Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2015 Supporting Information Sandmeyer Cyanation of Arenediazonium Tetrafluoroborate Using Acetonitrile as Cyanide Source Wenbin Xu a,qinghui Xu a, Jizhen Li a, *, Zhenfa Zhang b, * a Department of Organic Chemistry, College of Chemistry, Jilin University, 2519 Jiefang Road, Changchun, 130023, China b Department of Environmental science and Engineering, School of Public Health, University of North Carolina at Chapel Hill, 135Dauer Drive, Chapel Hill, NC 27599-7431 * Corresponding author: ljz@jlu.edu.cn, zhenfaz@email.unc.edu Contents General...S2 Experimental procedures.. S3 S8 Spectroscopic data... S9 S43 References-------------------------------------------------------------------------------------S44 S1
General: All reagents were purchased from commercial sources and used without treatment, unless otherwise indicated. Acetonitrile was dried and newly distilled. NMR spectra were obtained on a Bruker AMX 400 system using chloroform-d as deuterated solvents, with proton and carbon resonances at 400 MHz and MHz, respectively. Mass spectra were measured on an Agilent1290-micrOTOF Q II system spectrometer. IR (KBr pellets) spectra were recorded in the 400-4000 cm -1 range on a Nicolet360 spectrophotometer. S2
General synthesis of arenediazonium tetrafluoroborates In an Erlenmeyer flask, the aniline (10 mmol) was dissolved in an aqueous solution of HBF 4 (50%, 5.0 ml, 40 mmol) and a saturated solution of sodium nitrite (760 mg, 11 mmol) was added dropwise at 0 C. The excess of oxidant was removed by the addition of urea. Then, the precipitated diazonium salt was filtered off and dissolved in the less amount of acetone. Diethyl ether was added to the clear solution, causing the precipitation of the arenediazonium tetrafluoroborate that was filtered off and washed with diethyl ether (3 10 ml). The arenediazonium tetrafluoroborate was dried in vacuo (10-3 mbar) for 10 minutes and then directly used without further purification. General synthesis of aryl nitriles from the corresponding arenediazonium salts. To a solution of arenediazonium tetrafluoroborate (0.5 mmol) in MeCN (3.0 ml) was added PdCl 2 (8.8mg, 0.05mmol) and Ag 2 O (116 mg, 0.5 mmol). The mixture was stirred at 55 for 24 h under air. Then the reaction mixture was cooled to room temperature and filtered through a pad of celite (1.0 g) and rinsed with CH 2 Cl 2 (10 ml). The resulting organic solution was concentrated under reduced pressure and further purified by flash chromatography (SiO 2, petroleum ether/ethyl acetate gradient), yielding the corresponding aryl nitriles 2a-2r. The byproducts 3a-3r and 4a-4r sometimes were also isolated depending on the substrates. R N 2 + BF 4 - R R R CN + NHCOCH 3 + R 1a-1r 2a-2r 3a-3r 4a-4r Scheme 1 Scope of the Sandmeyer reaction using CH 3 CN as cyanide source. S3
