23A)-H(23E) 109.7
H(23D)-C(23A)-H(23E) 109.5
C(22A)-C(23A)-H(23F) 107.1
H(23D)-C(23A)-H(23F) 109.5
H(23E)-C(23A)-H(23F) 109.5
C(23B)-C(22B)-O(03B) 115.5(13)
C(23B)-C(22B)-H(22C) 112.4
O(03B)-C(22B)-H(22C) 110.7
C(23B)-C(22B)-H(22D) 101.2
O(03B)-C(22B)-H(22D) 108.0
H(22C)-C(22B)-H(22D) 108.3
______
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (Å2x 103)for du_phq12. The anisotropic
displacement factor exponent takes the form: -22[ h2a*2U11 + ... + 2 h k a* b* U12 ]
______
U11U22U33U23U13U12
______
N(01B)54(5) 35(4)36(4) 2(3)-5(3) 0(4)
O(03A)56(4) 72(4)68(5) 34(4)2(4) -4(4)
C(23B)148(15) 199(18)83(10) 81(11)-5(10) 32(14)
C(15B)30(4) 39(4)45(5) 26(4)-4(4) -1(4)
O(01A)94(5) 46(4)32(3) 12(3)11(3) -5(4)
C(11B)27(4) 47(4)38(4) 26(4)0(3) 3(4)
C(12B)31(5) 41(5)58(5) 30(4)1(4) -3(4)
C(14B)32(5) 45(5)30(4) 18(4)-6(3) -6(4)
C(15A)52(6) 42(5)47(5) 23(4)-9(4) 10(4)
C(16B)41(5) 52(5)39(5) 27(4)-2(4) 1(4)
N(01A)72(6) 58(5)34(4) 11(4)6(4) 6(5)
C(13B)37(5) 42(5)43(5) 17(4)3(4) 2(4)
C(12A)52(6) 44(5)34(4) 16(4)-8(4) 9(4)
C(06A)40(5) 44(5)43(5) 25(4)1(4) -4(4)
C(01B)38(5) 46(5)41(4) 24(4)-4(4) 2(4)
C(06B)51(6) 60(5)48(5) 43(4)19(4) 25(5)
C(11A)38(5) 43(5)49(5) 21(4)-9(4) 4(4)
O(03B)91(6) 131(7)49(4) 43(5)-12(4) 47(5)
C(01A)41(5) 41(4)41(4) 23(4)-12(4) -7(4)
C(19B)67(6) 52(5)35(4) 23(4)3(4) 7(5)
C(17B)58(6) 48(5)61(6) 31(5)2(5) 8(5)
C(21A)45(6) 56(6)62(6) 17(5)-6(5) -3(5)
C(05A)53(6) 62(6)57(6) 42(5)-15(5) -13(5)
C(21B)49(6) 53(5)53(6) 34(5)2(4) 13(5)
C(05B)53(6) 87(7)70(7) 51(6)21(5) 28(6)
C(02B)46(6) 58(6)61(6) 33(5)0(5) -4(5)
C(20B)44(6) 50(5)66(6) 23(5)9(5) 8(5)
C(16A)54(6) 44(5)57(6) 24(5)-9(5) 3(5)
C(07B)89(8) 44(5)42(5) 11(4)12(5) 17(5)
O(02B)111(7) 107(6)94(6) 53(5)-2(5) 59(6)
C(14A)56(6) 55(5)34(5) 23(4)14(4) 5(5)
C(02A)58(6) 56(6)56(6) 25(5)1(5) 22(5)
C(13A)54(6) 44(5)46(5) 17(4)-20(4) 7(5)
C(07A)64(7) 61(6)44(5) 24(5)5(5) -5(5)
O(02A)111(7) 128(7)75(6) 25(5)-10(5) -64(6)
C(03B)39(6) 69(7)133(11) 65(8)-7(7) -11(5)
C(04B)58(7) 73(7)91(8) 51(7)29(6) 13(6)
C(10A)81(9) 87(8)73(8) 59(7)-3(7) -9(7)
C(04A)80(8) 66(6)77(7) 49(6)-20(6) 9(6)
C(03A)77(8) 73(7)92(8) 40(6)4(7) 38(7)
C(20A)79(8) 70(7)38(5) -7(5)-25(5) 7(6)
C(17A)96(9) 48(6)64(7) 20(5)13(6) 0(6)
C(18B)66(7) 68(6)64(6) 41(5)-11(5) 8(6)
C(09A)92(10) 109(10)45(6) 43(7)-8(7) -32(8)
C(08A)84(9) 100(9)42(6) 21(6)13(6) -14(7)
C(22A)59(7) 92(9)107(10) 48(8)18(7) -16(7)
C(19A)103(9) 58(6)68(7) 39(6)20(7) 18(6)
C(08B)105(11) 112(10)65(7) 47(7)31(7) 17(8)
C(10B)98(10) 88(8)90(9) 55(7)51(8) 28(8)
C(09B)132(13) 116(11)56(7) 51(8)40(8) 46(10)
C(18A)106(10) 72(8)88(9) 34(7)41(8) -2(7)
C(23A)73(9) 135(12)136(13) 90(11)-2(9) -17(9)
C(22B)126(12) 182(15)62(8) 56(9)-8(8) 84(12)
O(01B)90(5) 50(4)56(4) 26(3)0(4) 13(4)
Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
for du_phq12.
