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1.
2.
The reactions of symmetrical and unsymmetrical 2,2'-dipyridylamines with 1,2-dibromoethane and 1,3-dibromopropane give imidazopyridinium and pyridopyrimidium bromides, respectively. These acetone/CH(2)Cl(2)-insoluble, highly fluorescent quaternary ammonium salts undergo addition/ring opening upon treatment with methanolic KOH to give pyridin-2-one derivatives. A sequential N,N-dialkylation/ring-opening hydrolysis/N,N-dialkylation/ring-opening hydrolysis strategy was developed for the construction of unsymmetrical bis(pyridin-2-ones).  相似文献   

3.
A convenient and efficient synthesis of highly functionalized dihydropyrido[2,3-d]pyrimidines via a double [5 + 1] annulation strategy starting from easily available alpha-alkenoyl-alpha-carbamoyl ketene-(S,S)-acetals 1 and cheap reagents (NH4OAc, DMF, and POCl3) has been developed. In the first step of the double annulation route, 2-amino-3-carbamoyl-5,6-dihydro-4-pyridones 2 were created in high to excellent yields by a formal [5C + 1N] annulation reaction of ketene-(S,S)-acetals 1 with ammonia (from ammonium acetate). In the second step of the double annulation strategy, the highly functionalized dihydropyrido[2,3-d]pyrimidine derivatives, 7,8-dihydropyrido[2,3-d]pyrimidin-4(3H)-ones 3 (when R1 = aryl) and 7,8-dihydropyrido[2,3-d]pyrimidines 4 (when R1 = H), were constructed, respectively, in fair to good yields by reacting 2 with excessive Vilsmeier reagent (DMF/POCl3). A mechanism involved in the second [5 + 1] annulation step, including a formal [5 + 1] annulation and accompanied chlorovinylation, chloroformylation, amination, and aromatization reactions, is proposed.  相似文献   

4.
The rearrangement reactions of protonated and lithium-cationized 2-pyrimidinyloxy-N-arylbenzylamine derivatives were studied by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and infrared multiphoton dissociation mass spectrometry (IRMPD). Our results show that three kinds of rearrangement reactions occur in IRMPD processes. First, nearly all protonated 2-pyrimidinyloxy-N-arylbenzylamine derivatives undergo Pathway A to form the K ion series. It is proposed that this rearrangement (migration of a substituted benzyl group) proceeds by way of a gas-phase intramolecular S(N)2 reaction. Second, a gas phase intramolecular S(N)Ar type rearrangement mechanism is proposed to explain the formation of the F ion series from protonated and lithium-cationized 5 (or 6). This skeletal rearrangement reaction competes with the S(N)2 reaction of the Pathway A, which produces the K ion series, in IRMPD of protonated 5 and 6. Third, the formation pathway of the W ion series is explained by a gas phase Cope type rearrangement mechanism.  相似文献   

5.
The aminobis(phosphonite) PhN(P(OC6H4OMe-o)2)2 (PNP; 1) reacts with 2 equiv of CuI to give a binuclear complex, Cu2(mu2-I)2(NCCH3)2(mu-PNP) (2), whereas similar reactions with CuCl and CuBr furnish tetranuclear "ladder"-type complexes, Cu4(mu2-X)2(mu3-X)2(mu-PNP)2 (3, X = Cl; 4, X = Br), in excellent yield. The complex 2 when heated under vacuum turns into the tetranuclear complex 5 in a reversible fashion. Similarly, the complexes 3 and 4 on dissolution in CH3CN dissociate reversibly into the corresponding binuclear complexes from which the tetrameric complexes can be readily regenerated. Treatment of 2 with excess of pyridine produces the heterosubstituted derivative, Cu2(mu2-I)2(C5H5N)2(mu-PNP) (6). The interaction of 2 with 2,2'-bipyridine in 1:1 and 1:2 ratios produces the mono- and disubstituted derivatives, Cu2(mu2-I)I(C10H8N2)(mu-PNP) (7) and [Cu2(mu2-I)(C10H8N2)2(mu-PNP)]I (8), respectively. The chloro and bromo analogues of 7 are prepared by treating the tetranuclear derivatives 3 and 4 with 2,2'-bipyridine. Reaction of 2 with 4,4'-bipyridine in the presence of AgOTf gives the cationic complex [Cu4(NCCH3)4(C10H8N2)2(mu-PNP)2](OTf)4 (9), whereas the complex [Cu2(NCCH3)2(mu-PNP)2](OTf)2 (10) was obtained from the reaction of 2 with 1 equiv of 1 and AgOTf. The reactions of 3 and 4 with 2 equiv of 4,4'-bipyridine in acetonitrile afford one-dimensional copper(I) coordination polymers [Cu2(mu2-X)2(mu-PNP)(C10H8N2)]n (13, X = Cl; 14, X = Br). The molecular structures of 2-4, 6-8, 12, and 14 are confirmed by X-ray crystallography.  相似文献   

