Spiro-compounds,synthesis and catalytic dehydrogenation of substituted spiro[5,5] undecanes

Catalytic dehydrogenation of 1-propyl-8,9-benzospiro[5,5]undecane-7-ol (5: R = H), and 1-propyl-3′-methyl-8,9-benzospiro[5,5]undecane-7-ol (5: R = Me) has been carried out to study the effect of a bulky alkyl group on the ring in the ring transformation of the spiro[5,5]undecane system. The catalytic dehydrogenation of the spiro-compound 5(R = H) gave phenanthrene and 1-ethylpyrene (minor product) and spiro compound 5(R = Me) gave only 3-methylphenanthrene. For the synthesis of 5 (R = H or Me), the anhydride (1) of 1-carboxy-2-propylcyclohexane-1-acetic acid was condensed with benzene and toluene to give 2 (R = H or Me) which was reduced catalytically to 3(R = H or Me). Intramolecular acylation of 3(R = H or Me) gave the spiroketone (4: R = H or Me) which was reduced to 5(R = H or Me).     

Synthesis of analogues of the 2,3,6,-triazaphenothiazine ring system

Treatment of 2,3-dichloroquinoxalines with 2-amino-6-picoline-3-thiol gave a mixture of 2,3-bis(2-amino-6-picolinyl-3-thio)quinoxalines ( 16 , R = H, CI) and 2,3-bis (N,N-dimethylamino)quinoxalines ( 15 , R = H, CI) separated by fractional crystallization. A similar reaction of 3-amino-6-methoxypyridine-2(1H)-thione ( 9 ) with 4,5-dichloropyridazin-3(2H)-one ( 21 ) gave 4-chloro-5-(3-amino-6-methoxypyridyl-2-thio)pyridazin-3(2H)-one ( 22 ). Concentrated hydrochloric acid-catalysed cyclization of 22 gave the non-rearranged 7-methoxy-2,3,6-triazaphenothiazin-1(2H)-one. The action of compound 22 in refluxing glacial acetic acid gave, on the other hand, 7-methoxy-2,3,6-triazaphenothiazin-4(3H)-one via a Smiles rearrangement. These cyclized compounds are the first known derivatives of the new 2,3,6-triazaphenothiazine ring system.     

有机锗硫杂环戊酮化合物的合成

合成了14个1,1-二氯-1,2-锗硫杂-3-环戊酮等四类新型锗硫杂五元环化合物, 元素分析、红外光谱、氢核磁共振谱以及质谱分析验证了它们的组成及结构。     

Syntheses and characterization of mu,eta(1),eta(1)-3,5-di-tert-butylpyrazolato derivatives of aluminum

The 3,5-di-tert-butylpyrazolato (3,5-tBu(2)pz) derivatives of aluminum [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)R(1)R(2)](2) (R(1) = R(2) = Me 1; R(1) = R(2) = Et, 2; R(1) = R(2) = Cl, 3; R(1) = R(2) = I, 4; [(eta(2)-3,5-tBu(2)pz)(3)Al], 5; [Al(2)(eta(1),eta(1)-3,5-tBu(2)pz)(2)(mu-E)(C triple bond CPh)(2)] (E = S (6), Se (7), Te (8)) have been prepared in good yield. Compounds 1 and 2 were obtained by the reactions of H[3,5-tBu(2)pz] with Me(3)Al and Et(3)Al, respectively. Reaction of [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)H(2)](2) with the pyrazole H[3,5-tBu(2)pz] gave [(eta(2)-3,5-tBu(2)pz)(3)Al] (5). The reaction of [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)R(2)](2) (R = H, Me) and I(2) yielded 4, while the reaction of 1 equiv of K[3,5-tBu(2)pz] and AlCl(3) afforded 3. In addition, the reaction of [Al(2)(eta(1),eta(1)-3,5-tBu(2)pz)(2)(mu-E)H(2)] and HC triple bond CPh gave 6, 7, and 8. All compounds have been characterized by elemental analysis, NMR, and mass spectroscopy. The molecular structure analyses of compounds 1, 3, 6, and 7 by X-ray crystallography showed that complexes 1 and 3 are dimeric with two eta(1),eta(1)-pyrazolato groups in twisted conformation while 6 and 7 with two eta(1),eta(1)-pyrazolato groups display a boat conformation.     

