In this study, Hantzsch condensation was used to design and synthesize new analogues of dihydropyridine (DHP). Different diary carboxamides were inserted at positions 3 and 5 of the DHP ring. 4(5)-chloro-2-ethyl-5(4)-imidazolyl moiety was considered at position 4 of the DHP ring. The structures of prepared ligands were characterized using TLC followed by FT-IR, elemental analysis, Mass and proton NMR. Results of anti-tubercular activity have indicated all the prepared ligands 3a-f inhibit the mycobacterium tuberculosis growth and the most potent compounds were 3c  and 3b (4-Cl). The  After AIDS, tuberculosis (TB) is one of the most common reasons of death from infectious disease and around 1/3 of the world’s population are infected with mycobacterium tuberculosis . Since t1, 4-Dihydropyridine (DHP) acts as calcium channel modulators -14, and Using the aryl amide in the positions 3 and 5 of DHPs result in to increase the anti-tubercular activity and reduce the calcium channel modulatory activities -23. LipoChemistryAll of the prepared ligands were characterized using thin layer chromatography followed by FT-IR, Mass, elemental analysis and H-NMR. Melting points were firmed using a Thomas- Hoover capillary apparatus and were uncorrected. 1HNMR spectra were recorded on a Bruker FT-250 spectrometer TMS was used as an internal standard. Infrared spectra were acquired on a Nicolet 550-FT spectrometer. Mass spectra were measured with a Finnigan TSQ-70 spectrometer . Elemental analysis was done using a Perkin-Elmer model 240-C apparatus. The results of elemental analysis  were within ± 0.4% of the calculated amounts. Reagents and solvents were prepared from MERCK . DHPs 3a-f . were prGeneral procedure for the preparation of 3-oxo-N-aryl butanamide (1a-g) A solution of an appropriate arylamine and 2, 2, 6-trimethyl-1, 3-dioxin-4-one in xylene was placed in an Erlenmeyer flask. The flask was immersed in an oil bath that had been preheated to 150 °C, and the solution was vigorously stirred. The evolution of acetone became apparent within several minutes and heating was continued for 3-4 h. The xylene was then removed, and the product was filtered and recrystallized from appropriate organic solvents.N-(4-fluorophenyl)-3-oxobutanamide (1a)−1 (CO). 1H-NMR (CDCl3): δ (ppm) 2.29 , 3.70 , 7.15-7.25 , 7.56-7.78 , 9.40 .Using the general procedure and 4-fluoroaniline provided the title compound after 3 h of reflux: White crystals , Yield 88%, mp 98-101 °C. IR (KBr): ν 3315(NH), 1716, 1671 cmN-(4-chlorophenyl)-3-oxobutanamide (1b)−1 (CO). 1H-NMR (CDCl3): δ (ppm) 2.30 , 3.58 , 7.23 , 7.50 , 9.37 . Using the general procedure and 4-chloroaniline provided the title compound after 3 h of reflux: White crystals , Yield 79%, mp 127-129 °C. IR (KBr): ν 3300(NH), 1720, 1670 cmN--3-oxobutanamide (1c)−1 (CO). 1H-NMR (CDCl3): δ (ppm) 2.39 , 3.65 , 7.30-7.47 , 8.05 , 9.45 .Using the general procedure and 3, 4-dichloroaniline provided the title compound after 4 h of reflux: White crystals , Yield 65%, mp 79-81 °C. IR (KBr): ν 3378(NH), 1710, 1665 cmN-(3-bromophenyl)-3-oxobutanamide (1d)−1 (CO). 1H-NMR (CDCl3): δ (ppm) 2.29 , 3.54 , 7.18-7.45 , 7.78 , 9.25 . Using the general procedure and 3-bromoaniline provided the title compound after 3 h of reflux: Light yellow crystals , Yield 80%, mp 98-101 °C. IR (KBr): ν 3300(NH), 1712, 1673 cmN-(2-nitrophenyl)-3-oxobutanamide (1e)−1 NO2. 1H-NMR (DMDO-d6): δ (ppm) 2.20 , 3.61 , 7.35 , 7.73 , 7.98 , 10.50 .Using the general procedure and 2-nitroaniline provided the title compound after 4 h of reflux: Yellow crystals (from petroleum ether), Yield 70%, mp 142-143 °C. IR (KBr): ν 3180 (NH), 1716 (CO), 1350 and 1550cmN--3-oxobutanamide (1f)−1 NO2. 1H-NMR (DMDO-d6): δ (ppm) 2.17 , 3.51 , 8.01 , 8.52 , 8.70 , 10.71 .Using the general procedure and 2,4-dinitroaniline provided the title compound after 4 h of reflux: Yellow crystals (from petroleum ether), Yield 68%, mp 162-165 °C. IR (KBr): ν 3300 (NH), 1726 (CO), 1350 and 1550cmGeneral procedure for preparation of diaryl 4-(4(5)-chloro-1H-imidazol-5 (4)-yl)-2, 6-dimethyl-1, 4-dihydropyridine-3, 5-di- carboxamide (3a-f)A light protected solution of compound 2 (1 mmol), ammonium acetate (1 mmol), and compounds 1a-f (2 mmol) in methanol (2.5 mL) was refluxed. The reaction mixture was cooled to room temperature, filtered and recrystallized from diethyl ether to give the title compounds.4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis (4-fluorophenyl)-1, 4-dihydropyridine-3, 5-dicarboxamide (3a)oC. IR (KBr): ν (cm−1) 3221 (NH), 1680, 1649(CO).; 1H-NMR (DMSO- d6): δ (ppm) 1.10 , 2.09 , 2.48 , 5.12 , 7.10 , 7.49-7.67 , 8.23 , 9.23 , 11.36 .; Mass: m/z (rel.int.) 511, 509.3(6), 473.2(100), 404.3(22), 401.3(74), 365(45), 334.7(23), 271.1(47), 259.7(36), 158.7(21), 131.8(30), 129.8(37). Molecular Formula = C26H24ClF2N5O2; Calculated = C(61.00%) H(4.73%) N(13.68%), Found = C(61.05%) H(4.74%) N(13.70%).Using the general procedure and compound 1a provided the title compound after 24 h of reflux: white crystals, yield 56%; mp 240-247 4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis (4-chlorophenyl)-1, 4-dihydropyridine-3, 5-dicarboxamide (3b)oC. IR (KBr): ν (cm−1) 3226 (NH), 1680, 1634 (CO). 1H-NMR (DMSO- d6): δ (ppm) 1.10 , 2.10 , 2.49 , 5.10 , 7.28 , 7.59 , 8.39 , 9.08 , 510.1(30), 505.8(39), 436(23), 417(80), 380.7(100), 378.5(44), 286.9(29), 262.1(15), 154.9(8), 152.8(14), 127(22), 98.8(16). Molecular Formula = C26H24Cl3N5O2; Calculated = C(57.31%) H(4.44%) N(12.85%) , Found = C(57.39%) H(4.45%) N(12.83%).amides), 11.32 .; Mass: m/z (rel.int.) 544(M4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis -1, 4-dihydropyridine-3, 5-dicarboxamide (3c)oC. IR (KBr): ν (cm−1) 3298, 3262 (NH), 1654 (CO). 1H-NMR (DMSO- d6): δ (ppm) 1.08 , 2.08 , 2.48 , 5.07 , 7.49 , 7.97 , 8.39 , 9.48 , 11.32 .; Mass: m/z (rel.int.) 612.9, 575.8(3), 480(21), 414.8(8), 389(13), 320.7(87), 260.9(41), 186.8(63), 123.7(73), 106.2(100), 79.7(42). Molecular Formula = C26H22Cl5N5O2; Calculated = C(50.88%) H(3.61%)N(11.41%), Found = C(50.91%) H(3.62%)N(11.43%). Using the general procedure and compound 1c provided the title compound after 24 h of reflux: White crystals, yield 60.7%; mp 170.8-176.2 4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis (3-bromophenyl)-1, 4-dihydropyridine-3, 5-dicarboxamide (3d)oC. IR (KBr): ν (cm−1) 3308, 3277 (NH), 1640, 1634 (CO). 1H-NMR (DMSO- d6): δ (ppm) 1.12 , 2.12 , 2.52 , 5.12 , 7.2-7.3 , 7.5-7.6 , 7.8 , 8.3 , 9.4 , 11.3 .; Mass: m/z (rel.int.) 633, 598(15), 580(7), 504.6(23), 434.2(22), 333.1(31), 264.2(25), 235.9(37), 196.6(100), 132.1(78), 90.4(95). Molecular Formula = C26H24Br2ClN5O2; Calculated = C(49.27%) H(3.82%) N(11.05%), Found = C(49.24%) H(3.83%) N(11.03%).Using the general procedure and compound 1d provided the title compound after 28 h of reflux: White crystals, yield 66%; mp 160.2-170.6 4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis (2-nitrophenyl)-1, 4-dihydropyridine-3, 5-dicarboxamide (3e)oC. IR (KBr): ν (cm−1) 3359, 3231 (NH), 1644 (CO), 1347, 1495(NO2). 1H-NMR (DMSO- d6): δ (ppm) 1.12 , 2.18 , 2.51 , 5.01 , 7.28 , 7.68  7.78 , 7.98 , 8.63 , 9.89 , 11.38 .; Mass: m/z (rel.int.) 565, 564.4(4), 528.1(10), 436.6 (22), 402(31), 400.4(85), 298.1(68), 232.7(100), 220.3(90), 164.4(65), 90(92), 63.3(92). Molecular Formula = C26H24ClN7O6; Calculated = C(55.18%) H(4.27%) N(17.32%), Found = C(55.23%) H(4.28%) N(17.34%).Using the general procedure and compound 1e provided the title compound after 32 h of reflux: Orange crystals, yield 68%; mp 180.1-190.2 4-(4(5)-chloro-2-ethyl-1H-imidazol-5(4)-yl)-2, 6-dimethyl-N3, N5-bis -1, 4-dihydropyridine-3, 5-dicarboxamide (3f)oC. IR (KBr): ν (cm−1) 3339(NH), 1639, 1680 (CO), 1337, 1265 (NO2). 1H-NMR (DMSO- d6): δ (ppm) 1.10 , 2.27 , 2.57 , 5.06 , 8.06 , 8.51 , 8.70, 8.97 , 10.40 , 11.41 .; Mass: m/z (rel.int.) 469.9(6), 342.7(21), 287.9(48), 260.9(23), 245.9(16), 180.9(42), 107.2(29), 91.1(50), 62.1(75). 52.3 (100). Molecular Formula = C26H22ClN9O10; Calculated = C(47.61%) H(3.38%) N(19.22%), Found = C(47.66%) H(3.39%) N(19.25%).Using the general procedure and compound 1f provided the title compound after 36 h of reflux: Yellow crystals, yield 62%; mp 139.5-143.3 Computational studies -1. The optimized conformer was transferred to Gaussian software to calculation of HOMO, LUMO and partial atomic charge (Muliken) using RHF method and 3-21G basis set.The chemical structure of desired DHPs 3a-f was built and optimized using HYPERCHEM software . Optimization of the compounds was performed through MM+ and PM3 methods and total energy gradient was calculated as a root mean square (RMS) value, until the RMS gradient was 0.01 Kcal molIn-vitro evaluation of anti-mycobacterial activityThe test compounds 3a-f, were initially dissolved in DMSO to give a concentration of 1 or 2 mg/L. All wells of micro plates received 100 µL of freshly prepared Middle broke 7H9 medium , except first column. 200 µL of distilled water was added to the first column of 96 well plates to minimize evaporation of the medium in the test wells during incubation. Then 100 µL of test compounds with desired concentrations (1000 or 2000 µL) were added to the wells of the first row (each concentration was assayed in duplicate) and serial dilution was made from the first row to the last. Microbial suspension of BCG (1173P2) (100 µL), which had been prepared with standard concentration of 0.5 McFarland and diluted with 1:10 proportion by the distilled water, was added to all test wells. Plates were then sealed and incubated for 4 days at 37 °C. After that 12 µL Tween 80 10% and 20µL Alamar blue 0.01%  were added to each test well. The results were assessed after 24 and 48 h. A blue color was interpreted as no bacterial growth, and color change to pink was scored as bacterial growth. Wells with a well-defined pink color were scored as positive for growth. The MIC (minimum inhibitory concentration) was defined as the lowest drug concentration, which prevented a color change from blue to pink. Ethambutol  were used as positive control and DMSO as negative control .ChemistrySix new derivatives of dihydropyridine, compounds 3a-f ., were sComputational studies Based on the subjects that mentioned in the introduction section, Partial atomic charge (PAC) of carbon atom of carbonyl moiety at the C-3 and C-5 position of dihydropyridine ring and the lipophilicity (log p) of DHPs 3a-f was calculated using HyperChem and Gaussian software. To calculation the PAC, at first all of the compounds was optimized using HyperChem with molecular mechanics (MM+) and semi-empirical (PM3) methods. To finding the global minima, the best conformer from the previous stage was transferred to Gaussian and more optimization was performed using RHF method and 3-21G basis set. Confirmers with the global minima were used to calculation of partial atomic charges. Results of calculated PAC are presented in Based on the results of the log p calculation (3c>3d>3b>3a>3c>3f), the compounds 3c and 3f are the more and less lipophilic ligands respectively. So it seems that the penetration of these ligands into the cell wall of mycobacterium is according to sequence of 3c>3d>3b>3a>3c>3f. PAC calculation shows in the designed compounds the carbon atom of carbonyl group at the C-3 and C-5 positions are efficiently positive, hence are susceptible to bio hydrolytic activation. Based on the results of mean of PAC at the C-3 and C-5 (3f>3d>3c>3e>3b>3a), the compounds 3f and 3a have the more and less positive PAC respectively. According to the PAC results compound 3f has high value of PAC, it is expected that compound 3f is more susceptible to enzymatic hydrolysis to produce the active compound and so it should be more potent than compound 3a. Considering both of parameters, compound 3f has the worse and the best value of logp and PAC respectively but fortunately the logp of this compound is still enough to penetration into the mycobacterium cells so it is expected to has a good biological activity. Compounds 3b, 3c and 3d have good values of both of parameters so it is expected they have very good potency against the TB.Anti-tubercular activityin-vitro assay. The results are summarized in the in-vitro screening data  and 3c (6.35 µm/mL) which contain one and two Cl group respectively, show the importance of both of parameters (logp and PAC) on the anti-TB activity in which the compounds 3b and 3c are the most potent compounds. The ability of DHPs 3a-f to inhibition of mycobacterium tuberculosis growth was determined using ing data . indicatIn comparison to DHPs which contain the N-substituted imidazole with an electron donating group , our pha1-NMR. The elemental analysis has confirmed the purity of products. Their ability to inhibition of mycobacterium growth was investigated in vitro evaluation. Based on the in vitro screening data all the designed and synthesized compounds 3a-f have the ability to inhibit the mycobacterium tuberculosis growth in term of MIC. The most potent compounds were 3b (4-Cl) and 3c , which our computational studies was predicted this in terms of PAC and logp.Six DHPs analogs (3a-f) were synthesized and characterized by TLC followed by FT-IR, Mass and HThe results so far indicated that the activity of these ligands against the mycobacterium can significantly be influenced by log p of molecules and partial atomic charge of carbon atom of carbonyl moiety at C-3 C-5 position of DHPs ring. The results have also confirmed that anti-tubercular activity can efficiently be increased using the N-unsubtituted imidazole with an electron withdrawing group. Currently, our research group is exploring this idea for designing newer ligands with better anti-tubercular activity.


