Autorecycling oxidation of alcohol catalyzed by 1,3,7,9,11,12,14-heptazapentacene-2,4,8,10 (14H,3H,9H,12H)-tetraones (mixed flavins)

1,3,7,9,11,12,14-Heptazapentacene-2,4,8,10 (14$\text{H}$,3$\text{H}$,9$\text{H}$,12$\text{H}$)-tetraones (mixed flavins) were prepared by the cyclization of 1,5-dihydro-8-[N-alkyl-N-(5-nitrouracil-6-yl)-amino-5-deazaflavins with Vilsmeier reagent. The mixed flavins oxidized alcohol under neutral condition in sunlight and a remarkable autorecycling was observed.     

Syntheses of 1,3,6,8,10,11,14-heptaazapentaphene-2,4,7,9(14H,3H,8H, -11H)-tetrones (angular mixed flavins), 1,3,5,6,8,10,11,14-octaazapentaphene-2,4,7,9(14H,3H,8H,11H)-tetrones (angular doubled flavins), and their related compounds

Cyclization of N, N′-dialkyl-N-(3-methyluracil-6-yl)-N′-(5-nitro-3-methyluracil-6-yl)- p-phenylenediamines with the Vilsmeier reagent gives the corresponding 1,3,6,8,10,11,14-heptaazapentaphene-2,4,7,9-(14H,3H,8H,-11H) -tetrones (angular mixed flavins) 2. Cyclization of N, N′-di(5-nitro-3-methyluracil-6-yl)-p-phenylenedi-amines with the Vilsmeier reagent gives the corresponding 1,3,5,6,8,10,11,14-octaazapentaphene-2,4,7,9-(14H,3H,8H,11H)-tetrones (angular doubled flavins) 11 along with the angular mixed flavins 2.     

Syntheses of 1,3,8,10,12-pentazanaphthacene-2,4,7,9-(12H,3H,8H,10H)-tetraones (linear pyrimidine-fused 5-deazaflavins), 1,3,6,8,12-pentazabenz[a]anthracene-2,4,7,9(12H,3H,6H,8H)-tetraones(bent pyrimidine-fused 5-deazaflavins), and their flavin analogs

1,3,8,10,12-Pentazanaphthacene-2,4,7,9(12H,3H,8H,10H)-tetraones (linear pyrimidine-fused 5-deazaflavins) and 1,3,6,8,12-pentazabenz[a]anthracene-2,4,7,9(12H,3H,6H,8H)-tetraones (bent pyrimidine-fused 5-deazaflavins) were synthesized by condensation of 7-alkylaminoquinazoline with 6-chloro-5-formyl-3-methyluracil. Also, their flavin analogs, 1,3,5,8,10,12-hexazanaphthacene-2,4,7,9(12H,3H,8H,10H)-tetraones (linear pyrimidine-fused flavins) and l,3,5,6,8,12-hexazabenz[a]anthracene-2,4,7,9(12H,3H,6H,8H)-tetraones (bent pyrimidine-fused flavins) were synthesized by cyclization of 7-[N-alkyl-N-(5-nitrouracil-6-yl)]aminoquin-azolines with the Vilsmeier reagent.     

Synthesis, properties, and oxidizing ability of 9,11-dimethylbenzocyclohepta[6,7-b]pyrimido[5,4-d]furan- 10(9H),12(11H)-dionylium tetrafluoroborate

Convenient preparation of novel 9,11-dimethylbenzocyclohepta[6,7-b]pyrimido[5,4-d]furan-10(9H),12(11H)-dionylium tetrafluoroborate 11*BF4- consisted of a condensation reaction of benzo[d]tropone with dimethylbarbituric acid and following oxidative cyclization reaction by using DDQ-Sc(OTf)3 or photoirradiation under aerobic conditions. Alternative synthesis of 11*BF4- was also accomplished by a condensation reaction of 2-methoxybenzo[d]tropone with dimethylbarbituric acid and a subsequent cyclization reaction by using 42% aq HBF4. The X-ray crystal analysis and MO calculation were carried out to clarify the structural characteristics. Properties of the cation 11 were studied by the pKR+ value (4.7) and reduction potentials (-0.46 and -1.07 V vs Ag/AgNO3) as well as the reaction with some nucleophiles. The oxidizing ability of 11*BF4- toward alcohols in the autorecycling process was demonstrated as well.     