R = EtO MeO n-buo a Cl b OMe c MeO MeO MeO MeO d e f Br Cl Br g h i Br j O 2 N k O EtO l O m n o p q r Scheme 2. Scope of the Sandmeyer reaction using CH 3 CN as cyanide source Table 1 Pd-Catalyzed Sandmeyer cyanation of aryldiazonium tetrafluoroborate in acetonitrile: products distribution a, b. R N 2 + BF 4 - R R R CN + NHCOCH 3 + R 1a-1r 2a-2r 3a-3r 4a-4r 1 Yield (%) 2 Yield (%) 3 Yield (%) 4 (1) Yield (%) 2 Yield (%) 3 Yield (%) 4 a 64 nd 24 j 30 nd 28 b 61 nd 12 k 38 nd trace c 61 nd 26 l 32 nd 16 d 50 nd 20 m 35 nd trace e 62 nd trace n nd 83 nd f 55 nd 18 o nd 92 nd g 35 nd 12 p nd 92 nd h 31 nd 15 q nd 85 nd i 45 nd 13 r nd 87 nd a isolated yields. b under the optimized conditions. nd: not detected. 4-Ethoxybenzonitrile (2a). Yield: 64%; White solid; m.p. 55-57 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 1.47 (t, J = 7.2 Hz, 3H), 4.01-4.14 (m, 2H), 6.95 (d, J = 8.0 Hz, 2H), 6.60 (d, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 14.6, 93.9, 103.7, 115.2, S4
119.3, 133.9, 162.3; IR (KBr, cm -1 ): = 2978, 2936, 2225, 1609, 1506, 1264, 1036, 842, 545; HRMS (ESI-TOF): calcd for C 9 H 9 NO 148.0757 (M+H) +, found 148.0759. 4-Methoxybenzonitrile (2b) 1. Yield: 61%; White solid; m.p.51-53 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 3.88 (s, 3H), 6.97 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 55.6, 103.9, 114.8, 119.2, 113.9, 162.9; IR (KBr, cm - 1 ): = 2919, 2844, 2216, 1603, 1506, 1260, 1027, 825, 549. 4-Butoxybenzonitrile(2c) 2.Yield: 61%;Yellow liquid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 0.98 (t, J=7.2, 3H), 1.44-1.51(m, 2H), 1.74-1.82 (m, 2H), 4.00 (t, J=6.4, 2H), 6.93(d, J=8.0,2H), 7.56 (d, J=8.0, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 13.7, 19.1, 31.0, 68.1, 103.7, 115.2, 119.3, 133.9, 162.5; IR (KBr, cm -1 ): =2960, 2226, 1609, 1504, 1255, 1169, 833. 3-Chloride- 4-Methoxybenzonitrile (2d). Yield: 50%; Yellow solid; m.p. 108-110 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 4.00 (s, 3H), 6.99-7.02 (m, 1H), 7.57-7.60 (m, 1H), 7.68-7.69 (m, 1H). 13 C NMR (CDCl 3, MHz, ppm): δ 56.6, 104.7, 112.3, 117.9, 123.5, 132.5, 133.5, 158.6; IR (KBr, cm -1 ): = 2854, 2232, 1596, 1499, 1298, 1063, 814, 717, 594; HRMS (ESI-TOF): calcd for C 8 H 6 NClO 168.0211 (M+H) +, found 168.0223. 2, 4-Dimethoxybenzonitrile (2e) 3. Yield: 62%; Yellow solid; m.p. 92-94 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 3.88 (s, 3H), 3.92 (s, 3H), 6.48 (s, 1H), 6.52-6.55 (m, 1H), 7.50 (d, J = 8.0, 1H); 13 C NMR (CDCl 3, MHz, ppm): δ 55.7, 56.0, 93.9, 98.5, 105.8, 117.0, 134.9, 162.9, 164.7; IR (KBr, cm -1 ): = 2923, 2847, 2225, 1602, 1506, 1215, 1022, 842, 517. 3, 4-Dimethoxybenzonitrile (2f) 4. Yield: 55%; White solid; m.p. 56-58 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 3.92 (s, 3H), 3.95 (s, 3H), 6.92 (d, J = 8.0 Hz, 1H), 7.09-7.10 (m, 1H), 7.29-7.32 (m, 1H); 13 C NMR (CDCl 3, MHz, ppm): δ 56.1, 56.2, 103.9, 111.3, 113.9, 119.2, 126.5, 149.2, 152.9; IR (KBr, cm -1 ): = 2936, 2840, 2218, 1596, 1513, 1271, 1139, 1022, 759, 614. 3-Methyl-4-Bromide benzonitrile (2g).Yield: 35%; Brown solid; m.p. 47-49 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.46 (s, 3H), 7.34-7.37 (m, 1H), 7.54 (s, 1H), 7.67 (d, J = 8.0 Hz, 1H). 13 C NMR (CDCl 3, MHz, ppm): δ 22.9, 111.4, 118.2, 130.5, 130.6, 133,4, 133.8, 139.7; IR (KBr, cm -1 ): = 2232, 1589, 1471, 1029, 822, 586. S5