______
x y z U(eq)
______
H(01A) 2930 2683 3705 80
H(23A) 6576 4873 9451 80
H(23B) 5377 5266 9174 80
H(23C) 5217 4085 8723 80
H(11A) 3945 5168 6722 80
H(01B) 2187 -1238 -1139 80
H(11B) 610 -188 1619 80
H(19A) 1682 3542 3221 80
H(19B) 2976 4490 3500 80
H(17A) 2742 6260 4713 80
H(17B) 1325 6289 5087 80
H(02A) 1105 2978 5366 80
H(20A) 5116 2159 5002 80
H(20B) 3820 1575 4171 80
H(20C) 5174 2292 4089 80
H(07A) 3738 5936 8066 80
H(02B) 3161 -1498 725 80
H(07B) 708 266 3025 80
H(03A) -917 2338 5889 80
H(04A) -1239 3225 7443 80
H(10A) 3730 -722 4524 80
H(04B) 4642 -1560 3090 80
H(03B) 4599 -2028 1515 80
H(20D) -607 -3118 -1375 80
H(20E) -191 -2455 -1893 80
H(20F) 880 -2979 -1680 80
H(17C) 4316 2557 1993 80
H(17D) 3114 2371 1220 80
H(18A) 409 4538 4094 80
H(18B) 1043 5015 3468 80
H(09A) 2245 117 5324 80
H(08A) 697 670 4599 80
H(22A) -1864 -3125 1388 80
H(22B) -2969 -2657 1127 80
H(19C) 2859 956 -430 80
H(19D) 3930 308 -601 80
H(08B) 3327 6741 9595 80
H(10B) -423 4646 8998 80
H(09B) 1279 6171 10047 80
H(18C) 4999 1283 939 80
H(18D) 4964 2049 546 80
H(23D) -2956 -2397 2701 80
H(23E) -1338 -1819 2941 80
H(23F) -2447 -1349 2679 80
H(22C) 6843 4152 7956 80
H(22D) 7002 5324 8404 80
______
Table 6. Selected torsion angles [°] for du_phq12.