6.
Straka M  Pyykkö P 《Inorganic chemistry》2003,42(25):8241-8249
High-energy nitrogen-rich pentazolides of groups 6 and 13-16 are studied theoretically. Many of them have experimentally known azide analogues. Our highest nitrogen-to-element ratio of 40:1 is achieved in the systems [M(N5)8](2-) (M=Cr, Mo, W). The thermodynamic and kinetic stability of the studied systems grows with the negative charge on the system and is highest for tetra-pentazolides and hexa-pentazolides of B, Al, and Si. Systems such as B(N5)4- or Si(N5)6(2-) are examples of the most stable candidates for these new species. N(N5)2- is a candidate for a new all-nitrogen system. Neutral and positive systems were less stable. Pentazole derivatives of "dinuclear" C2Hn and N2Hn systems were investigated and were found to be of comparable stability as their "mononuclear" analogues. Pentazole derivatives of benzene, the C6H(6-n)(N5)n (n=2, 3, 6) systems, have a similar stability as the experimentally known phenylpentazole. A borazine analogue, N3B3H3(N5)3 is predicted to be one of the most stable systems of this family.  相似文献   

7.
4-Heteroarylidene-2-phenyl-1,3-oxazol-5(4H)-ones were prepared by reactions of hippuric acid with substituted furan-2-carboxaldehydes or furo[b]pyrrole type aldehydes. The reactivity of various furan-2-carboxaldehyde derivatives in this reaction is discussed. The effect of microwave irradiation on some condensation reactions was compared with "classical" conditions. The results show that microwave irradiation shortens the reaction times while affording comparable yields. Elementary analysis, UV, IR and 1D NMR proved the structure of new synthesised compounds. 2D NMR spectroscopic measurements confirmed that the configuration at the carbon-carbon double bond corresponds to the pure E isomers of the products.  相似文献   

8.
The multigram syntheses of the protio ligands (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHSiMe(2)R)(2) (R = Me, H(2)N(2)NN' 3; R = (t)Bu, H(2)N(2)NN() 4) are described via reactions of the previously reported (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NH(2))(2) (1). A new synthesis of 1 is reported starting from 2-aminomethylpyridine and N-tosylaziridine, proceeding via (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2) (2). Reaction of H(2)N(2)NN' or H(2)N(2)NN* with (n)BuLi gives good yields of the dilithiated derivatives Li(2)N(2)NN' and Li(2)N(2)NN*. Reaction of H(2)N(2)NN' or H(2)N(2)NN* with [MCl(2)(CH(2)SiMe(3))(2)(Et(2)O)(2)] gives the cis-dichloride complexes [MCl(2)(L)] (L = N(2)NN', M = Zr 7 or Hf 8; L = N(2)NN(), M = Zr 9). The corresponding reactions of H(2)N(2)NN' or H(2)N(2)NN* with [Zr(NMe(2))(4)] afford the bis(dimethylamide) derivatives [Zr(NMe(2))(2)(L)] (L = N(2)NN' 10 or N(2)NN* 11). All of these protonolysis reactions proceed smoothly and in good yields. Attempts to prepare the titanium complexes [Ti(X)(2)(N(2)NN')] (X = Cl or NMe(2)) were unsuccessful. The X-ray crystal structures of (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2).EtOH, [ZrCl(2)(N(2)NN')].0.5C(6)H(6), [Zr(NMe(2))(2)(N(2)NN')], and [Zr(NMe(2))(2)(N(2)NN*)] are reported.  相似文献   

9.
Tong BM  Chen H  Chong SY  Heng YL  Chiba S 《Organic letters》2012,14(11):2826-2829
K(2)CO(3)-mediated reactions of 6-bromo-2-hexenoates and 7-bromo-2-heptenoate with active methylene compounds deliver highly substituted cyclopentane and cyclohexane derivatives, respectively via a sequence of S(N)2-conjugate addition reactions (formal [4 + 1]- and [5 + 1]-annulation) in a diastereoselective manner.  相似文献   