Xylaria sp. isolated from the stems of Isodon sculponeatus afforded six new compounds, xylariahgins A–F (1–6), two new natural products (7 and 8), along with two known compounds (9 and 10)  contains supplementary material, which is available to authorized users. Isodon is an abundant source of diterpenoids with diverse chemical structures, of which some ones exhibit antitumor and anti-inflammatory activities + at m/z 249.0730 , corresponding to the molecular formula C11H14O5. Comparison of its 1H and 13C NMR spectra  to C-10 and C-9, H2-10  to C-9, C-8 and C-12, H2-8  to C-10, C-9, C-12 and C-4 suggested that the furanone ring of 1 was opened in 2  to C-6 and C-3, from H-3  to C-4, C-7 and C-2, from H-6  to C-4, C-2 and C-5 elucidated the planar structure of 2. The relative configuration of 2 was determined by a hydrolysis reaction of 1. 1 was exposed to K2CO3/MeOH at room temperature for 4 h, with HPLC–DAD analysis detecting conversion to 2 .Xylariahgin B  was obta3) was found by HRESIMS  to possess the molecular formula C12H16O6 as determined. Its IR absorptions at 3395, 1732 and 1660 cm−1 implied the presence of OH, lactone and C=C groups. The 1H and 13C NMR spectra  to C-4 and C-12, and from H-10  to C-12 determined the structure of 3 .Xylariahgin C (4) was found to have the molecular formula C11H14O4 established by HRESIMS at m/z 233.0784 [M+Na]+ , indicating five degrees of unsaturation. Its IR absorptions at 1779 and 1671 cm−1 implied the presence of lactone and C=C groups. The 1H NMR spectrum , one olefinic methine at δH . The 13C NMR and DEPT spectra of 4 displayed resonances for 11 carbons, ascribed to one methyls, four methylenes (including one oxygenated methylene), three methines , and three quaternary carbons (two carbonyls). These data accounted for all 1H and 13C NMR resonances and indicated 4 is a polyketide. The 1H-1H COSY correlations of H2-5/H2-6, suggested the connection from C-5 to C-6. The detailed planar structure of 4 was further constructed by the HMBC correlations. The HMBC correlations from H-3  to C-2, C-4 and C-5, H2-5  to C-4, and H2-6  to C-4, C-2, indicated the presence of pyrone. In the HMBC spectrum of 4, correlations from H2-8  to C-7, C-12 and C-10, coupled with the 1H–1H COSY correlations of H-7/H2-8/H-9/H2-10/H3-11 proved the presence of furanone moiety  was isolated as yellowish oil, and its molecular formula was established to be C13H18O5 by HRESIMS at m/z 253.1081 [M−H]− . Its IR absorptions at 2928, 1773 and 1745 cm−1 implied the presence of lactone and C=C groups. Comparison of the 1H and 13C NMR data  to C-1 and C-6, from H2-7  to C-4, and from 6-OMe  to C-6  was obtained as a yellowish amorphous powder and gave a HRESIMS ion peak at m/z 320.1108 , which corresponded to a molecular formula of C14H19NO6 with six degrees of unsaturation. Its IR absorptions at 2928, 1717 and 1429 cm−1 implied the presence of COOH, C=O and C=C groups. The 1H and 13C NMR spectra (Table δC 14.0), seven methylenes , two olefinic quaternary carbons , four carbonyl carbons . The 1H-1H COSY correlations of H2-4/H2-5/H2-6, and H2-9/H3-10 were observed, HMBC correlations from H3-10  to C-9 and C-8, from H2-4  to C-3, C-5 and C-7, from H-5  to C-7, from H-2  to C-1, C-3 and C-7 suggested compound 6 was a 2-propylcyclopenteneacetic acid derivative. The HMBC correlations of H2-3′  with C-2′ and C-4′, revealed compound 6 was a propanedioic acid derivative , (M+-CONHCOCH2COOH + 2H+), (M+-NHCOCH2COOH), respectively. Then the peak at m/z 181 was a daughter of m/z 195 by means of losing CH2. Similarly, the ion at m/z 137 was a daughter of m/z 181 via loss CO2. Herein, the ion m/z at 123, 137, 181, 252, 251, 169, and 209 in EI+ mass spectrum proved the presence of the fragment ion I–VII . Therefore, the structure of compound 6 was elucidated.Xylariahgin F . Its IR absorptions at 3416, 1711, 1602, 1570, 1457 and 1429 cm−1 implied the presence of OH, lactone and phenyl groups. Comparison of the 1H and 13C NMR data  to C-11, and the 1H–1H COSY correlations of Ha-10/H-11/H2-12  by comparison with the values of specific rotation of orthosporin dimethyl ether  on account of the values of specific rotation was too small to discriminate whether it was experimental error or not D23 − 56.9 , UV (MeOH) λmax (log ε) 414 (1.70), 327 (2.48), 248 (3.97), 207 (3.86) nm, IR (KBr) vmax 2967, 2878, 1781, 1663, 1623, 1414, 1386, 1342, 1153, 1029, 956, 931, 871 cm−1. ESIMS m/z 231 [M+Na]+, HRESIMS m/z 231.0624 [M+Na]+ . 1H NMR  and 13C NMR , see Table Xylariahgin A  yellow o2) colorless oil. [α]D20 − 20.0 , UV (MeOH) λmax (log ε) 248 (3.97), 208 (3.83) nm, IR (KBr) vmax 3422, 2932, 1657, 1595, 1422, 1384, 1328, 1236, 1103, 935, 874 cm−1. ESIMS m/z 249 [M+ Na]+, HRESIMS m/z 249.0730 [M+Na]+ . 1H NMR  and 13C NMR , see Table Xylariahgin B  yellow oil. [α]D24 − 23.1 , UV (MeOH) λmax (log ε) 248 (4.15), 207 (3.99) nm, IR (KBr) vmax 3395, 2964, 2933, 1783, 1732, 1660, 1422, 1384, 1157, 1103, 933, 873 cm−1. ESIMS m/z 263 [M+Na]+, HRESIMS m/z 263.0884 [M + Na]+ . 1H NMR  and 13C NMR , see Table Xylariahgin C (4) yellow oil. [α]D23 − 44.9 , UV (MeOH) λmax (log ε) 295 (3.07), 260 (3.98) nm, IR (KBr) vmax 2966, 2934, 2878, 1779, 1671, 1618, 1464, 1384, 1291, 1229, 1186, 1163, 1076, 984 cm−1. ESIMS m/z 233 [M + Na]+, HRESIMS m/z 233.0784 [M + Na]+ . 1H NMR  and 13C NMR , see Table Xylariahgin D  yellowish oil. UV (MeOH) λmax (log ε) 206 (3.94) nm, IR (KBr) vmax 2956, 2928, 2856, 1773, 1745, 1582, 1384, 1275, 1174, 924, 765 cm−1. ESIMS m/z 253 [M−H]−, HRESIMS m/z 253.1081 [M−H]− . 1H NMR  and 13C NMR , see Table Xylariahgin E (6) yellowish amorphous power. UV (MeOH) λmax (log ε) 225 (4.15) nm, IR (KBr) vmax 2928, 2860, 1717, 1429, 1313, 1194, 1124, 980, 944, 765, 616 cm−1. ESIMS m/z 320 [M+Na]+, HRESIMS m/z320.1108 [M+Na]+ . 1H NMR  and 13C NMR , see Table Xylariahgin F (7): yellowish solid. [α]D24 − 6.7 . UV (MeOH) λmax (log ε) 323 (3.74), 287 (3.72), 278 (3.77), 242 (4.55) nm. IR (KBr) vmax 3416, 2928, 2854, 1711, 1602, 1570, 1457, 1429, 1382, 1246, 1217, 1205, 1165, 1061 cm−1. ESIMS m/z 303 [M+Na]+, HRESIMS m/z 303.0838 [M+Na]+ . 1H NMR  and 13C NMR , see Table 3--6,8-dimethoxyisocoumarin (8): yellowish solid. UV (MeOH) λmax (log ε) 272 (4.44) nm. IR (KBr) vmax 2955, 2930, 1720, 1664, 1601, 1534, 1407, 1281, 1175, 1111, 1019, 771 cm−1. ESIMS m/z 250 [M+H]+, HRESIMS m/z 250.1439 [M+H]+ . 1H NMR  and 13C NMR , see Table Methyl 4-(hexanoylamino) benzoate . Supplementary data associated with this article including 1D and 2D NMR, HRESIMS, UV, IR of Below is the link to the electronic supplementary material.