Synthesis and structural characterization of silanethiolato complexes having tert-butyldimethylsilyl and trimethylsilyl groups

Treatment of cyclotrisilathiane (Me2SiS)3 with 3 equiv. of RLi (R = Me, But) in hexane-Et2O afforded the lithium silanethiolates LiSSiMe2R, and the tmeda adduct [(tmeda)LiSSiMe2But]2 1 (tmeda =N,N,N',N'-tetramethylethylenediamine) was isolated in the case of R = But. Reaction of Fe(CH3CN)2(CF3SO3)2, CoCl2, and [Cu(CH3CN)4](PF6) with 1 gave rise to the silanethiolato complexes M(SSiMe2But)2(tmeda)(M = Fe 2, Co 3), and [Cu(SSiMe2But)]4 4, respectively. Complexes (C5H5)2Ti(SSiMe2R)2(R = Me 5, But 6) and Ni(SSiMe2R)2(dppe)[R = Me 7, But 8; dppe = 1,2-bis(diphenylphosphino)ethane] were prepared from treatments of (C5H5)2TiCl2 and NiCl2(dppe) with the corresponding lithium silanethiolates. Complex 7 readily reacted with (C5H5)TiCl3 to produce the Ti-Ni heterobimetallic compound (C5H5)TiCl(mu-S)2Ni(dppe) 9, in which silicon-sulfur bond cleavage took place. Characterization of all compounds through spectroscopic techniques and elemental analyses are also described. X-Ray structural data for compounds 1 and 3-9 are reported.     

Chemistry of the phosphinidene oxide ligand

Reaction of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] with DBU followed by O2 gives the first anionic phosphinidene oxide complex (H-DBU)[MoCp{P(O)R*}(CO)2] (1) (DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene; R* = 2,4,6-C6H2tBu3). This anion displays three different nucleophilic sites located at the O, P, and Mo atoms, as illustrated by the reactions reported. Thus, reaction of 1 with excess HBF4.OEt2 gave the fluorophosphide complex [MoCp(PFR*)(CO)2] via the hidroxophosphide intermediate [MoCp{PR*(OH)}(CO)2]. Related alkoxyphosphide compounds [MoCp{P(OR)R*}(CO)2] (R = Me, C(O)Ph) were prepared by reaction of 1 with [Me3O]BF4 and PhC(O)Cl, respectively, whereas reaction of 1 with MeI or C3H5Br gave the P,O-bound phosphinite complexes [MoCp(kappa2-OPRR*)(CO)2] (R = Me, C3H5). Metal-based electrophiles were found to bind at either O or Mo positions. Thus, reaction of 1 with [ZrCl2Cp2] gave the phosphinidene oxide bridged [MoCp{P(OZrClCp2)R*}(CO)2], whereas reaction with SnPh3Cl gave trans-[MoCp{P(O)R*}(CO)2(SnPh3)], an heterometallic complex having an intact terminal P(O)R* ligand.     

Self-assembly of diorganotin(IV) moieties and 2-pyrazinecarboxylic acid: syntheses, characterizations and crystal structures of monomeric, polymeric or trinuclear macrocyclic compounds

A series of diorganotin(IV) compounds of the type [R(2)Sn(pca)Cl](3)(R = CH(3); (n)Bu; C(6)H(5); C(6)H(5)CH(2); Hpca = 2-pyrazinecarboxylic acid), R(2)Sn(pca)(2)(mH(2)O)xnH(2)O (m= 1: R = CH(3), n= 2, R =(n)Bu, n= 0; m= 0, n= 0: R =(n)Bu, C(6)H(5), C(6)H(5)CH(2)) and (Et(3)NH)(+)[R(2)Sn(pca)(2)Cl](-)xmH(2)O (m= 0: R = CH(3), (n)Bu, C(6)H(5)CH(2); m= 1: R = C(6)H(5)) have been obtained by reactions of 2-pyrazinecarboxylic acid with diorganotin(iv) dichloride in the presence of sodium ethoxide or triethylamine. All compounds were characterized by elemental, IR and NMR spectra analyses. Except for compounds, and, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that compounds and were trinuclear macrocyclic structures with six-coordinate tin(IV) atoms, compounds and were monomeric structures with seven-coordinate tin(IV) atoms, compounds and were polymeric chain structures with seven-coordinate tin(IV) atoms and compounds and were stannate with seven-coordinate tin(IV) atoms.     