4-Chloride benzonitrile (2h) 3.Yield: 31%; Yellow solid; m.p. 84-86 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 7.49 (d, J = 8.0 Hz, 2H), 8.06 (d, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 110.8, 117.9, 129.7, 113.4, 139.6; IR (KBr, cm -1 ): = 3089, 3033, 2923, 2225, 1596, 1485, 1091, 828, 538. 2, 6-Dimethyl-4-Bromide benzonitrile (2i) 5. Yield: 45%; Yellow solid; m.p. 133-136 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.53 (s, 6H), 7.33 (s, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 20.6, 112.4, 116.6, 127.1, 130.6, 143.8; IR (KBr, cm -1 ): = 2916, 2854, 2218, 1581, 1464, 1257, 1174, 856, 738, 5. 4-Bromide benzonitrile (2j) 1. Yield: 30%; Yellow solid; m.p. 106-108 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 7.55 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 111.3, 118.1, 128.0, 132.7, 133.4; IR (KBr, cm -1 ): = 2923, 2847, 2218, 1581, 1478, 1063, 821, 538. 4-Nitro benzonitrile (2k) 1. Yield: 38%; Yellow solid; m.p. 133-135 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 7.91 (d,j = 8.0 Hz, 2H), 8.38 (d, J = 8.0 Hz, 2H); 13 C NMR, (CDCl 3, MHz, ppm): δ 116.8, 118.4, 124.3, 133.5, 150.1; IR (KBr, cm -1 ): = 3109, 2234, 1602, 1527, 1347, 863, 746, 684, 538. Ethyl 4-cyanobenzoateate (2l) 6. Yield: 32%; Yellow solid; m.p. 48-50 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 1.43 (t, J=7.2 Hz, 3H), 4.41-4.46 (m, 2H), 7.76 (d, J = 8.0 Hz, 2H), 8.16 (d, J=8.0 Hz, 2H); 13 C NMR, (CDCl 3, MHz, ppm): δ 14.2, 61.8, 116.3, 118.0, 130.1, 132.2, 134.3, 164.9; IR (KBr, cm -1 ): =3096, 2958, 2902, 2225, 1727, 1277, 1105, 870, 766, 690, 545. 4-Acetylbenzonitrile (2m) 3. Yield: 35%; White solid; m.p. 49-51 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.67 (s, 3H), 7. (d, J = 8.0 Hz, 2H),8.06 (d, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3, MHz, ppm): δ 26.8, 116.4, 117.9, 128.7, 132.5, 139.9, 196.5; IR (KBr, cm -1 ): = 2923, 2232, 1685, 1402, 1246, 828, 594, 538. NHCOCH 3 NHCOCH 3 NHCOCH 3 3n, 83% 3o, 92% 3p, 92% NHCOCH 3 NHCOCH 3 3q, 85% 3r, 87% S6