______
C13B N01B C14B 123.8
C13B N01B H01A 118
C14B N01B H01A 118.1
C21A O03A C22A 115.2
C22B C23B H23A 115.1
C22B C23B H23B 112.1
H23A C23B H23B 109.5
C22B C23B H23C 100.8
H23A C23B H23C 109.5
H23B C23B H23C 109.5
C14B C15B C16B 118.7
C14B C15B C11B 122.7
C16B C15B C11B 118.6
C12B C11B C01B 112.2
C12B C11B C15B 109.7
C01B C11B C15B 110.7
C12B C11B H11A 107.7
C01B C11B H11A 108.5
C15B C11B H11A 107.9
C13B C12B C21B 119.4
C13B C12B C11B 122.1
C21B C12B C11B 118.4
C15B C14B N01B 117.3
C15B C14B C19B 126.2
N01B C14B C19B 116.5
C14A C15A C16A 121.5
C14A C15A C11A 121.5
C16A C15A C11A 116.9
O01B C16B C15B 121.9
O01B C16B C17B 119.6
C15B C16B C17B 118.4
C14A N01A C13A 121.8
C14A N01A H01B 119
C13A N01A H01B 119.2
C12B C13B N01B 118.1
C12B C13B C20B 128.7
N01B C13B C20B 113.2
C13A C12A C21A 119.5
C13A C12A C11A 121.5
C21A C12A C11A 118.6
C07A C06A C01A 125.4
C07A C06A C05A 116.0
C01A C06A C05A 118.6
C02B C01B C06B 116.5
C02B C01B C11B 119.1
C06B C01B C11B 124.3
C05B C06B C01B 119.2
C05B C06B C07B 119.5
C01B C06B C07B 121.3
C15A C11A C12A 110.4
C15A C11A C01A 109.0
C12A C11A C01A 111.9
C15A C11A H11B 109.3
C12A C11A H11B 108.4
C01A C11A H11B 107.8
C21B O03B C22B 119.0
C02A C01A C06A 120.1
C02A C01A C11A 116.2
C06A C01A C11A 123.7
C18B C19B C14B 111.8
C18B C19B H19A 109.7
C14B C19B H19A 109.4
C18B C19B H19B 109.1
C14B C19B H19B 108.5
H19A C19B H19B 108.2
C16B C17B C18B 112.9
C16B C17B H17A 107.7
C18B C17B H17A 107.2
C16B C17B H17B 109.7
C18B C17B H17B 111.4
H17A C17B H17B 107.7
O02A C21A O03A 120.1
O02A C21A C12A 128.2
O03A C21A C12A 111.7
C10A C05A C04A 121.9
C10A C05A C06A 118.6
C04A C05A C06A 119.5
O02B C21B O03B 121.2
O02B C21B C12B 127.6
O03B C21B C12B 111.1
C04B C05B C06B 123.0
C04B C05B C10B 118.6
C06B C05B C10B 118.4
C01B C02B C03B 122.3
C01B C02B H02A 117.6
C03B C02B H02A 120
C13B C20B H20A 108.9
C13B C20B H20B 109.7
H20A C20B H20B 109.5
C13B C20B H20C 109.8
H20A C20B H20C 109.5
H20B C20B H20C 109.5
O01A C16A C15A 121.8
O01A C16A C17A 122.5
C15A C16A C17A 115.5
C08B C07B C06B 118.4
C08B C07B H07A 121
C06B C07B H07A 120.6
C15A C14A N01A 121.0
C15A C14A C19A 121.9
N01A C14A C19A 117.1
C01A C02A C03A 119.6
C01A C02A H02B 119.5
C03A C02A H02B 120.9
C12A C13A N01A 119.8
C12A C13A C20A 131.3
N01A C13A C20A 109.0
C08A C07A C06A 123.8
C08A C07A H07B 118.6
C06A C07A H07B 117.6
C04B C03B C02B 121.1
C04B C03B H03A 119.4
C02B C03B H03A 119.4
C03B C04B C05B 117.8
C03B C04B H04A 121.4
C05B C04B H04A 120.7
C09A C10A C05A 123.3
C09A C10A H10A 118
C05A C10A H10A 118.6
C03A C04A C05A 120.5
C03A C04A H04B 119.5
C05A C04A H04B 119.9
C04A C03A C02A 121.7
C04A C03A H03B 120.3
C02A C03A H03B 117.9
C13A C20A H20D 108.8
C13A C20A H20E 109.9