Compounds 1–13 are mexicanolides with one double bond or two conjugated double bonds, while 14 belongs to a small group of mexicanolides with an oxygen bridge between C1 and C8. Compounds 15–19 are khayanolides containing a Δ8,14 double bond, whereas 20 and 21 are rare khayanolides containing a Δ14,15 double bond and Δ8,9, Δ14,15 conjugated double bonds, respectively. Compounds 22 and 23 are unusual limonoids possessing a (Z)-bicyclo[5.2.1]dec-3-en-8-one motif, while 24 and 25 are 30-ketophragmalins with Δ8,9, Δ14,15 conjugated double bonds. Compounds 26 and 27 are phragmalin 8,9,30-ortho esters, whereas 28 and 29 are azadirone and andirobin derivatives, respectively. The structures of these compounds, including absolute configurations of 15–19, 21–23, and 26, were established by HRESIMS, extensive 1D and 2D NMR investigations, and the comparison of experimental electronic circular dichroism (ECD) spectra. The absolute configuration of 1 was unequivocally established by single-crystal X-ray diffraction analysis, obtained with Cu Kα radiation. The diverse cyclization patterns of 1–29 reveal the strong flexibility of skeletal plasticity in the limonoid biosynthesis of X. moluccensis. Compound 23 exhibited weak antitumor activity against human triple-negative breast MD-MBA-231 cancer cells with an IC50 value of 37.7 μM. Anti-HIV activities of 1, 3, 8, 10, 11, 14, 20, 23–25, and 27 were tested in vitro. However, no compounds showed potent inhibitory activity.Twenty-nine new limonoids—named xylomolins A Xylocarpus is a well-known genus of mangrove plants which has been found to produce various types of limonoids with a broad range of bioactivities, such as insect antifeedant, antitumor, neuroprotective, gastroprotective, and antidepressant-like activities dec-3-en-8-one substructure , two 30-ketophragmalins , two phragmalin 8,9,30-ortho esters , an azadirone derivative (28), and an andirobin derivative (29) (Further investigation of the seeds of ive (29) . Herein,viz. 1, 3–6, 8, 9, 12–14, 20, 21, 24, 26, 27, and 29) were obtained from seeds of the Thai X. moluccensis, whereas 13 compounds  were isolated from those of the Indian X. moluccensis.In this paper, 16 compounds  to be C33H42O11, implying thirteen degrees of unsaturation. According to the 1H and 13C NMR spectroscopic data (1H and 13C NMR spectroscopic data (H 7.52 br d (J = 0.8 Hz H-21), 6.45 br d (J = 1.2 Hz H-22), 7.44 t (J = 1.6 Hz H-23)], four tertiary methyl groups , a methoxy (δH 3.73 s H3-31), and a keto function (δC 216.7 qC), indicating a mexicanolide-type limonoid for 1.Compound pic data , five elpic data  showed t1 , 1.24 d (J = 7.2 Hz 3H); δC 175.9 qC, 34.5 CH, 19.9 CH3, 18.4 CH3] in 1. The presence of the isobutyryloxy group was corroborated by 1H-1H COSY correlations between H3-34/H-33 and H3-35/H-33. The significant HMBC correlation from H-3 (δH 4.97 s) to the carbonyl carbon (δC 175.9 qC) of the isobutyryloxy group placed it at C-3 , Flack x of −0.14 (11), and Hooft y of −0.04 (3); suitable crystals of 1 were obtained from acetone/methanol (1:2) at room temperature) was employed, which unequivocally assigned the absolute configuration of 1 as 2R,3S,5S,6R,9S,10R,13R,17R. The computer-generated perspective drawing of the X-ray structure of 1 is shown in 1 named xylomolin A1 was assigned as shown . The NMR spectroscopic data of 2 resembled those of 1 ; δC 173.3 qC, 28.0 CH2, 9.4 CH3) and a 6-OH group in 2, respectively. The presence of a 3-O-propionyl moiety was confirmed by 1H-1H COSY correlations between H3-34/H2-33 and HMBC cross-peaks between H3-34/C-33, H3-34/C-32, H2-33/C-32, and H-3/C-32. The relative configuration of 2 (except for that of C-6) was determined to be the same as that of 1 by NOE interactions between H-17/H-15β, H-15β/H-30β, H-17/H-12β, H-17/H-11β, H-11β/H-5, H-17/H-5, and H-5/H3-28, and those between H-9/H3-19, H3-19/H3-29, H3-29/H-3, and H3-18/H-15α. Thus, the structure of 2—named xylomolin A2—was assigned as shown in Compound ose of 1 , except 3 gave the molecular formula C32H42O11 as established by the HRESIMS ion peak at m/z 625.2620 . The NMR spectroscopic data of 3  and HMBC correlations from the proton of 30-OH to C-30, C-2, and C-8. NOE interactions between H-17/H-12β, H-17/H-11β, H-5/H-12β, H-5/H-17, H-5/H3-28, and H-5/H-30 revealed the β-orientation for H-5, H-17, H-30, and H3-28, and the corresponding 30α-OH. Similarly, those between H-3/2-OH, H3-29/2-OH, H-9/H3-19, H3-29/H3-19, and H3-18/H-11α assigned the α-orientation for H-3, H-9, H3-18, H3-19, H3-29, and 2-OH. Thus, the structure of 3—named xylomolin A3—was determined to be 30α-hydroxy-moluccensin S.Compound ata of 3  were sim4 provided the molecular formula of C34H44O13 as determined from the positive HRESIMS ion peak at m/z 683.2675 . The 1H and 13C NMR spectroscopic data of 4 resembled those of 3 (H 3.66 br s) and a 6-acetoxy group  in 4. The existence of a 15-OH function was corroborated by the downshifted C-15 signal  and HMBC correlations from the proton of 15-OH to C-14, C-15, and C-16. The HMBC correlation from H-6 to the carbonyl carbon (C-37) of the acetoxy group placed it at C-6. The relative configuration of 4 (except that of C-15) was assigned as the same as that of 3 on the basis of NOE interactions. Those between H-17/H-15 and H-5/H-30 assigned the β-oriented H-15 and H-30, and the corresponding 15α-OH group. Consequently, the structure of 4—named xylomolin A4—was identified as 15α-hydroxy-6-acetoxy-xylomolin A3.Compound ose of 3 , the dif5 was determined to be C31H38O12 by the positive HRESIMS ion peak at m/z 625.2252 . The 1H and 13C NMR spectroscopic data of 5 . HMBC correlations from the proton of 30-OH (δH 2.67 br s) to C-30 and C-8 demonstrated the above deduction. The NOE interaction between H-5/H-30 assigned the β-oriented H-30 and the corresponding 30α-OH. Thus, the structure of 5—named xylomolin A5—was assigned as 30α-hydroxy-khayalenoid H.The molecular formula of ata of 5  were clo6 was isolated as a white and amorphous powder. Its molecular formula was determined to be C31H38O11 from the positive HRESIMS ion peak at m/z 609.2311 . The 1H and 13C NMR spectroscopic data of 6  and a 6-OH group (δH 2.80 br s) in 6, respectively. HMBC correlations from the proton of the 6-OH group to C-5, C-6,and C-7 placed it at C-6. The presence of the 2-O-acetyl group in 6 was corroborated by the downshifted C-2 in 6 . HMBC correlations from H2-30 and H-3 to C-2 confirmed the above deduction. The relative configuration of 6 was determined to be the same as that of khayalenoid H based on diagnostic NOE interactions between H-17/H-15β, H-17/H-12β, H-17/H-5, and H-5/H3-28 and those between H-9/H3-19, H3-19/H3-29, and H3-18/H-15α. Therefore, the structure of 6—named xylomolin A6—was determined to be 2-O-acetyl-6-O-deacetyl-khayalenoid H.Compound ata of 6  closely 7 was determined to be C31H38O10 by the positive HRESIMS ion peak at m/z 593.2358 . The 1H and 13C NMR spectroscopic data of 7 , 2.42 dd , δC 33.3) in 7. 1H-1H COSY correlations between H2-6/H-5 and HMBC cross-peaks from H2-6 and C-5 and C-7 confirmed the above result. The analysis of diagnostic NOE interactions revealed that 7 possessed the same relative configuration as that of 6. Therefore, the structure of 7—named xylomolin A7—was assigned as 6-dehydroxy-xylomolin A6.The molecular formula of ata of 7  were clo8 was isolated as a white and amorphous powder. It had a molecular formula of C31H36O11 as deduced from the positive HRESIMS ion peak at m/z 607.2151 . The 1H and 13C NMR spectroscopic data of 8  and HMBC correlations between H-15/C-14, H-15/C-16, H-15/C-8, and H-15/C-13. The HMBC correlation from H-3 (δH 5.51 s) to the carbonyl carbon (δC 170.2 qC) of the acetoxy group placed it at C-3. The relative configuration of 8 was established to be the same as that of heytrijunolide E based on diagnostic NOE interactions between H3-28/H-5, H-5/H-11β, H-12β/H-17, H3-29/H-3, H-12α/H3-18, and H-11α/H3-19. Therefore, the structure of 8—named xylomolin B1—was assigned as 15-dehydroxy-3β-acetoxy-heytrijunolide E.Compound ata of 8  were sim9 provided the molecular formula C29H34O9 as established by the positive HRESIMS ion peak at m/z 527.2273 . The 1H and 13C NMR spectroscopic data of 9  and C-2  signals. A proton (δH 3.02 t (J = 6.0 Hz)) exhibiting 1H-1H COSY correlations to H-3 and H-30 and HMBC cross-peaks to C-1, C-3, C-4, and C-30 was assigned as H-2. The existence of H-15 (δH 5.89 s) was further confirmed by its HMBC correlations to C-8, C-13, C-14, and C-16. The relative configuration of 9 was determined to be the same as that of heytrijunolide E based on diagnostic NOE interactions between H3-28/H-5, H-5/H-11β, H-12β/H-17, H3-29/H-3, H-12α/H3-18, and H-11α/H3-19. Thus, the structure of 9—named xylomolin B2—was assigned as 2,15-dedihydroxy-heytrijunolide E.Compound ata of 9  were sim10 had a molecular formula of C29H34O10 as determined from the positive HRESIMS ion peak at m/z 543.2238 . The NMR data of 10 (O-(2-methyl)butyryl group in moluccensin U by an acetoxy group  in 10. The significant HMBC cross-peak from H-3 (δH 4.83 s) to the carbonyl carbon of the above acetoxy group placed it at C-3. NOE interactions between H-11β/H-17, H-12β/H-17, H-11β/H-5, H-5/H3-28, H-9/H3-18, H-9/H3-19, and H3-29/H-3 revealed the same relative configuration of 10 as that of moluccensin U. Therefore, the structure of 10—named xylomolin C1—was assigned as 3-O-acetyl-3-de(2-methyl) butyryloxy-moluccensin U.Compound ta of 10  closely 11 afforded the molecular formula C32H40O9 as established by the positive HRESIMS ion peak at m/z 591.2570 . The 1H and 13C NMR spectroscopic data of 11 , 1.25 d (J = 6.8 Hz 3H); δC 176.0 qC, 41.4 CH, 26.9 CH2, 11.9 CH3, 17.0 CH3) in 11. The deduction was confirmed by 1H-1H COSY correlations between H3-36/H-33, H3-35/H2-34, and H2-34/H-33, and HMBC correlations between H-3/C-32, H3-35/C-34, H3-35/C-33, H3-36/C-33, H3-36/C-32, and H3-36/C-34. NOE interactions between H-12β/H-17, H-17/H-11β, H-5/H-11β, H-5/H3-28, H-9/H3-18, H-9/H3-19, and H3-29/H-3 assigned the α-orientation for H-9, H3-18, H3-19, and H-3. Thus, the structure of 11—named xylomolin C2—was assigned as 3-O-(2-methyl)butyryl-3-deisobutyryloxy-swietmanin G.Compound ta of 11  closely 12 had the molecular formula C32H42O11 as determined from the positive HRESIMS ion peak at m/z 625.2612 . The 1H and 13C NMR spectroscopic data of 12  and C-30 (δC 45.9 CH2) signals as compared with those (δC 134.5 qC and 133.6 CH) of moluccensin U, respectively. The presence of the 8-OH group was confirmed by HMBC correlations from its proton to C-8, C-9, and C-30. NOE interactions between 8-OH/H-9 and 8-OH/H3-18 assigned the α-orientation for the 8-OH group. The relative configuration of 12 (except that of C-8) was established to be identical to that of moluccensin U based on diagnostic NOE interactions between H-12β/H-17, H-5/H3-28, H-9/H3-19, and H3-29/H-3. Thus, the structure of 12—named xylomolin D—was assigned as 8,30-dihydrogen-8α-hydroxy-moluccensin U.Compound ta of 12  were sim13 was obtained as an amorphous white power. The molecular formula was determined to be C31H38O12 by the positive HRESIMS ion peak at m/z 625.2250 . The 1H and 13C NMR spectroscopic data of 13  in 13, and the presence of an additional 14-OH group. HMBC correlations between H2-15/C-14, H2-15/C-16, H2-15/C-13, H-30/C-14, H-30/C-9, and H-9/C-8 demonstrated the above deduction. In order to establish the