氟化钾催化取代酚与硅氢化合物的反应

本文研究了氟化物存在下, 硅氢化合物与酚类反应的规律性。选择了在KF存在下, 以DMF为溶剂, 含有不同邻, 间, 对位取代酚作为反应底物与多种含氢硅烷进行了一系列反应, 在反应活性上获得了具有一定规律性的结果, 同时得到了21个末见报道的新芳氢基有机硅化合物, 所得化合物均经元素分析, IR和1H NMR测定, 确定了结构。     

Synthesis, characterization, and reaction of aluminum halide amides supported by a bulky beta-diketiminato ligand

Monomeric aluminum chloride amides with the general formula LAl(Cl)NR2 (1, R = Me; 2, R = iPr; 3, R = SiMe 3; L = HC[C(Me)N(Ar)]2; Ar = 2,6- iPr2C6H3) were prepared by selected routes. Treatment of LAlBr 2 (4) and LAlI2 with LiNMe2 yielded LAl(Br)NMe2 (5) and LAl(I)NMe2 (6), respectively. The alkylation of 1 and 2 with MeLi gave the corresponding methylated compounds LAl(Me)NR2 (7, R = Me; 8, R = iPr); however, no reaction of 3 with MeLi was observed because of steric hindrance. Subsequent fluorination of 1- 3 afforded LAl(F)NR2 (9, R = Me; 10, R = iPr; 11, R = SiMe3). Compounds 1-11 were characterized by multinuclear NMR, electron impact mass spectrometry, and IR. The constitution of compounds 1-3 was confirmed by single-crystal X-ray diffraction studies.     

Synthesis of 2,2′-dithiobis- and 2,2′-trithiobis-3-pyridinecarboxylic acid derivatives as new potential radiosensitizers/radioprotectors

This paper reports the synthesis of dithio and trithio derivatives of 1,2-dihydro-2-thioxopyridine, starting with 1,2-dihydro-2-thioxo-3-pyridine carboxylic acid 1 . This compound reacted with thionyl chloride to give the respective dithiobis (acyl chloride) 2 , which hydrolyzed to the corresponding dithio acid 3 . On the other hand, 1 reacted with sulfur dichloride to give trithio acid 4 , which on treatment with thionyl chloride gave the trithiobis (acyl chloride) 5 . Treatment of 2 and 5 with ethanol/pyridine, gave 8 and 12 respectively. Compounds 2–5, 8 and 12 were unstable in alkaline medium and they were degraded to 1 . The bis(acyl chloride) 2 and 5 reacted with ammonia and primary and secondary amines to give the respective bis(amide) 9 and 13 . Most of these amides (R = H, alkyl, aryl, R' = H) were found to be unstable in the presence of bases such as triethylamines, pyridine or excess of the starting amine, which promotes disproportion to give (see Scheme 3) the respective N-substituted (R) 1,2-dihydro-2-thioxo-3-pyridinecarboxamide 10 and the respective 2-substituted (R)-3-oxo-isothiazolo[5,4-b]pyridine 11 . On the other hand, compounds 11 were unstable to strong bases and they were transformed into the respective compounds 10 by an unknown mechanism. Boiling 11f with sodium hydroxide in ethanol gave 10f (50%). According to these last results, boiling 9h or 13d with sodium hydroxide in ethanol 10h (68%) and 10d (70%) were obtained.     

CO2 and formate complexes of phosphine/borane frustrated Lewis pairs

The reaction of a solution of B(C6F4H)3 and either iPr3P or tBu3P with CO2 afforded the species R3P(CO2)B(C6F4H)3 (R=iPr (1), tBu (2)). In a similar fashion the boranes, RB(C6F5)2 (R=hexyl, cyclohexyl (Cy), norbornyl), ClB(C6F5)2, or PhB(C6F5)2 were combined with tBu3P and CO2 to give the species tBu3P(CO2)BR(C6F5)2 (R=hexyl (3), Cy (4), norbornyl (5), Cl (6), Ph (7)). Similarly, the compounds [tBu3PH][RBH(C6F5)2] (R= hexyl (8), Cy (9), norbornyl (10)) were prepared by reaction of the precursor frustrated Lewis pair (FLP) with H2. Subsequent reactions of 9 and 10 with CO2 afforded the species [((C6F5)2BR)2(μ-HCO2)][tBu3PH] (R= Cy (11), norbornyl (12)). In related chemistry, combinations of the boranes RBG(C6F5)2 (R=hexyl, Cy, norbornyl) with tBu3P treated with an equivalent of formic acid gave [(C6F5)2BR(HCO2)][tBu3PH] (R=hexyl (13), Cy (14), norbornyl (15)). Subsequent addition of an additional equivalent of borane provides a second synthetic route to 11 and 12. Crystallographic studies of compounds 2-6 and 8-14 are reported and discussed. Further understanding of the FLP complexation and activation of CO2 is provided by computational studies.     