H20D C20A H20E 109.5
C13A C20A H20F 109.7
H20D C20A H20F 109.5
H20E C20A H20F 109.5
C18A C17A C16A 114.7
C18A C17A H17C 110.6
C16A C17A H17C 107.7
C18A C17A H17D 106.5
C16A C17A H17D 109.1
H17C C17A H17D 108
C19B C18B C17B 110.9
C19B C18B H18A 109.5
C17B C18B H18A 107.9
C19B C18B H18B 110.4
C17B C18B H18B 109.6
H18A C18B H18B 108.4
C10A C09A C08A 120.9
C10A C09A H09A 120.2
C08A C09A H09A 118.9
C07A C08A C09A 117.3
C07A C08A H08A 121.1
C09A C08A H08A 121.5
O03A C22A C23A 108.5
O03A C22A H22A 109.6
C23A C22A H22A 108.5
O03A C22A H22B 110.1
C23A C22A H22B 111.1
H22A C22A H22B 108.9
C18A C19A C14A 111.4
C18A C19A H19C 107.5
C14A C19A H19C 110.4
C18A C19A H19D 110.5
C14A C19A H19D 108.5
H19C C19A H19D 108.4
C07B C08B C09B 123.5
C07B C08B H08B 118.4
C09B C08B H08B 118.1
C09B C10B C05B 119.4
C09B C10B H10B 121.1
C05B C10B H10B 119.5
C08B C09B C10B 120.9
C08B C09B H09B 120.2
C10B C09B H09B 118.9
C17A C18A C19A 112.1
C17A C18A H18C 106.6
C19A C18A H18C 107
C17A C18A H18D 111.2
C19A C18A H18D 111.6
H18C C18A H18D 108
C22A C23A H23D 111.6
C22A C23A H23E 109.7
H23D C23A H23E 109.5
C22A C23A H23F 107.1
H23D C23A H23F 109.5
H23E C23A H23F 109.5
C23B C22B O03B 115.5
C23B C22B H22C 112.4
O03B C22B H22C 110.7
C23B C22B H22D 101.2
O03B C22B H22D 108
H22C C22B H22D 108.3
______
Spectral data for the known polyhydroquinolines 5
Ethyl-1,4,5,6,7,8-hexahydro-2,7,7-trimethyl-4-(phenyl)-5-oxoquinoline-3-carboxylate (5a) : IR (nujol, cm-1) - 3289, 3082, 2960, 1694, 1608, 1487, 1380, 1218; 1H NMR (CDCl3, 400 MHz) - δ : 0.93 (s, 3H, CH3), 1.07 (s, 3H, CH3), 1.19 (t, 3H, J = 7.12 Hz, CH3), 2.13-2.31(m, 4H, 2 x CH2), 2.37 (s, 3H, CH3), 4.06 (q, 2H, J = 7.08 Hz, CH2), 5.05 (s, 1H, CH-Ar), 5.86 (br s, 1H, NH), 7.07-7.31 (m, 5H, Ar-H); 13C NMR (CDCl3, 100 MHz) - δ : 19.5, 27.3, 29.0, 32.6, 36.8, 37.6, 41,4, 50.7, 60.4, 106.3, 112.1, 128.2, 143.8, 147.1, 149.6, 168.0, 195.8; Anal calcd. For C21H25NO3 : C, 74.31; H, 7.42; N, 4.13; Found : C, 74.11; H, 7.31; N, 4.20.
Ethyl-1,4,5,6,7,8-hexahydro-2,7,7-trimethyl-4-(4-methoxyphenyl)-5-oxoquinoline-3-carboxylate (5b) : IR (nujol, cm-1) - 3292, 3082, 2958, 1696, 1608, 1489, 1380, 1218; 1H NMR (CDCl3, 400 MHz) - δ : 0.92 (s, 3H, CH3), 1.05 (s, 3H, CH3), 1.19 (t, 3H, J = 7.12 Hz, CH3), 2.09-2.30 (m, 4H, 2 x CH2), 2.35 (s, 3H, CH3), 3.72 (s, 3H, OCH3), 4.05 (q, 2H, J = 7.08 Hz, CH2), 4.98 (s, 1H, CH-Ar), 5.95 (br s, 1H, NH), 6.71-7.21 (m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz) – δ : 14.4, 19.2, 27.2, 29.6, 32.7, 35.8, 40.6, 50.9, 55.2, 59.9, 106.1, 111.8, 113.3, 129.0, 139.9, 143.9, 149.6, 157.8, 167.8, 196.2; Anal calcd. For C22H27NO4 : C, 71.52; H, 7.37; N, 3.79; Found : C, 71.23; H, 7.12; N, 3.74.