relative configuration of the 14-OH group in 13, two possible 3D structures with a 14α-OH and 14β-OH groups, respectively, were simulated by using the ChemBio3D software  was determined to be the same as that of 8 on the basis of NOE interactions between H3-28/H-5, H-5/H-11β, H-12β/H-17, H3-29/H-3, H-12α/H3-18, and H-11α/H3-19. Thus, the structure of 13—named xylomolin E—was assigned as depicted.Compound ta of 13  were simsoftware . When thsoftware a, implyisoftware b, indica2–13 are analogues of 1. From the point of view of biogenetic origins, these mexicanolides should possess the same absolute configurations of carbon skeletons as that of 1. The absolute sterostructures of 2–13 are shown as in Compounds 14 was determined to be C33H42O13 by the positive HRESIMS ion peak at m/z 669.2521 . The NMR spectroscopic data of 14  and an additional 6-OH function (δH 2.93 s) in 14. The existence of the Δ14,15 double bond was corroborated by HMBC correlations between H3-18/C-14, H-15/C-8, and H-15/C-16. The downshifted C-6 signal , along with HMBC cross-peaks from H-6 to C-5 and C-7, supported the location of a hydroxy group at C-6. Similar NOE interactions of 14 as those of xylorumphiin H suggested that both mexicanolides possessed the same relative configuration. Thus, the structure of 14—named xylomolin F—was assigned as 6-hydroxy-14,15-dedihydrogen-xylorumphiin H.The molecular formula of ta of 14  were sim15 was established by the positive HRESIMS ion peak at m/z 587.2494  to be C31H38O11, implying thirteen degrees of unsaturation. According to the NMR spectroscopic data of 15 ) to C-5 , C-6 , and C-7   a reveale15 was assigned by analysis of NOE interactions  spectrum of 15 with that of thaixylomolin L dec-3-en-8-one substructure, revealed their close structural resemblance. However, the 3-O-isobutyryl function in trangmolin F was replaced by an acetoxy group  in 22, being unambiguously confirmed by HMBC cross-peaks between H-3/C-32 and H3-33/C-32 . The NMR spectroscopic data of 23 , 1.18 d ; δC 176.2 qC, 40.7 CH, 26.6 CH2, 11.5 CH3, 16.4 CH3) in 23. The presence of the 2-methylbutyryloxy group was further evidenced by 1H-1H COSY cross-peaks between H-33/H3-36, H-33/H2-34, and H2-34/H3-35 and HMBC correlations between H-33/C-32, H-34/C-32, and H3-36/C-32. The HMBC correlation from H-3 to the carbonyl carbon (C-32) of the above 2-methylbutyryloxy group placed it at C-3. The relative configuration of 23 was confirmed to be the same as that of 22 by analysis of NOE interactions. Comparison of ECD spectra of compounds 23, 22, and trangmolin F . The NMR spectroscopic data of 24 (H 3.12 br s) and the replacement of the 1-O-isobutyryl group in moluccensin I by a 1-OH function (δH 2.81 s) in 24. The downshifted C-6 signal  and HMBC correlations from the active proton (δH 3.12 br s) to C-5, C-6, and C-7 revealed the presence of the 6-OH group  and strong HMBC cross-peaks from the active proton (δH 2.81 s) to C-1, C-2, and C-10 . The NMR spectroscopic data of 25 butyryl in 24 by an isobutyryloxy group , 1.11 d ; δC 174.8 qC, 34.2 CH, 18.8 CH3, 19.0 CH3) in 25. The HMBC correlation from H-3 to the carbonyl carbon (C-32) of the isobutyryloxy group placed it at C-3. The relative configuration of 25 was determined to be the same as that of 24 based on NOE interactions between H-17/H-12β, H-11β/H-5, H-5/H3-28, H-12α/H3-18, H3-18/H-11α, Hpro-R-29/H-3, and Hpro-S-29/H3-19. Thus, the structure of 25—named xylomolin K2—was identified as 3-O-isobutyryl-3-de(2-methyl)butyryloxy-xylomolin K1.Compound ta of 25  were sim26 was obtained as an amorphous white powder. Its molecular formula was determined to be C33H38O14 by the positive HRESIMS ion peak at m/z 681.2149 . The NMR spectroscopic data of 26 , the 1H-1H COSY cross-peak between H-5/H-6 and HMBC correlations between H-6/C-5 and H-6/C-7. The upshifted C-12 signal , 1H-1H COSY cross-peaks between H2-11/H2-12, and HMBC correlations between H3-18/C-12 . The NMR spectroscopic data of 27 , 1H-1H COSY cross-peaks between H2-11/H-12, and HMBC correlations between H3-18/C-12. The strong NOE interaction between H-17/H-12 assigned the β-oriented H-12 and the corresponding α-orientation for the 12-OH group. The NOE interaction between H3-37/H3-38 assigned the E configuration for the double bond of 3-tigloyloxy group. Therefore, the structure of 27—named xylomolin L2—was identified as 12α-hydroxy-swietephragmin G.The molecular formula of ta of 27  closely 28 had the molecular formula C28H37O6 as determined from the positive HRESIMS ion peak at m/z 469.2603 . The NMR spectroscopic data of 28 . The NMR spectroscopic data of 29  and HMBC correlations from H2-21 (δH 4.85 br d (J = 18.3 Hz), 5.03 dd ) to C-20 and C-22. The relative configuration of 29 was assigned as the same as that of moluccensin O based on NOE correlations. Thus, the structure of compound 29—named xylomolin N—was assigned as 21-dehydroxy-moluccensin O.Compound ta of 29  closely 1, 3, 8, 10, 11, 14–16, 20, 23, 25, and 27 were tested by the MTT cytotoxity assay against five human tumor cell lines, including human colorectal HCT-8 and HCT-8/T, human ovarian A2780 and A2780/T, and human breast MD-MBA-231  were used. ECD spectra were measured on a Jasco J-810 spectropolarimeter  in MeCN.Optical rotations were recorded on a MCP500 modular circular polarimeter . UV spectra were obtained on a GENESYS 10S UV-Vis spectrophotometer . HRESIMS were measured on a Bruker maXis ESI-QTOF mass spectrometer . NMR spectra were recorded on a Bruker AV-400 spectrometer with TMS as the internal standard. Single-crystal X-ray diffraction analyses were made on an Agilent Xcalibur Atlas Gemini Ultra-diffractometer  with mirror monochromated CuKα radiation (λ = 1.54178 Å) at 150 K. Semi-preparative HPLC  was performed on a Waters 2535 pump equipped with a waters 2998 photodiode array detector and YMC C18 reverse-phased columns . For column chromatography, silica gel (100–200 mesh)  and CXylocarpus moluccensis were collected at the mangrove swamp of Trang Province, Thailand, in June 2013, whereas another batch of seeds of the same mangrove plant were collected in Godavari estuary, Andhra Pradesh, India, in October 2009, respectively. The identification of the plant was performed by one of the authors (J.W.) and Mr. Tirumani Satyanandamurty . Voucher samples  were maintained in the Marine Drugs Research Center, College of Pharmacy, Jinan University.A batch of seeds of X. moluccensis were extracted with 95% (v/v) EtOH at room temperature (5 × 20 L) to afford the EtOH extract (680.0 g), which was suspended in water and extracted with EtOAc. The resulting EtOAc extract (296.0 g) was chromatographed on silica gel column and eluted with CHCl3/MeOH (100:0 to 5:1) to yield 160 fractions. The dried seeds  of 2O, 50:50 to 100:0) to afford 57 subfractions. Subfraction 23 was purified by preparative HPLC  to afford compound 1 (45.0 mg).Fractions 26–28 (31.6 g) were combined and further purified with an RP-18 column  to afford 360 subfractions. The combination of subfractions 90–95 was subjected to preparative HPLC  to give compound 8 (72 mg), along with five other subfractions (SFr.90-95-1 to SFr.90-95-5). Recrystallization of SFr.90-95-1 afforded compound 20 (15.3 mg). Further purification of SFr.90-95-2 with preparative HPLC  yielded compounds 3 (7.1 mg), 5 (4.3 mg), 12 (37 mg), 13 (2.8 mg), and 21 (1.2 mg), whereas that of SFr.90-95-3 with preparative HPLC  afforded compounds 6 (4.3 mg) and 9 (3.1 mg). SFr.90-95-4 was further purified with preparative HPLC  to afford compound 14 (57.0 mg). Subfractions 78–83 were combined and further purified by preparative HPLC  to give compounds 24 (3.5 mg), 26 (2.0 mg), 27 (7.0 mg), and 29 (2.5 mg).Fractions 29–40 (111.0 g) were combined and further purified with an RP-18 column  to afford 45 subfractions. Subfraction 27 was purified by preparative HPLC  to afford compound 4 (1.2 mg).Fractions 157–175 (14.5 g) were combined and further purified with an RP-18 column (acetone/Hv/v) EtOH (5 × 20 L) at room temperature to afford the EtOH extract (1.1 kg), which was partitioned between EtOAc and water to afford the EtOAc portion (572.0 g). Then, 252.0 g of the EtOAc extract was further subjected to a silica gel column (105.0 cm × 9.5 cm i.d.) and eluted with a gradient mixture of CHCl3/MeOH (100:1 to 5:1) to afford 184 fractions. The air-dried seeds  were powdered and extracted with 95% (2O (40:60 to 100:0) to afford 74 subfractions. Fractions 38–43 (26.0 g) were combined and further separated on an RP-18 column (64.0 cm × 6.3 cm i.d.), and eluted with a gradient mixture of acetone/H2O, 36:64) to afford seven parts (SFr.12-16-1 to SFr.12-16-7). SFr.12-16-2 was further purified by preparative HPLC  to yield compounds 10 (49.3 mg) and 25 (25.7 mg). SFr.12-16-4 and SFr.12-16-5 were further purified by preparative HPLC  to afford compounds 15 (13 mg) and 22 (3.0 mg), respectively. SFr.12-16-6 was further subjected to preparative HPLC  to yield compound 2 (2.0 mg), whereas SFr.12-16-7 was further purified by preparative HPLC  to yield compound 28 (1.5 mg).Subfractions 12–16 (1.5 g) were combined and separated by preparative HPLC  was performed on subfraction 27 (2.9 g) to gain compound 16 (4.0 mg). Subfractions 32–35 (1.5 g) were combined and separated by preparative HPLC  to give four parts (SFr.32-35-1 to SFr.32-35-4). SFr.32-35-2 and SFr.32-35-3 were purified by preparative HPLC  to yield compounds 23 (27.0 mg) and 11 (27.5 mg), respectively, whereas recrystallization (acetone) of SFr.32-35-4 afforded compound 7 (23.8 mg).Preparative HPLC , to afford 81 subfractions. Subfraction 4 (6.5 g) was purified by preparative HPLC  to yield compound 17 (5.5 mg). Subfractions 8–14 (10.4 g) were combined and further separated on an RP-18 column (62.0 cm × 6.5 cm i.d.) and eluted with a gradient mixture of acetone/H2O (50:50 to 100:0) to afford 37 subsubfractions, among which subsubfractions 12–15 (2.1 g) were combined and separated on the preparative HPLC  to give compound 18 (2.1 mg). Subfraction 17 (1.78 g) was subjected to preparative HPLC  to yield compound 19 (1.2 mg). Fractions 48–86 (43.9 g) were combined and further performed on an RP-18 column (46.7 cm × 6.4 cm i.d.), and eluted with a gradient mixture of MeCN/H1 (1): Colorless crystal; c = 0.06, acetone); UV (MeCN) λmax (log ε) 199.7 (3.7) nm; ECD  λmax (Δε) 190.0 (−12.0), 289.6 (−2.2) nm; 1H and 13C NMR spectroscopic data see m/z 615.2785 [M + H]+ .Xylomolin A2 (2): White, amorphous powder; c 0.04, acetone); UV (MeCN) λmax (log ε) 194.0 (4.5), 279.0 (3.3) nm; 1H and 13C NMR spectroscopic data see m/z 593.2143 [M + Cl]− .Xylomolin A3 (3): White, amorphous solid; c 0.05, acetone); UV (MeCN) λmax (log ε) 198.9 (3.9) nm; ECD  λmax (Δε) 191.0 (−14.5) nm; 1H and 13C NMR spectroscopic data see m/z 625.2620 [M + Na]+ .Xylomolin A4 (4): White, amorphous powder; c 0.08, acetone); UV (MeCN) λmax (log ε) 197.0 (3.9), 201.8 (3.8) nm; ECD  λmax (Δε) 190(−8.1), 200.4 (−5.0), 211.6 (−6.6) nm; 1H and 13C NMR spectroscopic data see m/z 683.2675 [M + Na]+ .Xylomolin A5 (5): White, amorphous powder; c 0.04, acetone); UV (MeCN) λmax (log ε) 201.0 (3.8) nm; ECD  λmax (Δε) 191.0 (−8.6) nm; 1H and 13C NMR spectroscopic data see m/z 625.2252 [M + Na]+ .Xylomolin A6 (6): White, amorphous powder; c 0.10, acetone); UV (MeCN) λmax (log ε) 197.8 (4.0) nm; ECD  λmax (Δε) 190.0 (−12.8), 216.4 (+1.5), 294.2 (−2.3) nm; 1H and 13C NMR spectroscopic data see m/z 609.2311 [M + Na]+ .Xylomolin A7 (7): White powder; c 0.08, acetone); UV (MeCN) λmax (log ε) 193.0 (4.5) nm; 1H and 13C NMR spectroscopic data see m/z 593.2358 [M + Na]+ .Xylomolin A1 (8): White, amorphous powder; c 0.08, acetone); UV (MeCN) λmax (log ε) 204.0 (3.9), 285.4 (4.0) nm; ECD  λmax (Δε) 252.1 (−1.6), 278.9 (+8.6) nm; 1H and 13C NMR spectroscopic data see m/z 607.2151 [M + Na]+ .Xylomolin B2 (9): White, amorphous solid; c 0.10, acetone); UV (MeCN) λmax (log ε) 207.2 (3.7), 285.2 (4.0) nm; ECD  λmax (Δε) 190.0 (+3.6), 213.7 (−1.1), 282.2 (+9.5) nm; 1H and 13C NMR spectroscopic data see m/z 527.2273 [M + H]+ .Xylomolin B1 (10): White, amorphous powder; c 0.07, acetone); UV (MeCN) λmax (log ε) 191.0 (4.3), 275 (4.1) nm; 1H and 13C NMR spectroscopic data see m/z 543.2238) [M + H]+ .Xylomolin C2 (11): White, amorphous powder; c 0.09, acetone); UV (MeCN) λmax (log ε) 194.0 (4.7), 277 (4.6) nm; 1H and 13C NMR spectroscopic data see m/z 591.2570 [M + Na]+ .Xylomolin C12): White, amorphous powder; c 0.05, acetone); UV (MeCN) λmax (log ε) 208.2 (3.8) nm; ECD  λmax (Δε) 190.0 (−2.6), 217.5 (+13.7), 244.5 (−0.3), 261 (+ 1.5), 291.2 (−3.8) nm; 1H and 13C NMR spectroscopic data see m/z 625.2612 [M + Na]+ .Xylomolin D (13): White, amorphous powder; c 0.04, acetone); UV (MeCN) λmax (log ε) 207.2 (3.9) nm; ECD  λmax (Δε) 190.0 (−9.5), 213.7 (+2.5) nm; 1H and 13C NMR spectroscopic data see m/z 625.2250 [M + Na]+ .Xylomolin E (14): White, amorphous powder; c 0.03, acetone); UV (MeCN) λmax (log ε) 211.0 (4.1) nm; ECD  λmax (Δε) 192.0 (−7.1), 219.0 (+4.0), 265.0 (+3.2) nm; 1H and 13C NMR spectroscopic data see m/z 669.2521 [M + Na]+ .Xylomolin F (1 (15): White, amorphous solid; c 0.1, acetone); UV (MeCN) λmax (log ε) 190.2 (4.20) nm; ECD  λmax (Δε) 207 (+2.3), 238 (−3.8), 290 (+1.4), 321 (−0.32), 344 (+0.32) nm; 1H and 13C NMR spectroscopic data see m/z 587.2494 [M + H]+ .Xylomolin G2 (16): White, amorphous solid; c 0.05,acetone); UV (MeCN) λmax (log ε) 190.2 (4.03); ECD  λmax (Δε) 205.0 (+1.7), 239.0 (−4.3), 302.0 (+0.34), 339.0 (+1.1) nm; 1H and 13C NMR spectroscopic data see m/z 615.2809 [M + H]+ .Xylomolin G3 (17): White, amorphous solid; c 0.04, acetone); UV (MeCN) λmax (log ε) 196.6 (4.03), 285.0 (2.93) nm; ECD  λmax (Δε) 193.0 (−4.5), 197.0 (−3.4), 205.0 (−7.5), 216.0 (−5.0), 233.0 (−7.9), 298 (+4.3) nm; 1H and13C NMR spectroscopic data see m/z 543.2246 [M + H]+ .Xylomolin G4 (18): White, amorphous solid; c 0.01,acetone); UV (MeCN) λmax (log ε) 196.6 (4.08) nm; ECD  λmax (Δε) 203.0 (−8.7), 215.0 (−6.2), 233.0 (−10.3), 301.0 (+5.0) nm; 1H and13C NMR spectroscopic data see m/z 555.2593 [M + H]+ .Xylomolin G5 (19): White, amorphous solid; c 0.024, acetone); UV (MeCN) λmax (log ε) 195.0 (4.27), 284.2 (2.86) nm; ECD  λmax (Δε) 195.0 (+ 0.70), 206.0 (−4.9), 214.0 (−3.5), 231.0 (−6.1), 299.0 (+2.7) nm; 1H and13C NMR spectroscopic data see m/z 569.2753 [M + H]+ .Xylomolin G20): White, amorphous powder; c 0.06, acetone); UV (MeCN) λmax (log ε) 212.3 (4.0) nm; ECD  λmax (Δε) 223 (+10.9), 245 (+0.19),270 (+8.1) nm; 1H and 13C NMR spectroscopic data see m/z 667.2359 [M + Na]+ .Xylomolin H (21): Light yellow, amorphous gum; c 0.08, acetone); UV (MeCN) λmax (log ε) 208.4 (3.8), 287.6 (4.1) nm; ECD  λmax (Δε) 200.0 (+4.6), 213.0 (+2.3), 232.0 (+4.6), 259.0 (−3.9), 291.0 (+10.3) nm; 1H and 13C NMR spectroscopic data see m/z 621.2304 [M + Na]+ Xylomolin I (1 (22): White, amorphous powder; c 0.11, acetone); UV (MeCN) λmax (log ε) 197.0 (4.9), 213.4 (4.8), 260.8 (4.6) nm; ECD  λmax (Δε) 204.0 (−3.3), 229.0 (+3.3), 266.0 (+6.3), 310.0 (−0.19), 346.0 (+0.95) nm; 1H and 13C NMR spectroscopic data see m/z 541.2077 [M + H]+ .Xylomolin J2 (23): White, amorphous powder; c 0.1, acetone); UV (MeCN) λmax (log ε) 196.8 (5.2), 211.0 (5.1), 260.8 (5.0) nm; ECD  λmax (Δε) 190.0 (−3.9), 199.0 (−2.0), 206.0 (−2.9), 225.0 (+3.9), 267.0 (+9.1), 310.0 (−0.17), 335.0 (+1.0) nm; 1H and 13C NMR spectroscopic data see m/z 583.2548 [M + H]+ .Xylomolin J1 (24): White, amorphous powder; c 0.1, acetone); UV (MeCN) λmax (log ε) 194.0 (4.3), 271.0 (4.3) nm; ECD  λmax (Δε) 209.0 (+3.0), 211.0 (+2.9), 232.0 (+8.5), 275.0 (−2.8), 300.0 (+6.4) nm; 1H and 13C NMR spectroscopic data see m/z 621.2306 [M + Na]+ .Xylomolin K2 (25): White, amorphous powder; c 0.07, acetone); UV (MeCN) λmax (log ε) 191.0 (4.3), 272.0 (4.5) nm; 1H and 13C NMR spectroscopic data see m/z 607.2164 [M + Na]+ .Xylomolin K1 (26) : White, amorphous powder; c 0.09, acetone); UV (MeCN) λmax (log ε) 213.0 (4.0) nm; ECD  λmax (Δε) 220.0 (+12.5), 249.0 (+ 1.1), 270.0 (+ 0.8), 236.0 (+ 1.9) nm; 1H and 13C NMR spectroscopic data see m/z 681.2149 [M + Na]+ .Xylomolin L2 (27): White, amorphous powder; c 0.06, acetone); UV (MeCN) λmax (log ε) 214 (4.5) nm; ECD  λmax (Δε) 198.0 (+3.2), 213.0 (−3.6), 234.0 (+11.6) nm; 1H and 13C NMR spectroscopic data see m/z 679.2374 [M + Na]+ .Xylomolin L28): White, amorphous powder; c 0.03, acetone); UV (MeCN) λmax 200.0 (4.0), 232 (4.1) nm; 1H and 13C NMR spectroscopic data see m/z 469.2603 [M + H]+ .Xylomolin M (29): White, amorphous powder; c 0.05, acetone); UV (MeCN) λmax (log ε) 196 (3.7), 211 (3.7) nm; ECD  λmax (Δε) 200.0 (−7.0), 224.0 (+2.1), 252.0 (−0.3) nm; 1H and 13C NMR spectroscopic data see m/z 509.2147 [M + Na]+ . Xylomolin N (34H46O12 (C33H42O11·CH3OH), space group P2(1)2(1)2(1), a = 8.82730 (5) Å, b = 17.93740 (10) Å, c = 20.84108 (13) Å, α = 90°, β = 90°, γ = 90°, V = 3299.95 (3) Å3, Z = 4, Dcalcd. = 1.302 Mg/m3, μ = 0.816 mm−1. Crystal size: 0.40 × 0.40 × 0.28 mm3. 47,329 measured reflections, 5877 [Rint = 0.0378] independent reflections, 426 parameters, 0 restraints, F(000) = 1384.0, R1 = 0.0296, wR2 = 0.0773, R1 = 0.0286, wR2 = 0.0763 [I > 2σ(I)], and goodness-of-fit (F2) = 1.065. The absolute structural parameter is −0.06(10), Flack x is −0.14(11), and Hooft y is −0.04(3). Orthorhombic, C1) contains the supplementary crystallographic data for this paper (excluding structure factors). These data are provided free of charge by The Cambridge Crystallographic Data Centre.CCDC-1590301 , and streptomycin (50 mg/L) at 37 °C in a humidified atmosphere of 5% CO2. Cells were collected with trypsin and resuspended in a final concentration of 5 × 104/mL. One hundred microliter aliquots for each cell suspension were distributed evenly into 96-well multiplates (number of cells per well is 5 × 103). Different concentrations of the compounds were added into the designated wells. After 72 h, a 10 μL MTT solution (5 mg/mL) was added to each well, and the plate was further incubated for 4 h, allowing viable cells to reduce the yellow MTT into dark-blue formazan crystals which were dissolved in DMSO 100 μL. The absorbance in individual wells was determined at 490 nm by a microplate reader  dec-3-en-8-one motif, while 24 and 25 are 30-ketophragmalins. Compounds 26 and 27 are phragmalin 8,9,30-ortho esters, whereas 28 and 29 are azadirone and andirobin derivatives. These results demonstrate that X. moluccensis continues to be an abundant resource for the production of novel limonoids with structural diversity. Compound 23 exhibited selective antitumor activity against human triple-negative breast MD-MBA-231 cancer cells with an IC50 value of 37.7 μM, whereas compounds 1, 11, 23, and 24 showed inhibitory rates of 17.49 ± 6.93%, 24.47 ± 5.04%, 14.77 ± 5.91%, and 14.34 ± 3.92% against HIV-I virus, respectively, at the concentration of 20 μM.Twenty-nine new limonoids were isolated from the seeds of the mangrove plant,


Metal phthalocyanine tetrasulfonic acids, metal phthalocyanine octacarboxylic acids, metal octakis(hexyloxymethyl)phthalocyanines, and metal anthraquinocyanines have been synthesized. Then, zinc bis-bisporphyrazines, the cyclotetramerization products of a 1:1 mixture of 3,6-didecylphthalonitrile and 3,4-dicyanopyridine, were synthesized. Futher, subphthalocyanine and its derivatives, with substituents such as thiobutyl and thiophenyl moieties were synthesized. Electrochemical measurements were performed on the abovementioned phthalocyanine derivatives and analogues in order to examine their electron transfer abilities and electrochemical reaction mechanisms in an organic solvent. Moreover, 1,4,8,11,15,18,22,25-octakis(thio-phenylmethyl)phthalocyanes were synthesized. The Q-bands of the latter compounds appeared in the near-infrared region. Furthermore, non-colored transparent films in the visible region can be produced. A phthalocyanine containing one or two metal ions is called a metal phthalocyanine (M-PC). In the last decade, as a result of their high electron transfer abilities, M-PCs have been utilized in many fields such as molecular electronics, optelectronics, photonics, etc undec-7-ene (DBU) as a catalyst  and ultraviolet-visible (UV-Vis) spectra, and elemental analytical data of ure data ,24.2 were synthesized from benzene-1,2,4,5-tetracarboxylic dianhydride (pyromellitic dianhydride), a metal halide and urea under the reaction conditions used for the monomer preparation . The position of the absorption peaks in the IR and UV-Vis spectra and elemental analysis data of 2 are in agreement with the proposed structure and literature data . Co. Co6a wa6d-g were synthesized from the precursors 1,2-dicyano-3,6-bis(thiobutyl)-4,5-difluoro-benzene (14a), 1,2-dicyano-3,4,5,6-tetrakis(thiobutyl)benzene (14b), 1,2-dicyano-3,6-bis(thiophenyl)-4,5-difluorobenzene (14c) and 1,2-dicyano-3,4,5,6-tetrakis(thiophenyl)benzene (14d), respectively. The precursors of the SubPC derivatives were analyzed and the analytical data were in good agreement with the proposed structures.Compounds 1H-NMR spectroscopy and the analytical data were in good agreement with the proposed structures. Absorption bands in the IR spectra of SubPC and its derivatives are assigned as follows: peaks around 1,600 cm-1 are aromatic ring absorptions; those in the 1,200–1,050 cm-1 region are mainly absorption from out-of-plane bending of CH and NH in pyrrole rings, in which cyclotrimerization is found. These absorption bands in the IR spectrum are characteristic peaks of M-PCs.The target SubPC and derivatives were analyzed by UV-Vis, IR and The absorption maxima of SubPC and its derivatives appeared around 560 - 630 nm in benzene solution. The Q band absorption of SubPC and its derivatives is shifted by around 100 nm to a shorter wavelength in comparison with normal metal phthalocyanine derivatives, in which they appear around 650 nm. The shift of absorption maxima depends upon the change in electron distribution and the size of the macrocycle. Absorption maxima of SubPC derivatives shifted to longer wavelength with increasing molecular weight. The synthesized SubPC and its derivatives were sufficiently soluble in some organic solvents such as dichloromethane, chloroform, acetone and DMF.15 were synthesized in three steps via the intermediates phthalonitrile-3,6-ditriflate (16) and 3,6-bis(thiophenyl)phthalonitriles (17). Intermediate 16 was synthesized from 2,3-dicyanohydroquinon and trifluoromethanesulfonic anhydride for 24 h in accordance with a description from the literature . As. As15a),Cyclic voltammetry (CV) is often used in electrochemistry studies. It consists of the cyclic potential of a stationary electrode immersed in a quiescent solution and measuring the resulting current. The excitation signal is a linear potential scan with a triangular waveform. This triangular potential excitation signal sweeps the potential of the working electrode. The