10.
Herein, a divergent synthesis of a variety of 2α- and 5α-substituted furan derivatives from 2-hydroxy-1,4-diones is reported. By using appropriate substrates and an acid catalyst, the reactions occurred selectively through cyclization/1,6-conjugate addition or cyclization/Friedel–Crafts-type cascade reactions. A broad range of nucleophilic reagents (>10 types for the 1,6-conjugate addition for 5α substitution and >20 types for the Friedel–Crafts-type cascade reaction for 2α substitution), including alcohols, amides, furan, thiophene, pyrrole, indole, phenols, and many others, can successfully participate in the reactions, providing a universal strategy for a diversity-oriented synthesis of α-substituted furan derivatives. Deuteriation experiments and DFT calculations were carried out to support the proposed reaction mechanisms. Antifungal activity experiments revealed that products with an indole or 4-hydroxycoumarin core substituted at the 2α position showed moderate activities against Rhizoctorzia solani and Botrytis cinerea, respectively.  相似文献   

11.
Cyclotriphosphazene derivatives containing a P-NHR group in the side-chain react in the presence of a strong base to form stable intermolecular bridged products. Reaction of sodium hydride with mono-spiro cyclophosphazene derivatives having a P-NH group, N(3)P(3)Cl(4)[O(CH(2))(3)NH], (1a) or N(3)P(3)Cl(4)[CH(3)N(CH(2))(3)NH], (1b) leads to formation of bis-cyclophosphazenes bridged with an eight-membered cyclophosphazene ring in an ansa arrangement (2a, 2b) whereas reaction of sodium hydride with mono-amino cyclophosphazene derivatives [N(3)P(3)Cl(5)(NHR), R = n-hexyl, 3a; i-Pr, 3b; Ph, 3c] give bis-cyclophosphazenes bridged with a four-membered cyclophosphazane ring in a spiro arrangement (4a-c). In the latter reaction P-O-P bridged compounds (5a-c) were also obtained as a result of hydrolysis reactions associated with the amount of moisture in the solvent tetrahydrofuran. In addition, it was found that reaction of a mixture of cyclotriphosphazene with either mono spiro compound, (1a) or (1b), in the presence of sodium hydride lead to formation of the first examples of asymmetrically-bridged cyclophosphazenes (6a-b).  相似文献   

12.
A series of dimesitylboryl acceptor (mesityl=2,4,6-trimethylphenyl) and/or diphenylamino donor (-N(Ph)2)-substituted truxene derivatives, classified as D-or-A substituted compounds and D-and-A substituted charge-transfer compounds, have been synthesized. Two D-and-A substituted truxene compounds, namely, 2-dimesitylboryl-7,12-di(N,N-diphenylamino)-5,5',10,10',15,15'-hexaethyltruxene (BN2) and 2,7-di(dimesitylboryl)-12-(N,N-diphenylamino)-5,5',10,10',15,15'-hexaethyltruxene (B2N), exhibit extraordinarily large solvatochromism ranging from 420 nm (in hexane) to 580 nm (in acetonitrile) in aprotic solvents, which can be used to probe the polarity of the solution environment. Due to proton-donor interactions, the solvatochromic red shift of BN2 and B2N in protic solvents has been significantly decreased, and this effect can be used to identify local protic and aprotic environment. Furthermore, because of the interaction between F- and acceptor, BN2 and B2N show sharp spectral response to fluoride ion concentration. The simultaneous "turn-off" at 500 nm and "turn-on" at 380 nm of the fluorescence signal have provided a good example of a fluorescent ratiometric method, which can greatly enhance the sensitivity of the fluoride ion probe. Underlying these interesting spectral phenomena and multifunctional probe properties is the charge-transfer strategy of grafting donor and acceptor moieties, as A-pi-D2 or A2-pi-D style, to the triangular truxene.  相似文献   