Scheme 3. Unexpected byproducts of substrates under the standard conditions Acetanilide (3n) 7. Yield: 83%; Yellow solid; m.p. 110-112 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.20 (s, 3H), 7.11-7.15 (m, 1H), 7.25 (s, 1H), 7.73-7.36 (m, 2H), 7.51-7.53 (m, 2H); IR (KBr, cm -1 ): = 3289, 1665, 1430, 1430, 1319, 745, 690, 510. 4-Methylacetanilide (3o) 8. Yield: 92%; White solid; M.P. 145-147 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.18 (s, 3H), 2.33 (s, 3H), 7.14 (d, J = 8.0 Hz, 2H), 7.23 (s, 1H), 7.39 (d, J = 8.0 Hz, 2H); IR (KBr, cm -1 ): = 3289, 3117, 2943, 1665, 1506, 1319, 821, 510. 2-Methylacetanilide (3p) 9. Yield: 92%; White solid; m.p. 104-106 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.24 (s, 3H), 2.29 (s, 3H), 6.96 (s, 1H), 7.09-7.13 (m, 1H), 7.20-7.26 (m, 1H), 7. (d, J = 8.0 Hz, 1H); IR (KBr, cm -1 ): = 3283, 3033, 1658, 1527, 1458, 1271, 752. 3-Methylacetanilide (3q) 10. Yield: 85%; White solid; m.p. 235-237 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.13 (s, 3H), 2.16 (s, 3H), 6.93 (d, J = 8.0 Hz, 1H), 7.17-7.21 (m, 1H), 7.29-7.32 (m, 1H), 7.38 (s, 1H), 7.89 (s, 1H); IR (KBr, cm -1 ): = 3289, 2916, 1665, 1547, 1492, 1367, 7, 690. N-Acetyl-2-aminonaphthalene (3r) 11. Yield: 87%; White solid; m.p. 127-129 ºC; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 2.26 (s, 3H), 7.41-7.48 (m, 4H), 7.81 (d, J = 8.0 Hz, 3H), 8.20 (s, 1H); IR (KBr, cm -1 ): = 3283, 1671, 1561, 1277, 814, 745, 476. EtO OEt MeO OMe n-buo OBu-n 4a, 24% 4b, 12% 4c, 26% Cl MeO OMe MeO OCH 3 MeO OMe Br Br Cl 4d, 20% 4f, 18% 4g, 12% Cl Cl Br Br 4h,15% 4j,28% Scheme 4. Biaryls products 4, 4 -Diethoxybiphenyl (4a) 12. Yield: 24%; white solid; 1 H NMR (CDCl 3, 400 MHz, S7
ppm): δ 1.55-1.59 (t, J=7.2Hz, 6H), 4.17-4.23 (m, 4H), 7.06-7.09 (d, J=8.0Hz, 4H), 7.58-7.61 (d, J=8.0Hz, 4H);IR (KBr, cm -1 ): = 2976, 2928, 1604, 1500, 1272, 1252, 1051, 817, 796, 590, 521. 4, 4 -Dimethoxybiphenyl (4b) 13. Yield: 12%; white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ3.87 (s, 6H), 6.97-7.01 (d, J=8.Hz, 4H), 7.49-7.52 (d, J=8.0Hz, 4H); IR (KBr, cm - 1 ): =2960, 2834, 1605, 1504, 1277, 1251, 1182, 1037, 823, 810, 514. 4, 4 -Dibutoxybiphenyl (4c) 14. Yield: 26%; white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ0.96-1.01 (t, J=7.2Hz, 6H), 1.48-1.52 (m, 4H), 1.71-1.84 (m, 4H), 3.97-4.02 (t, J=6.8Hz, 4H), 6.93-6.96 (d, J=8.0Hz, 4H), 7.44-7.47 (d, J=8.0Hz, 4H); IR (KBr, cm - 1 ): = 2955, 2929, 1617, 1498, 1277, 1251, 1037, 817, 4. 3, 3 -Dichloro-4, 4 -Dimethoxybiphenyl (4d). Yield: 20%; white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 3.94 (s, 6H), 6.96-6.99 (d, J=8.0Hz, 2H), 7.36-7.39 (d, J=8.0Hz, 2H), 7.54 (s, 2H), IR (KBr, cm -1 ): = 2923, 1561, 1491, 1251, 1069, 1019, 873, 811, 728. 3, 3-4, 4 -Tetramethoxybiphenyl (4f) 14. Yield: 18%; white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ3.85 (s, 6H), 3.86 (s, 6H), 6.76-6. (m, 2H), 6.-6,93(m, 4H); IR (KBr, cm -1 ): = 2929, 2828, 1511, 1460, 1258, 1220, 1119, 1025, 956, 741. 3, 3 -Dimethyl-4, 4 -Dibromobiphenyl (4g). Yield: 12%, white solid; 1 H NMR (CDCl 3, 400MHz, ppm): δ 2.46 (s, 6H), 7.20-7.26 (m, 2H), 7.45 (s, 2H), 7.56-7.59 (d, J=8.0Hz, 2H); IR (KBr, cm -1 ): = 2918, 2855, 1557, 1469, 1025, 4. 4, 4 -Dichlorobiphenyl (4h) 15.Yield:15%, white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ7.39-7.42 (d, J=8.0Hz, 4H), 7.46-7.49 (d, J=8.0Hz, 4H); IR (KBr, cm -1 ): = 1564, 1095, 0, 817, 506. S8