triangle returns at the same speed and permits the display of a complete voltammogram. Therefore, if a molecular is reduced in the forward scan, it will be reoxidized on the reverse scan. The current response shows the upper half, cathodic (reduction) and the lower half, an anodic (oxidation) peak.1, 2, 3 and 4, respectively. The reduction and oxidation potentials of cobalt-1, 2, 3 and 4 are summarized in 1 showed two cathodic peaks at -0.63 and -1.00 V vs. silver (Ag)/ silver chloride (AgCl) saturated sodium chloride, and four anodic peaks at 0.89, 0.67, -0.60 and-0.90 V vs. Ag/AgCl. The peaks of cobalt-1 are attributed to a five reduction stage. The first reversible reduction potential at -0.62 V vs. Ag/AgCl and the first oxidation potential of cobalt-1 appeared at 0.67 V vs. Ag/AgCl.The CV of cobalt-2, three cathodic peaks and six anodic peaks appeared. The peaks were sorted into three reversible reduction couples at -0.24, -0.66 and -1.39 V vs. Ag/AgCl, and three irreversible oxidation waves at 0.67, 0.87 and 1.06 V vs. Ag/AgCl. The reduction and oxidation of metal phthalocyanine derivatives are due to the interaction between the phthalocyanine ring and the central metal  + 1. The mutistep equibrium between 6 derivatives and TCT is shown in Equations (28) and (29):The sensitization mechanisums between SubPC derivatives and TCT are thought as equations (28–41), where Iqi is much larger than any decay rate. Equation (40) is described Equation (41) of the dynamic and static quenching terms.Equation (30) implies that SubPC derivatives and (SubPC–iTCT) are excited to an excited state *SubPC by absorbing laser pulse. Equations (31) and (32) mean that the *SubPC undergoes nonradiative and radiative deactivation. Then, the *SubPC reacted with TCT forms radicals such as chloro or dichloromethyl radicals as shown in Equation (33). Further, the SubPC becomes triplet state by intersystem crossing in Equation (34). The (SubPC–iTCT) also undergones (*SubPC–iTCT) by absorbing laser pulse (Equation 35). The activate state (*SubPC–iTCT) takes statically sensitized decomposition of TCT (Equation 36). Then, (*SubPC–iTCT) undergoes radiative, monoradiative deactivation and intercrossing as described in Equatons (38) and (39). The attention of fluorescence with the concentration of TCT in film is described as Equation (40). When (*SubPC–iTCT) does not emit fluorescence, meaning k6 in a PMMA films was also quenched by TCT. The initial absorptions were decreased with the concentration of TCT. The triplet life times measured almost the same. The logarithmic plots of the initial absorption at various concentration of TCT were fitted to the Perrin equation, the triplet quenching radius (Rt) were calculation to be 1.3 nm, which was almost same as Rf. The results indicate the triplet initial absorption was not quenched by TCT, since the triplet state generally came from the fluorescent singlet state, and the triplet is apparently reduced with the decrease of the singlet state.The triplet state of 6 to the higher TCT state. The derivatives of 6 derivatives present similar phenomena to 6. It is suggested that the static-singlet-quenching process from the singlet photoexcited 6 to TCT is predominant in the sensitization.The reduction and oxidation behavior of M-PCs are due to the interaction between the phthalocyanine ring and the central metal . In the 2-PCs, a strong absorption, termed the Q band, is detected in the visible region between 650 and 690 nm, and another in the UV-Vis between 320 and 370 nm, called the Soret band. A typical value for the extinction coefficient (ε) of the Q band is around 105 cm2· mol−1. The absorption spectra of the synthesized compounds 7 show typical shapes for M-PCs , benzene-d6 or chloroform-d (CDCl3) using tetramethylsilane (TMS) as the internal standard. Elemental analysis was carried out using a Perkin-Elmer 2400CHN instrument. Mass spectra were taken with a Nihon Denshi Joel JMS-AX500 mass spectrometer. Melting points were measured with a Stanford Research Systems MPA100 Optimelt automated system.UV-Vis spectra were measured on a Shimadzu UV-2400PC spectrometer. Each sample was prepared in toluene at 5.0 × 10All chemicals were purchased from Aldrich or Tokyo Chemical Industry Co. Ltd. They were used as received without further purification. For chromatographic separation, silica gel was used .1-Fe (75%) Found: C, 43.20%; H, 1.99%; N, 12.45%. Calcd. for C32H16N8O12S4Fe: C, 43.25%; H, 1.81%; N, 12.60%. IR (KBr): νmax/cm−1 3000 (νC-H), 1700 (νC-C), 1450 (δC-H), 1380 (νS-O), 1050 (δC-H), 770 (δC-H). UV-Vis: λmax Py/nm: 688.5, 649.0, 354.0, 213.0; 1-Co (75%) Found: C, 42.92%; H, 2.08%; N, 12.67%. Calcd. for C32H16N8O12S4Co: C, 43.10%; H, 1.80%; N, 12.56%. IR (KBr): νmax/cm−1 3000 (νC-H), 1700 (νC-C), 1450 (δC-H), 1380 (νS-O), 1050 (δC-H), 770 (δC-H). UV-Vis: λmax Py/nm: 688.5, 649.0, 354.0, 213.0; 1-Cu (75%) Found: C, 42.86%; H, 1.67%; N, 12.45%. Calcd. for C32H16N8O12S4Cu: C, 42.88%; H, 1.79%; N, 12.50%. IR (KBr): νmax/cm-1 3000 (νC-H), 1700 (νC-C), 1450 (δC-H), 1380 (νS-O), 1050 (δC-H), 770 (δC-H). UV-Vis: λmax Py/nm: 688.5, 649.0, 354.0, 213.0; 1-Zn (75%) Found: C, 42.67%; H, 1.80%; N, 12.53%. Calcd. for C32H16N8O12S4Zn: C, 42.79%; H, 1.79%; N,12.47%. IR (KBr): νmax/cm-1 3000 (νC-H), 1700 (νC-C), 1450 (δC-H), 1380 (νS-O), 1050 (δC-H), 770 (δC-H). UV-Vis: λmax Py/nm: 688.5, 649.0, 354.0, 213.0.A mixture of 4-sulfophthalic acid , urea , metal chloride (30 mmol) and DBU (1 g) as a catalyst dissolved in 150 mL of 1,2,4-trichlorobenzene as solvent was heated to 210 ºC for 180 min . The pro2-Fe (yield: 30%) Found: C, 52.11%; H, 1.41%; N, 12.25%. Calcd. for C40H16N8O16Fe: C, 52.19%; H, 1.75%; N, 12.17%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1750 (νC-O), 1720 (νC-O), 1480 (νC-C), 1060 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 684; 2-Co (yield: 30%) Found: C, 52.44%; H, 1.74%; N, 12.25%. Calcd. for C40H16N8O16Co: C, 52.04%; H, 1.74%; N, 12.13%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1750 (νC-O), 1720 (νC-O), 1480 (νC-C), 1060 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 684; 2-Cu (yield: 30%) Found: C, 52.03%; H, 1.86%; N, 11.97%. Calcd. for C40H16N8O16Cu: C, 51.76%; H, 1.73%; N, 12.07%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1750 (νC-O), 1720 (νC-O), 1480 (νC-C), 1060 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 684; 2-Zn (yield: 30%) Found: C, 51.60%; H, 1.66%; N, 12.16%. Calcd. for C40H16N8O16Zn: C, 51.66%; H, 1.73%; N, 12.04%. IR (KBr): νmax/cm-1 3300(νC-H), 2900(νC-H), 1750 (νC-O), 1720 (νC-O), 1480 (νC-C), 1060 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 684.A mixture of pyromellitic dianhydride , urea , metal chloride (23.5 mmol) and 0.1g of DBU was heated to 250 ºC until the reaction mixture was fused. The reaction product was washed with water, acetone and 6 M-hydrochloric acid (HCl). After drying, the solid obtained was hydrolyzed. Thirty grams of crude product, 30 g of KOH and 90 mL of water were heated for 480 min at 100 ºC. The mixture was diluted with 200 mL of water and filtered. The filtrate was acidified to pH 2 with concentrated HCl . At this point the product precipitated as a blue colored solid, which was separated from the solution by a centrifuge. The solid was washed with water three times, and dried. 3 were synthesized from a metal chloride and 1,2-dicyano-4,5-bis(hexoxymethyl)-benzene (10), which was synthesized from o-xylene via 1,2-dibromo-4,5-dimethylbenzene (7), 1,2-dibromo-4,5-bis(bromo-methylbenzene) (8) and 1,2-dibromo-4,5-bis(hexoxymethyl)benzene (9) (Compounds zene (9) .o-xylene , iodine (2 g) and iron (3 g), during a 420 min period while stirring at 5-10 °C. After the reaction, the reaction mixture was poured into water and filtered. The precipitate was washed with a 3%-NaOH solution and recrystallized from methylcyclohexane; yield 49%. mp 86.6°C. Found: C, 36.18%; H, 2.64%. Calc for C8H8Br2: C, 36.66%; H, 3.08 %. IR (KBr): νmax/cm-1 2950 (νC-H), 1601 (νC-C), 1440 (νC-C), 1340 (νC-C), 1120 (νC-C), 880 (δC-H), 640 (δC-H). 1H-NMR (CDCl3): δ, ppm 2.10 , 7.36 . MS m/z = 264. Bromine  was added dropwise to a mixture of 7  dissolved in 100 mL of carbon tetrachloride, 42.7 g (0.24 mol) of N-bromosuccinimide (NBS) and 0.08 g of 2,2’-azobis(isobutyro)nitrile was heated to 80 °C and refluxed for 480 min. After removing the carbon tetrachloride, the crude product was recrystallized from heptanes and dried under vacuum; yield 21%. mp 84.7°C, Found: C, 22.72%; H, 1.15%;. Calc for C10H10Br2: C, 22.78%; H, 1.43%. IR (KBr): νmax/cm-1 3000 (νC-H), 1650 (νC-C), 1460 (νC-C), 1200 (νC-C), 950 (δC-H), 620 (δC-H). 1H-NMR (CDCl3): δ, ppm 4.43 , 7.53 ; MS m/z = 422.A mixture of 8 was added. The temperature was gradually raised to 155 °C, and then the mixture was stirred for 90 min. The excess hexanol was removed by distillation and one hundred grams of water were added to the reaction mixture to dissolve the salt by-product. The resultant mixture was extracted with diethyl ether. The organic layer was washed with a small quantity of water and dried over calcium chloride. The diethyl ether was distilled off. The product 9 is a brown liquid; yield 88%. IR (KBr): νmax/cm-1 2900 (νC-H), 1670 (νC-C), 1240 (νC-C), 1050(δC-H), 630(δC-H). 1H-NMR (CDCl3): δ, ppm 0.89 , 1.28 , 3.52 , 4.45 , 7.64 .A piece of sodium was added to 120 g (1.18 mol) of hexanol. After the added sodium dissolved, 5.00 g (0.13 mol) of 3), 13.6 g (96.6 mmol) of copper cyanide and 100 cm3 of DMF was refluxed for 300 minutes, then cooled, and poured into 170 cm3 of aqueous ammonia. The mixture was stirred for 10 min, and was filtered. The bluish residue was washed with water and dried. The product was extracted with diethyl ether for 1,440 min using a Soxhlet apparatus and the solvent was evaporated; yield 66%. mp 360.0°C, Found: C, 80.58%; H, 9.37%;. N, 8.26%; Calc for C22H32N2O2: C, 81.43%; H, 9.94%; N, 8.63%. IR (KBr): νmax/cm-1 3200 (νC-H), 2100 (νC-N), 1460 (νC-C), 1240 (νC-C), 1095(δC-H), 60(δC-H). 1H-NMR (CDCl3): δ, ppm 4.43 , 7.53 . MS m/z = 357.A mixture of 15.2 g (33.8 mmol) of 1,2-dibromo-4,5-bis(hexoxymethyl) benzene (3-M were synthesized as follows: a mixture of 2.00 g (5.61 mmol) of 10, 11.8 mmol of metal chloride, 0.1 g of DBU, and 20 mL of hexanol as solvent was refluxed for 600 min at 155 ºC and then filtered; 3-Fe (yield: 10%) Found: C, 71.18%; H, 8.66%; N, 7.49%. Calcd. for C88H128N8O8Fe: C, 71.22%; H, 8.70%; N, 7.56%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1590 (νC-O), 1150 (νC-C), 1090 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 665. 3-Co (yield: 10%) Found: C, 71.18%; H, 8.63%; N, 7.43%. Calcd. for C88H128N8O8Co: C, 71.17%; H, 8.68%; N, 7.54%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1590 (νC-O), 1150 (νC-C), 1090 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 665. 3-Cu (yield: 10%) Found: C, 71.32%; H, 8.91%; N, 7.18%. Calcd. for C88H128N8O8Cu: C, 70.95%; H, 8.66%; N, 7.52%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1590 (νC-O), 1150 (νC-C), 1090 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 665. 