Ethyl-1,4,5,6,7,8-hexahydro-2,7,7-trimethyl-4-(4-chlorophenyl)-5-oxoquinoline-3-carboxylate (5c) : IR (nujol, cm-1) - 3293, 3082, 2959, 1692, 1610, 1487, 1380, 1219; 1H NMR (CDCl3, 400 MHz) - δ : 0.92 (s, 3H, CH3), 1.08 (s, 3H, CH3), 1.20 (t, 3H, J = 7.04 Hz, CH3), 2.12-2.32 (m, 4H, 2 x CH2), 2.38 (s, 3H, CH3), 4.06 (q, 2H, J = 7.32 Hz, CH2), 5.02 (s, 1H, CH-Ar), 5.70 (br s, 1H, NH), 7.14-7.24 (m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz) – δ : 14.3, 19.4, 27.1, 29.6, 32.7, 36.3, 40.9, 50.8, 60.0, 105.7, 111.6, 128.1, 129.5, 131.7, 144.1, 145.8, 149.2, 167.4, 195.9; Anal calcd. For C21H24ClNO3 : C, 67.46; H, 6.47; N, 3.75; Found : C, 67.23; H, 6.33; N, 3.72.
Ethyl-1,4,5,6,7,8-hexahydro-2,7,7-trimethyl-4-(3-nitrophenyl)-5-oxoquinoline-3-carboxylate (5d) : IR (nujol, cm-1) - 3295, 3084, 2959, 1692, 1609, 1486, 1379, 1218; 1H NMR (CDCl3, 400 MHz) - δ : 0.93 (s, 3H, CH3), 1.08 (s, 3H, CH3), 1.19 (t, 3H, J = 7.04 Hz, CH3), 2.12-2.28 (m, 4H, 2 x CH2), 2.41 (s, 3H, CH3), 4.06 (q, 2H, J = 7.32 Hz, CH2), 5.15 (s, 1H, CH-Ar), 5.75 (br s, 1H, NH), 7.34-7.98 (m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz) – δ : 14.3, 19.5, 27.1, 29.5, 29.8, 31.5, 32.8, 37.1, 40.9, 50.6, 60.2, 105.1, 111.2, 114.8, 121.1, 121.4, 123.0, 128.7, 129.2, 134.9, 144.7, 148.3, 149.2, 167.0, 195.7; Anal calcd. For C21H24N2O5 : C, 65.61; H, 6.29; N, 7.29; Found : C, 64.74; H, 6.17; N, 6.24.
Ethyl-1,4,5,6,7,8-hexahydro-2,7,7-trimethyl-4-(benzo[1,3]dioxol-5-yl)-5-oxoquinoline-3-carboxylate (5e) : IR (nujol, cm-1) - 3293, 3081, 2959, 1694, 1608, 1486, 1381, 1218; 1H NMR (CDCl3, 400 MHz) - δ : 0.96 (s, 3H, CH3), 1.07 (s, 3H, CH3), 1.21 (t, 3H, J = 7.2 Hz, CH3), 2.14-2.30 (m, 4H, 2 x CH2), 2.36 (s, 3H, CH3), 4.06 (q, 2H, J = 7.12 Hz, CH2), 4.97 (s, 1H, CH-Ar), 5.84 (s, 2H), 6.42 (br s, 1H, NH), 6.76-7.22 (m, 3H, Ar-H); 13C NMR (CDCl3, 100 MHz) - δ : 14.2, 19.2, 27.2, 29.4, 32.6, 36.2, 40.8, 50.7, 59.8, 100.6, 106.1, 107.6, 108.6, 111.9, 121.0, 141.4, 143.4, 145.6, 147.1, 148.7, 167.5, 195.8; Anal calcd. For C22H25NO5 : C, 68.91; H, 6.57; N, 3.65; Found : C, 68.66; H, 6.44; N, 3.63.