4, 4 -Dibromobiphenyl (4j) 16. Yield: 28%, white solid; 1 H NMR (CDCl 3, 400 MHz, ppm): δ 7.42-7.45 (d, J=8.0Hz, 4H), 7.57-7.60 (d, J=8.0Hz, 4H); IR (KBr, cm -1 ): = 1664, 1627, 1475, 13, 1101, 0, 4, 538, 500. Spectroscopic data Compound 2a 1 H NMR(400MHz,CDCl 3 ) Compound 2a 13 C NMR(MHz,CDCl 3 ) S9
Compound 2a IR (KBr, cm -1 ) 2936 T/% 60 2978 2225 40 20 545 1506 EtO CN 1264 1609 1036 842 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 2a HRMS S10
Compound 2b 1 H NMR(400MHz,CDCl 3 ) S11
Compound 2b 13 C NMR(MHz,CDCl 3 ) Compound 2b IR (KBr, cm -1 ) T/% 60 2919 2844 683 40 549 MeO 2216 CN 825 1027 20 1506 1603 1260 0 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 2c 1 H NMR(400MHz,CDCl 3 ) S12
n-buo CN Compound 2c 13 C NMR(MHz,CDCl 3 ) S13
n-buo CN Compound 2c IR (KBr, cm -1 ) 99.83387 98.26028 (99.6797) n-buo 2960 CN 2226 1609 1504 1169 833 1255 3500 3000 2500 2000 1500 0 500 399.2123 (401.1409) S14
Compound 2d 1 H NMR(400MHz,CDCl 3 ) Compound 2d 13 C NMR(MHz,CDCl 3 ) S15
Compound 2d IR (KBr, cm -1 ) 2854 T/% 60 1596 717 594 Cl 2232 1063 814 40 MeO CN 1298 20 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 1499 Compound 2d HRMS S16
Compound 2e 1 H NMR(400MHz,CDCl 3 ) Compound 2e 13 C NMR(MHz,CDCl 3 ) S17
Compound 2e IR (KBr, cm -1 ) 2847 2923 T/% 517 OMe 2225 1506 1022 842 60 MeO CN 1602 1215 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 2f 1 H NMR(400MHz,CDCl 3 ) S18
Compound 2f 13 C NMR(MHz,CDCl 3 ) Compound 2f IR (KBr, cm -1 ) 2840 2936 759 614 T/% MeO 2218 1596 1022 1139 60 MeO CN 1513 1271 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S19
Compound 2g 1 H NMR(400MHz,CDCl 3 ) Compound 2g 13 C NMR(MHz,CDCl 3 ) S20
Compound 2g IR (KBr, cm -1 ) 586 T/% 1589 822 Br CN 2232 1471 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 1029 Compound 2h 1 H NMR(400MHz,CDCl 3 ) S21
Compound 2h 13 C NMR(MHz,CDCl 3 ) Compound 2h IR (KBr, cm -1 ) 2923 3033 3089 T/% 60 2225 1596 1395 40 Cl CN 1485 1091 20 828 538 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S22
Compound 2i 1 H NMR(400MHz,CDCl 3 ) Compound 2i 13 C NMR(MHz,CDCl 3 ) S23
Compound 2i IR (KBr, cm -1 ) 0.12 0.10 0.08 T/% 0.06 0.04 2916 2854 2218 1464 1257 1174 5 0.02 Br CN 1581 738 0.00 856 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 2j 1 H NMR(400MHz,CDCl 3 ) S24
Compound 2j 13 C NMR(MHz,CDCl 3 ) Compound 2j IR (KBr, cm -1 ) 2847 2923 2218 T/% 1581 1063 538 Br CN 1478 821 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S25
Compound 2k 1 H NMR(400MHz,CDCl 3 ) Compound 2k 13 C NMR(MHz,CDCl 3 ) S26
Compound 2k IR (KBr, cm -1 ) 3109 T/% 60 2234 1602 684 538 746 40 O 2 N CN 1527 1347 863 20 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 2l 1 H NMR(400MHz,CDCl 3 ) S27