3-Zn (yield: 10%) Found: C, 71.11%; H, 8.53%; N, 7.50%. Calcd. for C88H128N8O8Zn: C, 70.87%; H, 8.65%; N, 7.51%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1590 (νC-O), 1150 (νC-C), 1090 (δC-H), 720 (δC-H). UV-Vis: λmax Py/nm: 665.Compounds 4 are a new type of phthalocyanine derivatives which were synthesized from a metal chloride, urea and 9,10-anthraquinone-2,3-dicarboxylic acid (13), which was synthesized from o-xylene and phthalic anhydride via o-benzoic acid (11) and 2,3-dimethyl-9,10-anthraquinone (12) (Compounds one (12) .o-xylene in 25 mL of chloroform was added. The reaction mixture was refluxed for 60 min and the liquor then poured into a mixture of 30 g ice and 20 mL concentrated HCl, and then filtered. The product was recrystallized from diethyl ether; yield 81%. mp 170.6 °C. Found: C, 75.03%; H, 5.49%;. Calc for C16H14O3: C, 75.57%; H, 5.55 %. IR (KBr): νmax/cm-1 3450(νO-H), 2950 (νC-H), 1760 (νC-O), 1680 (νC-O), 1601 (νC-C), 1400 (νC-C), 1225 (νC-C), 1100 (νC-C), 900(δC-H), 710(δC-H). 1H-NMR (CDCl3): δ, ppm 2.27 , 7.68 . MS m/z = 254.Into a mixture of 16.3 g (0.11 mol) of phthalic dianhydride and 14 g of anhydrous aluminium chloride, 10.7 g of 11 and 2 mL of concentrated sulfuric acid were heated to 150 °C, then cooled and the crude product was recrystallized from benzene; yield 35%. mp 212.5 °C. Found: C, 80.89%; H, 5.02%; Calc for C16H12O3: C, 81.33%; H, 5.12 %. IR (KBr): νmax/cm-1 2900 (νC-H), 1760 (νC-O), 1675 (νC-O), 1420 (νC-C), 1300 (νC-C), 780(δC-H), 710(δC-H). 1H- NMR (CHCl3): δ, ppm 2.22 , 7.46 . MS m/z = 236.Eighteen g of 12 in 4.36 mL concentrated sulfuric acid was added to 160 g of water, and 12 g of potassium permanganate (KMnO4) was added gradually to the solution. Reaction was allowed to continue at 90–95 °C for 10 min with stirring; excess KMnO4 was then removed with oxalic acid. The crude product was filtered and washed with hot water. The product dissolved in hot dilute ammonia solution, unreacted 12 being filtered off. Product 13 was precipitated from the filtrate by addition of HCl. The material was filtered, washed with hot water and dried; yield 66%. mp 325.0 °C. Found: C, 64.26%; H, 5.03%;. Calc for C16H8O6: C, 64.87%; H, 4.72 %. IR (KBr): νmax/cm-1 3300 (νO-H), 2900 (νC-H), 1690 (νC-O), 1600 (νC-C), 1400 (νC-C), 1260 (νC-C), 980(δC-H), 780 (δC-H). 1H-NMR (CDCl3): δ, ppm 7.27 .A solution of 4g of 4 were synthesized by the following procedure: a mixture of 1.00 g (3.30 mmol) of 13, 2 g (34.0 mmol) of urea, 6.75 mmol of metal chloride, and 0.1 g of DBU was heated to 210 ºC until the reaction mixture was fused. The reaction product was washed with water and was dried; 4-Fe (20%) Found: C, 70.60%; H, 2.22%; N, 10.29%. Calcd. for C64H24N8O8Fe: C, 70.96%; H, 2.28%; N, 10.13%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1690 (νC-O), 1470 (νC-C), 980 (δC-H), 780 (δC-H). UV-Vis: λmax Py/nm: 688. 4-Co (23%) Found: C, 70.46%; H, 2.22%; N, 10.27%. Calcd. for C64H24N8O8Co: C, 70.17%; H, 2.26%; N, 10.30%. IR (KBr): νmax/cm-1 3300(νC-H), 2900 (νC-H), 1690 (νC-O), 1470 (νC-C), 980 (δC-H), 780 (δC-H). UV-Vis: λmax Py/nm: 688. 4-Zn (22%) Found: C, 69.84%; H, 2.37%; N, 10.48%. Calcd. for C64H24N8O8Zn: C, 69.98%; H, 2.20%; N, 10.20%. IR (KBr): νmax/cm-1 3300 (νC-H), 2900 (νC-H), 1690 (νC-O), 1470 (νC-C), 980 (δC-H), 780 (δC-H). UV-Vis: λmax Py/nm: 688.Compounds 5, a mixture of 3,6-didecylphthalonitrile and 3,4-pyridinecarbodinitrile was dissolved in pentanol (7 mL) and zinc chloride (0.05 g) was added (5b), zinc bis-3,4-pyridoporphyrazine (5c) and zinc tris-3,4-pyridoporphyrazine (5d) were synthesized from mixtures of 3,6-didecylphthalonitrile and 3,4-dicyanopyridine in 3 :1 , 1 :1  and 1 :3  ratios, respectively. Zinc tetra-3,4-pyridoporphyrazine (5a) and zinc octadecylphthalocyanine (5e) were synthesized from 3,4-dicyanopyridine [In the synthesis of as added . Zinc 1,pyridine ,54 and 3pyridine ,59, resp5a (29%) Found: C, 57.81%; H, 2.11%; N, 28.90%. Calcd. for C28H12N12Zn: C, 57.79%; H, 2.08%; N, 28.89%. IR (KBr): νmax/cm-1 2960 (νC-H), 1500 (νC-C), 1470 (νC-C), 1450 (νC-C), 1210 (δC-H), 1090 (δC-H), 790 (δC-H). UV-Vis: λmax Py/nm: 675; 5b (65%) Found: C, 68.31%; H, 6.22%; N, 17.90%. Calcd. for C49H53N11Zn: C, 68.32%; H, 6.22%; N, 17.89%. IR (KBr): νmax/cm-1 2960 (νC-H), 1600 (νC-C), 1460 (νC-C), 1440 (νC-C), 1210 (δC-H), 1080 (δC-H), 720 (δC-H). 1H-NMR : δ, ppm 7.4 (11.0H), 2.8 (4.2H), 1.3 (33.4H), 0.9 (6.7H). UV-Vis: λmax toluene/nm: 686. 5c (84%) Found: C, 73.67%; H, 8.30%; N, 12.28%. Calcd. for C70H94N10Zn: C, 73.68%; H, 8.30%; N, 12.28%. IR (KBr): νmax/cm-1 2970 (νC-H), 1600 (νC-C), 1500 (νC-C), 1470 (νC-C), 1450 (νC-C), 1210 (δC-H), 1090 (δC-H), 720 (δC-H). 1H-NMR : δ, ppm 7.4 (10.0H), 2.8 (8H), 1.3 (63.8H), 0.9 (12.3H). UV-Vis: λmax toluene/nm: 686. 5d (84%) Found: C, 76.94%; H, 9.57%; N, 8.86%. Calcd. for C91H135N9Zn: C, 76.94%; H, 9.58%; N, 8.88%. IR (KBr): νmax/cm-1 2970 (νC-H), 1600 (νC-C), 1500 (νC-C), 1470 (νC-C), 1210 (δC-H), 1100 (δC-H), 720 (δC-H). 1H-NMR : δ, ppm 7.4 (9.0H), 2.8 (12.3H), 1.3 (95.9H), 0.9 (18.8H). UV-Vis: λmax toluene/nm: 686. 5e (96%) Found: C, 79.12%; H, 10.41%; N, 6.61%. Calcd. for C112H176N8Zn: C, 79.12%; H, 10.43%; N, 6.59%. IR (KBr): νmax/cm-1 2970 (νC-H), 1600 (νC-C), 1500 (νC-C), 1470 (νC-C), 1210 (δC-H), 1100 (δC-H), 720 (δC-H). 1H-NMR : δ, ppm 7.4 (8.0H), 2.8 (16.0H), 1.3 (128.0H), 0.9 (24.1H). UV-Vis: λmax toluene/nm: 703.The mixtures were heated for 240 min in the presence of DBU as a catalyst. After cooling, the reaction mixture was dissolved in toluene (50 mL) and the solution filtered. The solvent was removed by evaporation. The products were separated and purified by TLC (eluent: toluene). 5c were separated by TLC  into four green- to blue-colored fractions. These fractions were numbered from 1, 2, 3 and 4, according to their Rf values of 0.95, 0.91, 0.75 and 0.65, respectively. Each fraction was recovered by scraping from the TLC plate, dissolved in pyridine, the solution filtered, and the solvent removed. Fraction 1: 1H-NMR (benzene-d6); δ ppm 0.93 , 1.21-1.88 , 1.88-2.23 , 2.29-2.69 , 4.13 , 4.32 , 7.35 , 7.49 , 8.30 . Fraction 2: 1H-NMR (benzene-d6); δ ppm 0.92 , 1.24-1.80 , 1.82-2.29 , 2.32-2.62 , 4.12 , 4.30 , 7.36 , 7.49 , 8.31 . Fraction 3: 1H-NMR (benzene-d6); δ ppm 0.92 , 1.16-1.95 , 1.95-2.20 , 2.20-2.36 , 2.36-2.70 , 3.99 , 4.23 , 7.36 , 7.49 , 8.30 . Fraction 4: 1H-NMR (benzene-d6); δ ppm 0.92 , 1.27-1.83 , 1.83-2.26 , 2.30-2.68 , 4.07 , 4.29 , 7.35 , 7.48 , 8.31 .The regioisomers of 5c was performed as follows: zinc 5c  was reacted with quaternizing agents such as MCAA , DES  and DMS , respectively, in DMF as solvent at 140°C for 120 min. The reaction mixture was dissolved in acetone (20 mL), cooled to room temperature and the solution filtered. The solvent was removed. The products were purified by TLC . Each product was recovered by scraping from the TLC plate, dissolving in Py, filtering the solution, and removal of the solvent. 5c with MCAA: dark blue solid . 1H-NMR (DMSO-d6); δ ppm 0.85 , 1.19-1.71 , 1.79-2.12 , 2.27-2.68 , 4.15 , 4.39 , 6.19 , 7.37 , 8.32 . IR (KBr): νmax/cm-1 3050 (νC-H), 2980 (νC-H), 1730 (νC-O), 1620 (νC-C), 1400 (νC-C), 1210 (δC-H), 1080 (δC-H), 790 (δC-H), 690 (δC-H). UV-Vis (λmaxtoluene/nm) 686: (λmaxPy/nm) 690: (λmaxwater/nm) 681; Found: C, 45.02%; H, 2.49%; N, 17.48%. Calcd. for C74H100N10O4Zn: C, 45.05%; H, 2.52%; N.17.50%. 5c with DES: blue solid . 1H-NMR (DMSO-d6) δ, ppm 0.86 , 1.02-1.70 , 1.88-2.11 , 2.30-2.68 , 4.11 , 4.25 , 7.38 , 8.18 . IR (KBr) νmax/cm-1 3050 (νC-H), 2960 (νC-H), 1500 (νC-C), 1450 (νC-C), 1400 (νC-C), 1340 (νS-O), 1180 (νS-O), 1250 (δC-H), 920 (δC-H), 760 (δC-H), 590 (δC-S). UV-Vis (λmaxtoluene/nm) 687: (λmaxPy/nm) 731: (λmaxwater/nm) 679. Found: C,37.10%; H, 1.78%; N. 18.49%. Calcd. for C70H98N10S2O6Zn: C, 37.11%; H, 1.78%; N, 18.54%. 5c with DMS: dark blue solid . 1H-NMR (DMSO-d6): δ ppm 0.88 , 1.14-1.72 , 1.82-2.17 , 2.29-2.62 , 4.06 , 4.27 , 4.51 , 7.34 , 8.23 ; IR (KBr): νmax/cm-1 3060 (νC-H), 2980 (νC-H), 1500 (νC-C), 1450 (νC-C), 1400 (νC-C), 1250 (δC-H), 1100 (δC-H), 950 (δC-H), 830 (δC-H), 660 (δC-H). UV-Vis (λmaxtoluene/nm) 739: (λmaxPy/nm) 739: (λmaxwater/nm) 684. Found: C, 49.03%; H, 3.08%; N, 21.40%. Calcd. for C72H100N10Zn: C, 49.03%; H, 3.09%; N, 21.43%.Quaternization of 5c: Regioisomers of 5c  were reacted with a quaternizing agent such as DMS  in DMF as solvent at 140 °C for 120 min. The products were purified with TLC . Each product was recovered by scraping from the TLC plate, dissolving in pyridine, filtering the solution and removal of the solvent. Fraction 1 with DMS: dark blue solid . 1H-NMR (DMSO-d6): δ ppm 0.86 , 1.15-1.70 , 1.82-2.12 , 2.19-2.49 , 3.67 , 3.92 , 4.19 , 7.37 , 8.20 ; IR (KBr): νmax/cm-1) 3070 (νC-H), 2980 (νC-H), 1500 (νC-C), 1400 (νC-C), 1250 (δC-H), 1100 (δC-H), 950 (δC-H), 820 (δC-H), 660 (δC-H); UV-Vis (λmax toluene/nm) 680: (λmax Py/nm) 703: (λmax water/nm) 690; Fluorescence (Fmax Py/nm) 687: (Fmax water/nm) 695. Found: C, 49.00%; H, 3.01%; N, 21.33%. Calcd. for C72H100N10Zn: C, 49.03%; H, 3.09%; N, 21.43%. Fraction 2 with DMS: dark blue solid . 1H-NMR (DMSO-d6): δ ppm 0.87 , 1.16-1.73 , 1.73-2.10 , 2.10-2.55 , 3.90 , 3.99 , 4.17 , 7.23 , 8.25 . IR (KBr): νmax/cm-1 3070 (νC-H), 2980 (νC-H), 1500 (νC-C), 1400 (νC-C), 1250 (δC-H), 1100 (δC-H), 980 (δC-H), 830 (δC-H), 660 (δC-H); UV-Vis (λmax toluene/nm) 689: (λmax Py/nm) 675: (λmax water/nm) 686; Fluorescence (Fmax Py/nm) 684: (Fmax water/nm) 690; Found: C, 48.99%; H, 2.98%; N, 21.22%. Calcd. for C72H100N10Zn: C, 49.03%; H, 3.09%; N, 21.43%. Fraction 3 with DMS: dark blue solid . 1H-NMR (DMSO-d6): δ ppm 0.85 , 1.09-1.63 , 1.70-2.11 , 2.11-2.42 , 3.86 , 3.97 , 4.21 , 7.23-7.33 , 8.21 . IR (KBr): λmax/cm-1 3080 (νC-H), 2970 (νC-H), 1500 (νC-C), 1400 (νC-C), 1250 (δC-H), 1100 (δC-H), 950 (δC-H), 830 (δC-H), 660 (δC-H). UV-Vis (λmax toluene/nm) 681: (λmax Py/nm) 689: (λmax water/nm) 689; Fluorescence (Fmax Py / nm) 690: (Fmax water / nm) 698; Found: C, 49.03%; H, 3.03%; N, 21.40%. Calcd. for C72H100N10Zn: C, 49.03%; H, 3.09%; N, 21.43%. Fraction 4 with DMS: dark blue solid . 1H-NMR (DMSO-d6): δ ppm 0.87 , 1.20-1.63 , 1.71-2.17 , 2.17-2.47 , 3.85 , 4.09 , 4.27 , 7.21-7.36 , 8.22 . IR (KBr): λmax/cm-1 3070 (νC-H), 2980 (νC-H), 1500 (νC-C), 1400 (νC-C), 1250 (δC-H), 1100 (δC-H), 950 (δC-H), 830 (δC-H), 660 (δC-H); UV-Vis (λmax toluene/nm) 677: (λmax Py/nm) 730: (λmax water/nm) 673; Fluorescence (Fmax Py/nm) 686: (Fmax water/nm) 687; Found: C.49.02: H. 3.08: N. 21.43. Calcd. for C72H100N10Zn: C. 49.03: H. 3.09: N.21.43.Quaternized regioisomers of 6a was synthesized from 1,2-dicyanobenzene. Compound 6c was synthesized from 1,2-dicyano-3,4,5,6-tetrafluorobenzene. Compounds 6d-g were synthesized from the precursors, 1,2-dicyano-3,6-bis(thiobutyl)-4,5-difluorobenzene (14a) [14b) [14c) [14d) [Compound ne (14a) , 1,2-dica) [14b) , 1,2-dicb) [14c)  and 1,2-c) [14d) , respect6a: A solution of boron trichloride  was added into a mixture of 1,2-benzenedicarbonitrile  and 1-chloronaphtahalene (12 mL) under an argon atmosphere at -3°C. After addition, the reaction mixture was heated to 120 °C with stirring. Hexane was distilled off. It was heated to 250°C for 10 minutes and cooled to room temperature. The product was extracted with petroleum ether for 1440 min and then toluene for 120 min on a Soxhlet extractor. The obtained product was recrystallized from ethanol (Compound  ethanol .6b-g were synthesized in accordance with above-mentioned SubPC synthetic method. 6a (71%) Found: C, 66.88%; H, 2.81%; N, 19.50%. Calcd. for C24H12N6BCl: C, 66.88%; H, 2.81%; N, 19.59%. IR (KBr): νmax/cm-1 3200 (νC-H), 3070 (νC-H), 2370 (νC-N), 1611 (νC-C), 1452 (νC-C), 1304 (νC-H), 1130 (δC-H), 950 (δC-S). 1H-NMR (CDCl3): δ, ppm 7.21 . MS m/z = 431. UV-Vis: λmax (toluene)/nm: 564. 