Ethyl-1,4,5,6,7,8-hexahydro-2-methyl-4-(phenyl)-5-oxoquinoline-3-carboxylate (5g) : IR (nujol, cm-1) - 3287, 2922, 1696, 1607, 1481, 1379, 1222, 1181; 1H NMR (DMSO-d6, 400 MHz) - δ : 1.20 (t, 3H, J = 7.12 Hz, CH3), 1.97-2.39 (m, 6H, 3 × CH2), 2.41 (s, 3H, CH3), 4.06 (q, 2H, J = 7.14 Hz, CH2), 5.12 (s, 1H, CH-Ar), 5.77 (br s, 1H, NH), 7.12-7.22 (m, 5H, Ar-H); 13C NMR (DMSO-d6, 100 MHz) – δ : 13.9, 18.6, 20.8, 26.6, 36.0, 36.8, 59.2, 104.8, 112.3, 125.5, 127.5, 127.7, 144.3, 147.4, 150.8, 167.4, 195.6; Anal calcd. For C19H21NO3 : C, 73.29; H, 6.80; N, 4.50; Found : C, 73.20; H, 6.69; N, 4.38.
Ethyl-1,4,5,6,7,8-hexahydro-2-methyl-4-(2-thienyl)-5-oxoquinoline-3-carboxylate (5h) : IR (nujol, cm-1) - 3284, 2928, 1608, 1476, 1378, 1220, 1073; 1H NMR (DMSO-d6, 400 MHz) - δ : 1.23 (t, 3H, J = 7.08 Hz, CH3), 2.29 (s, 3H, CH3), 1.98-2.48 (m, 6H,3 × CH2), 4.13 (q, 2H, J = 7.04 Hz, CH2), 5.42 (s, 1H, CH-Ar), 6.11 (br s, 1H, NH), 6.80-7.02 (m, 3H, thienyl); 13C NMR (DMSO-d6, 100 MHz) – δ : 14.0, 18.3, 20.7, 26.3, 30.5, 36.7, 59.2, 103.8, 111.1, 122.5, 122.5, 126.0, 145.0, 151.6, 167.0, 195.4; Anal calcd. For C17H19NO3S : C, 64.33; H, 6.03; N, 4.41; Found : C, 64.20; H, 5.70; N, 4.25.
Ethyl-1,4,5,6,7,8-hexahydro-2-methyl-4-(4-nitrophenyl)-5-oxoquinoline-3-carboxylate (5i) : IR (nujol, cm-1) - 3291, 3078, 2952, 1694, 1606, 1485, 1379, 1226; 1H NMR (CDCl3, 400 MHz) - δ : 1.19 (t, 3H, J = 7.36 Hz, CH3), 1.91-2.45 (m, 6H, 3 × CH2), 2.40 (s, 3H, CH3), 4.06 (q, 2H, J = 7.3 Hz, CH2), 5.18 (s, 1H, CH-Ar), 6.48 (br s, 1H, NH), 7.27-7.49 (m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz) – δ : 14.1, 19.4, 21.0, 27.4, 36.8, 37.0, 60.1, 104.8, 112.3, 123.3, 128.9, 144.3, 146.2, 150.3, 154.5, 166.8, 195.7; Anal calcd. For C19H20N2O5 : C, 64.04; H, 5.66; N, 7.86; Found : C, 63.89; H, 5.53; N, 7.74.
Ethyl-1,4,5,6,7,8-hexahydro-2-methyl-4-(2-furanyl)-5-oxoquinoline-3-carboxylate (5k) : IR (nujol, cm-1) - 3291, 3080, 2918, 1610, 1484, 1379, 1222; 1H NMR (CDCl3, 400 MHz) - δ : 1.13 (t, 3H, J = 7.04 Hz, CH3), 2.20 (s, 3H, CH3), 1.87-2.46 (m, 6H, 3 × CH2), 4.02 (q, 2H, J = 7.04 Hz, CH2), 5.06 (s, 1H, CH-Ar), 5.76 (br s, 1H, NH), 7.06-7.56 (m, 3H, furanyl); 13C NMR (CDCl3, 100 MHz) – δ : 14.2, 19.2, 20.1, 21.7, 28.1, 29.5, 30.9, 36.5, 59.8, 103.2, 105.1, 110.2, 141.0, 143.5, 150.2, 157.7, 167.4, 195.2; Anal calcd. For C17H19NO4 : C, 67.76; H, 6.36; N, 4.65; Found : C, 67.56; H, 6.19; N, 4.42.