Compound 2l 13 C NMR(MHz,CDCl 3 ) Compound 2l IR (KBr, cm -1 ) 3096 2902 2985 T/% 2225 1105 690 870 545 EtOOC CN 1277 766 1727 60 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S28
Compound 2m 1 H NMR(400MHz,CDCl 3 ) Compound 2m 13 C NMR(MHz,CDCl 3 ) S29
Compound 2m IR (KBr, cm -1 ) 2923 T/% 2232 60 O CN 1685 1402 1257 594 835 538 40 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 3n 1 H NMR(400MHz,CDCl 3 ) S30
Compound 3n IR (KBr, cm -1 ) 1319 T/% 3289 1430 510 1665 690 NHCOCH 3 745 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 3o 1 H NMR(400MHz,CDCl 3 ) S31
Compound 3o IR (KBr, cm -1 ) 2943 3117 T/% 3289 510 NHCOCH 3 1506 1319 821 1665 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 3p 1 H NMR(400MHz,CDCl 3 ) S32
Compound 3p IR (KBr, cm -1 ) 3033 T/% 3289 1271 752 1458 NHCOCH 3 1658 1527 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 Compound 3q 1 H NMR(400MHz,CDCl 3 ) S33
Compound 3q IR (KBr, cm -1 ) T/% 60 3289 2916 1367 7 690 1492 40 NHCOCH 3 1547 1665 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S34
Compound 3r 1 H NMR(400MHz,CDCl 3 ) Compound 3r IR (KBr, cm -1 ) 3283 476 T/% 1277 814 745 NHCOCH 3 1671 1561 60 3500 3000 2500 2000 1500 0 500 0 σ/cm -1 S35
Compound 4a 1 H NMR(400MHz,CDCl 3 ) EtO OEt Compound 4a IR (KBr, cm -1 ) S36
99.32533 98.28787 (98.96395) 60 EtO 2976 2928 OEt 1604 590 1500 1272 796 1252 1051 817 521 40 3500 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) Compound 4b 1 H NMR(400MHz,CDCl 3 ) H 3 CO OCH 3 Compound 4b IR (KBr, cm -1 ) S37
94.77666 95.18626 (94.53796) 60 2960 2834 1605 H 3 CO OCH 3 1504 1182 1277 1251 1037 810 514 40 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) 823 Compound 4c 1 H NMR(400MHz,CDCl 3 ) n-buo OBu-n Compound 4c IR (KBr, cm -1 ) S38
99.63146 n-buo OBu-n (99.83599) 2929 2955 1498 1617 1277 1251 1037 4 817 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) Compound 4d 1 H NMR(400MHz,CDCl 3 ) S39
Compound 4d IR (KBr, cm -1 ) 87.85948 87.61448 (87.84789) 2923 Cl Cl 1561 1491 1251 1019728 873 811 1069 MeO OMe 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) Compound 4e 1 H NMR(400MHz,CDCl 3 ) H 3 CO OCH 3 H 3 CO OCH 3 Compound 4e IR (KBr, cm -1 ) S40
94.45323 H 3 CO OCH 3 H 3 CO OCH 3 93.94647 (93.92982) 2828 2929 956 1460 741 1119 1025 1258 1220 1511 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) Compound 4h 1 H NMR(400MHz,CDCl 3 ) Cl Cl S41
Compound 4h IR (KBr, cm -1 ) 85.6786 Cl Cl 85.836 (85.2578) 1564 0 1095 506 817 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) Compound 4j 1 H NMR(400MHz,CDCl 3 ) Br Br Compound 4j IR (KBr, cm -1 ) S42
97.93554 (98.57657) 1664 1475 1101 1627 13 0 538 500 60 Br Br 40 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) 4 Compound 4g 1 H NMR(400MHz,CDCl 3 ) Compound 4g IR (KBr, cm -1 ) S43
94.38457 Br Br 91.42554 (92.84297) 2855 2918 1557 1469 4 1025 3000 2500 2000 1500 0 500 0 399.2123 (401.1409) S44
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