α-(2-苯并噻唑氧基)烃基膦酸酯的合成性质和生物活性

为探索α-芳(杂 环)磷酸衍生物的生物活性,寻求含磷农药的新母体,合成了十六个未见文献报道的α-(苯并噻唑-2-氧代)烃基膦酸衍生物,所有化合物的结构均IR,HNMR, 元素分析等确证,并对生物活性进行了初步的研究.     

An investigation of Staudinger reactions involving cis-1,3,5-triazidocyclohexane and tri(alkylamino)phosphines

The reaction of 1,3,5-cis-triazidocyclohexane with the electron-rich tris(dialkylamino)phosphines P(NMe(2))(3) (1) and N(CH(2)CH(2)NMe)(3)P (2b) in acetonitrile for 3 h furnished the corresponding tris-phosphazides 1,3,5-cis-(R(3)PN(3))(3)C(6)H(9), 3a (R(3)P = 1) and 3b (R(3)P = 2b), in 90% and 92% yields, respectively. The same reaction with the relatively electron-poor tris(dialkylamino)phosphine MeC(CH(2)NMe)(3)P (4) for 2 days gave the tris-iminophosphorane, 1,3,5-cis-(R(3)PN)(3)C(6)H(9), 5a (R(3)P = 4), in 60% yield. Compound 3b is a thermally stable solid that did not lose dinitrogen when refluxed in toluene for 24 h or when heated as a neat sample at 100 degrees C /0.5 Torr for 10 h. By contrast, tris-phosphazide 3a decomposed to the tris-iminophosphorane 1,3,5-cis-(R(3)PN)(3)C(6)H(9), 5b (R(3)P = 1), in 3 h in quantitative yield upon heating to 100 degrees C in toluene. Factors influencing the formation of the phosphazides or the iminophosphoranes in these reactions are discussed. The reaction of 3b with 4 equiv of benzoic acid gave [N(CH(2)CH(2)NMe)(3)P=NH(2)]PhCO(2) ([6bH]PhCO(2)) in quantitative yield along with benzene (56% yield) and dinitrogen. The same reaction with 3a gave [(Me(2)N)(3)P=NH(2)]PhCO(2) ([7aH]PhCO(2)) (quantitative yield), benzene (15% yield), and dinitrogen(.) Treatment of [6bH]PhCO(2) with KO(t)Bu afforded N(CH(2)CH(2)NMe)(3)P=NH (6b) in 40% overall yield. Compound 6b upon treatment with PhCH(2)CH(2)Br produced [6bH]Br in 90% yield along with styrene. The new compounds were characterized by analytical and spectroscopic methods, and selected compounds (3b, 5a, and [6bH]Br) were structured by X-ray crystallography. A special feature of 3b is its capability to function as a starting material for 6b, which was not accessible by other synthetic routes.     

环氧化－6－豆甾酮的合成

以豆甾醇为原料，经Ａ／Ｂ环结构改造，所得双键化合物用过苯甲酸氧化，可高选择性、高产率地合成出２ａ，３ａ－二乙酰基－２２Ｒ，２３Ｒ－环氧－６－豆甾酮和２ａ，３ａ－环氧－２２Ｒ，２３Ｒ－环氧－６－豆甾酮。由此二化合物可较方便地制得２ａ，３ａ，２２Ｒ，２３Ｒ－四乙酰基－６－豆甾酮。     

固-液相转移催化合成V.醛亚胺的michael加成和羰基加成反应合成α-氨基 酸

报道了在以K~2CO~2为固体碱的固-液相转移催化条件下,用醛亚胺与亲电的 烯烃和醛类化合物进行Michael加成,羰基加成反应,合成了一系列醛亚胺亲核加成产物.并通过水解羰基加成产物制备了一系列丝氨酸衍生物.该法简便,温和,反应时间短,产率高,是合成具有取代基的甘氨酸,丙氨酸和丝氨酸及其酯的一种有用方法.     