13.
Our explorations of the reactivity of Fe/Mo/S clusters of some relevance to the FeMoco nitrogenase have led to new double-fused cubane clusters with the Mo2Fe6S8 core as derivatives of the known (Cl4-cat)2Mo2Fe6S8(PPr3)6 (I) fused double cubane. The new clusters have been obtained by substitution reactions of the PPr3 ligands with Cl-, BH4-, and N3-. By careful control of the conditions of these reactions, the clusters [(Cl4-cat)(PPr3)MoFe3S4(BH4)2]2(Bu4N)4 (II), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(BH4)]2(Bu4N)2 (III), [(Cl4-cat)(PPr3)MoFe3S4(N3)2]2(Bu4N)4 (IV), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(N3)]2(Bu4N)2 (V), and [(Cl4-cat)(PPr3)MoFe3S4Cl2]2(Et4N)4 (VI) have been obtained and structurally characterized. A study of their electrochemistry shows that the reduction potentials for the derivatives of I are shifted to more positive values than those of I, suggesting a stabilization of the reduced clusters by the anionic ligands BH4- and N3-. Using 1H NMR spectroscopy, we have explored the lability of the BH4- ligand in II in coordinating solvents and its hydridic character, which is apparent in its reactivity toward proton sources such as MeOH or PhOH.  相似文献   

14.
The "azido gauche effect" was examined both experimentally and theoretically and was found to determine the conformation of, for example, (4R)- and (4S)-azidoproline (Azp) derivatives. For (4R)Azp derivatives, the azido gauche effect induces a preferred C(4)-exo conformation of the pyrrolidine ring, which leads to stabilization of the s-trans amide conformer of, e.g., Ac-(4R)Azp-OCH(3) (5R) via an n-->pi interaction between the nonbonding electrons of the oxygen of the acetyl group and the carbonyl group of the ester. For (4S)Azp derivatives, the azido gauche effect results in a C(4)-endo conformation of the pyrrolidine ring that does not allow for this stabilizing n-->pi interaction of the s-trans conformer. Consequently, a significantly higher s-trans:s-cis amide conformer ratio is observed for (4R)Azp compared to (4S)Azp derivatives (e.g., 6.1:1 versus 2.6:1 in D(2)O for Ac-(4R)Azp-OCH(3) (5R) compared to Ac-(4S)Azp-OCH(3) (5S)). These conformational preferences are reflected in the higher tendency of (4S)Azp-containing peptides to form cyclic peptides with all-cis amide bonds compared to (4R)Azp derivatives. Ab initio calculations demonstrate that the strength of the azido gauche effect is comparable to that of the well-known "fluorine gauche effect". For azidoethane derivatives N(3)-CH(2)CH(2)-X (X = N(3), NHCOH, NHAc, or N(CH(3))Ac), the ab initio calculations revealed energy differences of 5-13 kJ mol(-)(1) between the anti and gauche conformations in favor of the gauche conformer. Calculations were also performed for the (4R)Azp and (4S)Azp derivatives 5R and 5S, supporting the experimentally observed data.  相似文献   

15.
A straightforward chemoenzymatic synthesis of optically active trans-N,N-dialkylcyclopentane-1,2-diamines has been efficiently developed starting out from their analogous (+/-)-trans-2-(N,N-dialkylamino)cyclopentanols. The route involves the one-pot stereospecific transformation of the racemic amino alcohols into racemic diamines and a subsequent kinetic resolution by means of lipase-B from Candida antarctica-catalyzed acylation reactions. The careful selection of both the alkyl substituents present in the diamine and the derivatization strategy applied to the enzymatic reaction enabled the easy preparation of other synthetically valuable optically active trans-cyclopentane-1,2-diamines derivatives.  相似文献   

16.
A set of 1,3-propanediamine derivatives connected to carbohydrates (5) has been prepared in four steps from peracetylated sugar and 1,3-dibromo-2-propanol in 60-73% yields. D-Glucose, D-mannose, D-galactose, D-xylose, D-ribose, and maltose are utilized as sugar molecules in this work. The diamine moiety was connected to the C1 carbon of the glycopyranose ring via an O-glycoside bond. All of the anomeric configurations and sugar puckering conformations, except in the D-maltose derivative, were determined by X-ray crystallography of the diazido or dibromo precursors. While glycosidation of peracetylated galactopyranose with 1,3-dibromo-2-propanol in the presence of boron trifluoride afforded both anomers, the neighboring group participation of the 2-acetoxy group yielded a single anomer for the other substrates. This method has been used to synthesize a library of sugar-pendant diamines including an OH-protected derivative (6), and an N,N'-diisopropyl-substituted derivative (7). A similar series of reactions using 2,3-dibromo-1-propanol gave ethylenediamine-type derivatives (11), and bis(bromomethyl)bis(hydroxymethyl)methane (12) gave bisglucose-pendant derivatives (16).  相似文献   