6b (39%) Found: C, 72.18%; H, 6.06%; N, 14.01%. Calcd. for C36H36N6BCl: C, 72.18%; H, 6.06%; N, 14.01%. IR (KBr): νmax/cm-1 2980 (νC-H), 1720 (νC-C), 1620 (νC-C), 1450 (νC-H), 1400 (νC-H), 1360 (δC-H), 1280 (δC-H), 1190 (δC-H), 760 (δC-H). 1H-NMR (CDCl3): δ, ppm 7.80 , 7.49 , 7.32 , 1.35 . MS m/z = 599. UV-Vis: λmax toluene/nm: 566. 6c (26%) Found: C, 50.39%; N, 14.70%. Calcd. for C24N6BClF12: C, 50.39%; H, 0.00%; N, 14.70%. IR (KBr): νmax/cm-1 1490 (νC-H), 1450 (νC-N), 1270 (νC-F), 1220 (νC-F), 1120 (νC-H), 960 (δC-H), 800 (δC-H), 760 (δC-S). MS m/z = 647. UV-Vis: λmax toluene/nm: 572. 6d (8%) Found: C, 53.99%; H, 5.10%; N, 7.84%. Calcd. for C48H54N6BClF6S6: C, 53.99%; H, 5.10%; N, 7.87%. IR (KBr): νmax/cm-1 2980 (νC-H), 2150 (νC-N), 1600 (νC-C), 1500 (νC-C), 1450 (νC-C), 1150 (δC-H), 850 (δC-H). 1H-NMR (CDCl3): δ, ppm 3.15 , 1.51 , 0.90 . MS m/z = 1068. UV-Vis: λmax (toluene)/nm: 596. 6e (5%) Found: C, 60.69%; H, 2.55%; N, 7.08%. Calcd. for C60H30N6BClF6S6: C, 60.66%; H, 2.55%; N, 7.08%. IR (KBr): νmax/cm-1 3050 (νC-H), 2250 (νC-N), 1580 (νC-C), 1450 (νC-C), 1250 (νC-F), 1090 (δC-H), 670 (δC-S). 1H-NMR (CDCl3): δ, ppm 7.26 . MS m/z = 1188. UV-Vis: λmax toluene/nm: 621. 6f (17%) Found: C, 58.07%; H, 7.31%; N, 5.65%. Calcd. for C72H108N6BClS12: C, 58.07%; H, 7.31%; N, 5.65%. IR (KBr): νmax/cm-1 2980 (νC-H), 2125 (νC-N), 1580 (νC-C), 1500 (νC-C), 1460 (νC-C), 1000 (νC-H), 800 (δC-H). 1H-NMR (CDCl3): δ, ppm 3.16 , 1.50 , 0.91 . UV-Vis: λmax toluene/nm: 612. 6g (13%) Found: C, 66.67%; H, 3.50%; N, 4.86%. Calcd. for C96H60N6BClS12: C, 66.67%; H, 3.50%; N, 4.86%. IR (KBr): νmax/cm-1 3080 (νC-H), 2190 (νC-N), 1600 (νC-C), 1500 (νC-C), 1460 (νC-C), 1000 (δC-H), 800 (δC-H). 1H-NMR (CDCl3): δ, ppm 7.26 . UV-Vis: λmax (toluene)/nm: 634.SubPC derivatives 15 were synthesized in three steps via intermediates 16 and 17a-c. Intermediate 16 was synthesized by the following procedure: 2,3-dicyanohydroquinone  in dichloromethane (100 mL) and Py  was treated with trifluoromethanesulfonic anhydride  under nitrogen at -78 °C. After the reaction, the mixture was allowed to warm slowly to room temperature; stirring was continued for 1,440 min. The mixture was poured into water (600 mL) and the organic layer was extracted using dichloromethane (5 × 100 mL). The extract was washed in turn with water, 2%-hydrochloric acid, water, brine and water, and dried on magnesium sulfate (MgSO4). The filtrate and the solvent evaporated. The crude product was recrystallized from dichloromethane to afford 16  as colorless needles. Found: C, 28.32%; H, 0.48%; N, 6.59%. Calcd. for C10H2F6N2S2O6: C, 28.31%; H, 0.48%; F, 26.87%; N, 6.60%; O, 22.63%; S, 15.12%. IR (KBr): cm-1 3115 (νC-H), 2550 (νC-N), 1601 (νC-C), 1472 (νC-C), 1439 (νC-C), 1134 (νS=O). 1H-NMR : δ, ppm 8.44 .The target compounds 17a-c were synthesized as follows: to a mixture of 16 , potassium carbonate (1.16 g) and DMSO (15 mL), thiophenols such as p-toluenethiol, 4-methoxybenzenethiol and tert-butylthiophenol (4 mmol) were added; the mixture was reacted at room temperature for 1,440 min in nitrogen atmosphere. The reaction products were poured into water (300 mL), and the organic layer extracted using dichloromethane (5 × 100 mL), and dried on MgSO4. The filtrate and the solvent evaporated. The crude product was washed with methanol (3 × 50 cm3) and recrystallized from toluene to afford 17 as a yellow solid. 3,6-bis(thiophenylmethyl)phthalonitrile (2a)  Found: C, 70.90%; H, 4.30%; N, 7.50%. Calcd. for C22H16N2S2: C, 70.93%; H, 4.33%; N, 7.52%; S, 17.22. IR (KBr): cm-1 3050 (νC-H), 2970 (νC-H), 2218 (νC-N), 1600 (νC-C), 1535 (νC-C), 1490 (νC-C), 1435 (νC-C), 1210, 809 (δC-H). 1H-NMR (DMSO-d6): δ, ppm 7.54 , 7.46 , 7.35 (s2H), 2.66 ; 3,6-bis(thiophenylmethoxy)phthalonitrile (2b)  Found: C, 65.30%; H, 4.00%; N, 6.93%. Calcd. for C22H16N2S2O2: C, 65.32%; H, 3.99%; N, 6.93%; S, 15.82%; O, 7.91%. IR (KBr): cm-1 3050 (νC-H), 2970 (νC-H), 2216 (νC-N), 1600 (νC-C), 1540 (νC-C), 1487 (νC-C), 1430 (νC-C), 1210, 810 (δC-H). 1H-NMR (DMSO-d6): δ, ppm 7.49 , 7.06 , 7.04 (s2H), 3.79 ; 3,6-bis(thiophenyl tert-butyl)phthalonitrile (2c)  Found: C, 73.65%; H, 6.18%; N, 6.11%. Calcd. for C28H28N2S2: C, 73.64%; H, 6.18%; N, 6.13%; S, 14.04%. IR (KBr): cm-1 3040 (νC-H), 2960 (νC-H), 2210 (νC-N), 1600 (νC-C), 1500 (νC-C), 1460 (νC-C), 1210, 808 (δC-H). 1H-NMR (DMSO-d6): δ, ppm 7.50 , 7.46 , 7.26 , 1.28 .Intermediates 15 were synthesized following procedure; A solution of 17 (0.25 mmol), the appropriate metal chloride or metal acetate (0.065 mmol), DBU (0.2 mL) as a catalyst and 1-pentanol (10 mL) was refluxed for 420 min. After cooling to room temperature, the reaction products were poured into methanol to form a precipitate, which was washed with water and methanol, and chromatographed on silica gel with toluene as eluent. The 1,4,8,11,15,18,22,25-octakis(thiophenyl-methyl)phthalocyanines (15a); 15a-Cu  Found: C, 67.98%; H, 4.51%; N, 7.01%. Calcd. for C88H65N8S8Cu: C, 67.99%; H, 4.21%; N, 7.21%; S, 16.50%; Cu, 4.09%. MS (FAB): m/z found 1554, Calcd. 1554.59: 15a-Co  Found: C, 68.10%; H, 4.20%; N, 7.25%. Calcd. for C88H65N8S8Co: C, 68.19%; H, 4.23%; N, 7.23%; S, 16.55%; Co, 3.80%. MS (FAB): m/z found 1550, Calcd. 1549.97: 15a-Ni  Found: C, 68.18%; H, 4.20%; N, 7.13%. Calcd. for C88H65N8S8Ni: C, 68.20%; H, 4.23%; N, 7.23%; S, 16.55%; Ni, 3.79%. MS (FAB): m/z found 1550, Calcd. 1549.73: 15a-Zn  Found: C, 67.87%; H, 4.23%; N, 7.11%. Calcd. for C88H65N8S8Zn: C, 67.91%; H, 4.21%; N, 7.20%; S, 16.48%; Zn, 4.20%. MS (FAB): m/z found 1556, Calcd. 1556.43: 15a-Pb  Found: C, 62.29%; H, 3.88%; N, 6.40%. Calcd. for C88H65N8S8Pb: C, 62.24%; H, 3.86%; N, 6.60%, S, 15.11%; Pb, 12.19%. MS (FAB): m/z found 1699, Calcd. 1698.24: 215a-H  Found: C, 70.85%; H, 4.66%; N, 7.51%. Calcd. for C88H66N8S8: C, 70.84%; H, 4.46%; N, 7.51%, S, 17.1%. MS (FAB): m/z found 1492, Calcd. 1492.04; 1,4,8,11,15,18,22,25-octakis(thiophenylmethoxy)phthalocyanines (15b); 15b-Cu  Found: C, 62.88%; H, 3.91%; N, 6.65%. Calcd. for C88H65N8S8 O8Cu: C, 62.82%; H, 3.89%; N, 6.66%; S, 15.25%; O, 7.61%; Cu, 3.77%. MS (FAB): m/z found 1682, Calcd. 1682.58: 15b-Co  Found: C, 63.00%; H, 3.89%; N, 6.59%. Calcd. for C88H65N8S8O8Co: C, 62.99%; H, 3.90%; N, 6.68%; S, 15.29%; O, 7.63%; Co, 3.51%. MS (FAB): m/z found 1678, Calcd. 1677.97: 15b-Ni  Found: C, 63.01%; H, 3.92%; N, 6.67%. Calcd. for C88H65N8S8O8Ni: C, 63.01%; H, 3.92%; N, 6.67%; S, 15.29%; O, 7.63%; Ni, 3.49%. MS (FAB): m/z found 1678, Calcd. 1677.73: 15b-Zn  Found: C, 62.75%; H, 3.95%; N, 6.65%. Calcd. for C88H65N8S8O8Zn: C, 62.75%; H, 3.89%; N, 6.65%; S, 15.23%; O, 7.60%; Zn, 3.88%. MS (FAB): m/z found 1684, Calcd. 1684.42: 15b-Pb  Found: C, 57.88%; H, 3.59%; N, 6.15%. Calcd. for C88H65N8S8O8Pb: C, 57.88%; H, 3.59%; N, 6.14%; S, 14.05%; O, 7.01%; Pb, 11.33%. MS (FAB): m/z found 1827, Calcd. 1826.23: 215b-H  Found: C, 65.24%; H, 4.11%; N, 6.93%. Calcd. for C88H66N8O8S8: C, 65.24%; H, 4.11%; N, 6.92%, O, 7.90, S, 15.18%. MS (FAB): m/z found 1620, Calcd. 1620.03; 1,4,8,11,15,18,22,25-octakis-(thiophenyl tert-butyl)phthalocyanines (15c); 15c-Cu  Found: C, 71.13%; H, 6.05%; N, 5.87%. Calcd. for C112H113N8S8Cu: C, 61.13%; H, 6.02%; N, 5.92%; S, 13.56%; Cu, 3.37%. MS (FAB): m/z found 1891, Calcd. 1891.22: 15c-Co  Found: C, 71.24%; H, 6.04%; N, 5.93%. Calcd. for C112H113N8S8Co: C, 71.30%; H, 6.04%; N, 5.94%; S, 13.60%, Co, 3.12%. MS (FAB): m/z found 1886, Calcd. 1886.61: 15c-Ni  Found: C, 71.31%; H, 6.04%; N, 5.89%. Calcd. for C112H113N8S8Ni: C, 71.31%; H, 6.04%; N, 5.94%; S, 13.60%; Ni, 3.11%. MS (FAB): m/z found 1886, Calcd. 1886.37: 15c-Zn  Found: C, 71.00%; H, 6.01%; N, 5.92%. Calcd. for C112H113N8S8Zn: C, 71.06%; H, 6.02%; N, 5.92%; S, 13.55%; Zn, 3.45%. MS (FAB): m/z found 1893, Calcd. 1803.07: 15c-Pb  Found: C, 66.12%; H, 5.63%; N, 5.53%. Calcd. for C112H113N8S8Pb: C, 66.11%; H, 5.60%; N, 5.51%; S, 12.61%; Pb, 10.17%. MS (FAB): m/z found 2035, Calcd. 2034.88: 215c-H  Found: C, 73.55%; H, 6.26%; N, 6.13%. Calcd. for C112H114N8S8: C, 73.56%; H, 6.28%; N, 6.13%, S, 14.03%. MS (FAB): m/z found 1829, Calcd. 1828.68.The target compounds -1 solution of TBAP in a stream of nitrogen. CVs were recorded by scanning the potential at the rate of 50 mV s-1. The working and counter electrodes were platinum wires and the reference electrode was a Ag/AgCl saturated sodium chloride electrode. The chronoamperometry was measured following an applied voltage pulse from -1200 to 0 mV vs. Ag/AgCl and from 0 to +1600 mV vs. Ag/AgCl, and the reversible pulse.CV of metal octakis(hexoxymethyl)phthalocyanines and metal anthraquinocyanine were carried out with a BAS CV-50W voltammetric analyzer at room temperature in DMSO containing a 0.10 mol·LLaser flash photolysis in film was performed using a total reflection sapphire cell , which was spin-coated with a 1.2 μm thick photopolymer film. An excitation light pulse  from a YAG laser was expanded and exposed over the entire sample cell. A monitoring light from a xenon lamp passed through the multireflection cell which was connected to the head of an optical fiber attached to a monochrometer equipped with a photomultiplier or to a spectral multichannel analyzer system. The films were prepared as follows: a 10 wt% PMMA solution was made up in cyclohexanone, and allylbenzopyridoporphyrazines were added to this solution by dissolving to a thickness of 1.2 μm thick by spin-coating a solution onto a sapphire cell. After that the films were covered with a PVA solution.1, 2, 3, and a new type of phthalocyanine derivative, 4 have been synthesized. Then, the cyclotetramerization products from a 1:1 mol mixture of 3,6-didecylphthalonitrile and 3,4-dicynopyridine, zinc bisbisporphyrazines, 5 were synthesized. The cyclotetramerization products have position isomers. The isomers of 5c was separated into fore fractions. Moreover, metal phthalocyanine analogous, SubPCs and its derivatives which possessed substituents such as thiobutyl and thiophenyl were synthesized.M-PCs Electrochemical measurements were performed above mentioned phthalocyanine derivatives and analogous in order to examine their electron transfer abilities and electrochemical mechanism in an organic solvent.5c and position isomers were measured, using laser-flash photolysis in a PMMA film. In generally, the triplet lifetime increased as the number of Py groups in the molecule increased. However, the lowest symmetric isomer having two Py rings in the molecule showed the longest triplet state lifetime. The compound was suitable for use as a photosensitizer in photodynamic cancer therapy.Photochemical properties such as the triplet state lifetime were measured using laser-flash photolysis. The triplet state of zinc non-peripheral substituted alkylbenzopyridoporphyrazines, 6 were measured sensitization properties. Sensitization properties of 6 with 2,4,6-tris(trichloromethyl)-1,3,5-triazine as radical generation reaction in a PMMA film have been investigated by laser-flash photolysis.Thiobutyl and thiophenyl substituted subPC derivatives 15 can be synthesized. Their strong Q band absorption peaks appear around 800 nm. The synthesized phthalocyanines have high solubility in organic solvents, high heat resistance without discotic liquid crystal behavior, no absorptions in the visible region, and a simple structure without any regioisomers.Phthalocyanines having S-aryl groups at non-peripheral position, i.e., 1,4,8,11,15,18,22,25-octakis(thio-phenylmethyl)phthalocyane compounds