螺［异苯并呋喃－1（3H），9＇－（9H）－2＇－N，N－二苄胺基－6＇－二乙胺基占吨］－酮－3的合成及晶体结构研究

合成了螺［异苯并呋喃－１（３Ｈ），９＇－（９Ｈ）－２＇－Ｎ，Ｎ－二苄胺基－６＇－二乙胺基占吨］－酮－３，Ｃ＿（３７）Ｈ＿（３４）Ｎ＿２Ｏ＿３，单斜晶系，空间群Ｃｃ，晶体学参数为ａ＝１６．８２６（４），ｂ＝１０．６４８（４），ｃ＝１７．６１８（７），β＝９２．２５（２）°，Ｖ＝３１５４（２），Ｚ＝４，Ｍ＿ｒ＝５６６．７，Ｄ＿ｘ＝１．１９ｇ／ｃｍ３，Ｆ（０００）＝１２００。结构由直接法解出，偏离因子Ｒ＝０．０８０。分子由占吨和异苯并呋喃两部分组成Ｙ形结构，占吨部分相连的苄基的两个苯环位于占吨部分的两侧。     

Synthesis of 2,4-(1H,3H)-quinazolinediones

Improved procedures for syntheses of kilogram quantities of quinazolinedione 5 and its intermediates 2,3 and 4 are described. The mechanism of formation of 5 is discussed as well as a side reaction resulting in 7 .     

配合物Cu(C14H9NO3)(C3H4N2)的合成、晶体结构及性质研究

合成了配合物Cu(C₁₄H₉NO₃)(C₃H₄N₂)[C₁₄H₉NO₃^2- 为N-(2-羧基苯基)-水杨醛亚胺,C₃H₄N₂为咪唑].晶体属正交晶系,空间群Pca2₁,晶胞参数a=0.94453(12)nm,b=1.12278(9)nm,c=2.9123(4)nm,V=3.0885(6)nm³,Mr=370.84,Z=8,最终的偏离因子R=0.036,wR=0.087,GOF=0.975.三齿Schiff碱配体中的二个氧原子、一个氮原子和咪唑的一个氮原子与铜原子配位,形成扭曲的平面正方形结构.通过元素分析,IR,UV,CV和TG表征了配合物的结构.     

Synthesis of 3-(aminooxoethyl)-6-methyl-1-(thiethan-3-yl)-pyrimidine-2,4-(1H,3H)-diones

A new approach to prepare 2-chloroacetamides has been developed, based on the reaction of chloroacetyl chloride with excess of secondary amines. Alkylation of 6-methyl-1-(thiethan-3-yl)pyrimidine-2,4(1H,3H)-dione with the synthesized 2-chloroacetamides in the presence of potassium carbonate has afforded N ³-acetamido-substituted 6-methyl-1-(thiethan-3-yl)pyrimidine-2,4(1H,3H)-diones.     

Novel synthesis, properties, and oxidizing ability of 11,13-disubstituted 3,8-methanocycloundeca[8,9-b]pyrimido[5,4-d]-furan-12(11H),14(13H)-dionylium tetrafluoroborates