17.
6‐Aryl‐5‐cyano‐4‐pyrimidinone‐2‐thion derivatives 1a‐c reacted with methyl iodide (1:2) to give the corresponding 2‐S,N‐dimethyl pyrimidine‐4‐one derivatives 2a‐c . Compounds 2a‐c were in turn, reacted with hydrazine hydrate to give the sulfur free reaction products 3a‐c . These reaction products were taken as the starting materials for the synthesis of several new heterocyclic derivatives. Reaction of 3a‐c with acetic anhydride and formic acid gave pyrimido triazines 4a‐c and 7a‐c , respectively. Their reactions with active methylene containing reagents gave the corresponding 2‐(1‐pyrazonyl)‐N‐methyl pyrimidine derivatives 9a‐c and 10a‐c , respectively. Their reactions with aromatic aldehydes afforded the corresponding 2‐hydrazono pyrimidine derivatives 11a‐c . The structure of these reactions products were established based on both elemental analysis and spectral data studies.  相似文献   

18.
Xu GL  Ren T 《Inorganic chemistry》2006,45(26):10449-10456
A series of diruthenium compounds, Ru2(DArF)3(L")Cl (2), where the auxiliary ligand DArF is DmAniF or D(3,5-Cl2Ph)F and L" is one of the diarylformamidinate ligands containing at least one biphenyl, were prepared from Suzuki reactions between Ru2(DArF)3(L')Cl (1), where L' is (4-I-Ph)NC(H)NPh (N-(4-iodophenyl)-N'-phenylformamidinate) or D(4-I-Ph)F (N,N'-di(4-iodophenyl)formamidinate), and ArB(OH)2 (Ar = Ph and 4-CH3C(O)Ph) in satisfactory yields. Alkynylation of the type 2 compounds with LiCCPh yielded the alkynyl derivatives Ru2(DArF)3(L")(CCPh) (3). Alternatively, type 3 compounds can be prepared from the Suzuki coupling reaction between Ru2(DArF)3(L')(C2Ph) and ArB(OH)2. A structural comparison between the type 1 and 2 compounds revealed minimal changes in the coordination sphere of Ru2 core. Cyclic voltammograms of Suzuki derivatives resemble those of the parent compounds, indicating the retention of the electrophore characteristic of diruthenium species upon peripheral modification.  相似文献   

19.
双枝[1,3,4]-噁二唑衍生物的合成与荧光性质   总被引:4,自引:0,他引:4  
孟康  钱鹰 《有机化学》2009,29(1):71-77
通过Wittig反应和Heck反应合成了三个双枝噁二唑衍生物: N-{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}二苯胺(BBOD-2), N,N-双{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}苯胺(BBOD-3), N,N,N-三{4-{2-{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}苯基}胺(BBOD-4). 化合物结构经过红外光谱、核磁共振谱、质谱和熔点确证, 测定了它们在不同溶剂中的紫外光谱和单光子荧光光谱. BBOD-1, BBOD-2, BBOD-3, BBOD-4在二氯甲烷中的最大吸收峰分别位于295, 390, 398和408 nm; 最大发射峰分别为360, 486, 483和487 nm. 讨论了Stokes位移与溶剂极性的关系.  相似文献   

20.
Chen WZ  Ren T 《Inorganic chemistry》2003,42(26):8847-8852
Metathesis reactions between Ru(2)(DMBA)(4)Cl(2) (DMBA = N,N'-dimethylbenzamidinate) and MX (M = Na and K) yielded bis-adduct derivatives Ru(2)(DMBA)(4)X(2) (X = CN (1), N(3) (2), N(CN)(2) (3)). Metathesis reactions between Ru(2)(DMBA)(4)(NO(3))(2) and KI resulted in Ru(2)(DMBA)(4)I(2) (4). Compound 1 is diamagnetic, while compounds 2-4 are paramagnetic (S = 1). Both compounds 1 and 2 undergo two reversible one-electron processes, an oxidation and a reduction, while compound 3 features a quasireversible reduction. Single-crystal X-ray diffraction studies revealed that the Ru-Ru bond lengths are 2.4508(9), 2.3166(7), 2.304[1], and 2.328(1) A for compounds 1-4, respectively. Structural and electrochemical data clearly indicate that the axial ligands impart a significant influence on the electronic structures of diruthenium species.  相似文献   

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