Synthesis of novel 4,9-methanoundecafulvene [5-(4,9-methanocycloundeca-2',4',6',8',10'-pentaenylidene)pyrimidine-2(1H),4(3H),6(5H)-trione] derivatives 10a-c was accomplished. Their structural characteristics were investigated on the basis of the 1H and 13C NMR and UV-vis spectra. Upon treatment with DDQ, 10a-c underwent oxidative cyclization to give novel 11,13-disubstituted 3,8-methanocycloundeca[8,9-b]pyrimido[5,4-d]furan-12(11H),14(13H)-dionylium tetrafluoroborates 11a-c*BF4- in good yields. The spectroscopic properties of 11a-c*BF4- were studied, and the structural characterization of 11b*BF4- was performed by the X-ray crystal analysis. Cations 11a-c were very stable, and their pKR+ values were determined spectrophotometrically to be 8.3-8.9. The electrochemical reduction of 11a-c exhibited low reduction potentials at -0.43 to -0.45 (V vs Ag/AgNO3) upon cyclic voltammetry (CV). In a search for reactivity, reactions of 11a*BF4- with some nucleophiles, hydride and diethylamine, were carried out to clarify that the methano-bridge controls the nucleophilic attacks to occur with endo-selectivity. The photoinduced oxidation reactions of 11a*BF4- toward some amines under aerobic conditions were carried out to give the corresponding carbonyl compounds in more than 100% yield.     

3-(3''''-羟基丁基)异苯并呋喃-1(3H)-酮的合成

由邻苯二甲酸酐为原料 ,经中间体 3 羟基苯酞 (3 ) ,再经溴丙烯及锡存在下 3的烯丙基化、硼氢化氧化、铬酐氧化、二甲基锌甲基化 ,共 6步反应合成了 3 (3’ 羟基丁基 )异苯并呋喃 1(3H) 酮。     

Two new groups of homoleptic rare earth pyridylbenzimidazolates: (NC12H8(NH)2)[Ln(N3C12H8)4] with Ln = Y,Tb, Yb,and [Ln(N3C12H8)2(N3C12H9)2][Ln(N3C12H8)4](N3C12H9)2 with Ln = La,Sm, Eu

The compounds (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y, Tb, Yb, and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), with Ln = La, Sm, Eu, were obtained by reactions of the group 3 metals yttrium and lanthanum as well as the lanthanides europium, samarium, terbium, and ytterbium with 2-(2-pyridyl)-benzimidazole. The reactions were carried out in melts of the amine without any solvent and led to two new groups of homoleptic rare earth pyridylbenzimidazolates. The trivalent rare earth atoms have an eightfold nitrogen coordination of four chelating pyridylbenzimidazolates giving an ionic structure with either pyridylbenzimidazolium or [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)](+) counterions. With Y, Eu, Sm, and Yb, single crystals were obtained whereas the La- and Tb-containing compounds were identified by powder methods. The products were investigated by X-ray single crystal or powder diffraction and MIR and far-IR spectroscopy, and with DTA/TG regarding their thermal behavior. They are another good proof of the value of solid-state reaction methods for the formation of homoleptic pnicogenides of the lanthanides. Despite their difference in the chemical formula, both types (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y (1), Tb (2), Yb (3), and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), Ln = La (4), Sm (5), Eu (6), crystallize isotypic in the tetragonal space group I4(1). Crystal data for (1): T = 170(2) K, a = 1684.9(1) pm, c = 3735.0(3) pm, V = 10603.5(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.053, wR2 = 0.113. Crystal data for (3): T = 170(2) K, a = 1683.03(7) pm, c = 3724.3(2) pm, V = 10549.4(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.047, wR2 = 0.129. Crystal data for (5): T = 103(2) K, a = 1690.1(2) pm, c = 3759.5(4) pm, V = 10739(2) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.050, wR2 = 0.117. Crystal data for (6): T = 170(2) K, a = 1685.89(9) pm, c = 3760.0(3) pm, V = 10686.9(11) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.060, wR2 = 0.144.     

Synthesis of 9-C6H5-3-(π-C5H5)-3,1,2-CoC2B9H10 by cross-coupling reaction of 9-I-3-(π-C5H5)-3,1,2-CoC2B9H10 with C6H5ZnCl catalyzed by palladium complexes

The cross-coupling reaction of 9-I-3-(π-C₅H₅)-3,1,2-CoC₂B₉H₁₀ with organozinc compounds catalyzed by palladium complexes was used to synthesize the first representative ofB-phenyl-substituted carboranes, 9-C₆H₅-3-(π-C₅H₅)-3,1,2-CoC₂B₉H₁₀. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No: 6, pp. 1253–1254, June, 1998.