Synthesis, structures and reactions of lithium complexes of [(o-RCHC6H4)PPh2=NSiMe3]-(R = H, SiMe3) ligands

N-Trimethylsilyl o-methylphenyldiphenylphosphinimine, (o-MeC6H4)PPh2=NSiMe3 (1), was prepared by reaction of Ph2P(Br)=NSiMe3 with o-methylphenyllithium. Treatment of 1 with LiBun and then Me3SiCl afforded (o-Me3SiCH2C6H4)PPh2=NSiMe3 (2). Lithiations of both 1 and 2 with LiBu(n) in the presence of tmen gave crystalline lithium complexes [Li{CH(R)C6H4(PPh(2=NSiMe3)-.tmen](3, R = H; 4, R = SiMe3). From the mother liquor of 4, traces of the tmen-bridged complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}]2(mu-tmen) (5) were obtained. Reaction of 2 with LiBun in Et2O yielded complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}.OEt2] (6). Reaction of lithiated with Me2SiCl2 in a 2:1 molar ratio afforded dimethylsilyl-bridged compound Me2Si[CH2C6H4(PPh2=NSiMe3)-2]2 (7). Lithiation of 7 with two equivalents of LiBun in Et2O yielded [Li2{(CHC6H4(PPh2=NSiMe3)-2)2SiMe2}.0.5OEt2](8.0.5OEt2). Treatment of 4 with PhCN formed a lithium enamide complex [Li{N(SiMe3)C(Ph)CHC6H4(PPh2=NSiMe3)-2}.tmen] (9). Reaction of two equivalents of 5 with 1,4-dicyanobenzene gave a dilithium complex [{Li(OEt2)2}2(1,4-{C(N(SiMe3)CHC6H4(PPh2=NSiMe3)-2}2C6H4)] (10). All compounds were characterised by NMR spectroscopy and elemental analyses. The structures of compounds 2, 3, 5, 6 and 9 have been determined by single crystal X-ray diffraction techniques.     

异-α-姜黄烯及其衍生物的合成

姜科姜黄属是一个重要的药用植物群其根茎和块根分别称为姜黄和郁金。中医中药认为, 郁金具有行气, 纠瘀和通经等功效。动物药理试验表明, 姜科植物温郁金具有抗生育活性, 而其挥发油主要含有姜烯、α-姜黄烯和异-α-姜黄烯等倍半萜类化合物。本文合成了温郁金挥发油的另一个成分异-α-姜黄烯和其衍生物2-甲基-6-对甲苯基-2-庚醇、脱氢异-α-姜黄烯和2-甲基-6-对甲苯基-5-庚烯-2-醇。它们的化学结构得到确证。     

Preparation of five- and six-coordinate aryl(hydrido) iridium(III) complexes from benzene and functionalized arenes by C-H activation

The reaction of the in situ generated cyclooctene iridium(I) derivative trans-[IrCl(C8H14)(PiPr3)2] with benzene at 80 degrees C gave a mixture of the five-coordinate dihydrido and hydrido(phenyl) iridium(III) complexes [IrH2(Cl)(PiPr3)2] 2 and [IrH(C6H5)(Cl)(PiPr3)2] 3 in the ratio of about 1 : 2. The chloro- and fluoro-substituted arenes C6H5X (X = Cl, F), C6H4F2 and C6H4F(CH3) reacted also by C-H activation to afford the corresponding aryl(hydrido) iridium(III) derivatives [IrH(C6H4X)(Cl)(PiPr3)2] 7, 8, [IrH(C6H3F2)(Cl)(PiPr3)2] 9-11 and [IrH[C6H3F(CH3)](Cl)(PiPr3)2] 12, 13, respectively. The formation of isomeric mixtures had been detected by 1H, 13C, 19F and 31P NMR spectroscopy. Treatment of 3 and 7-13 with CO gave the octahedral carbonyl iridium(III) complexes [IrH(C6H3XX')(Cl)(CO)(PiPr3)2] 5, 14-20 without the elimination of the arene. The reactions of trans-[IrCl(C8H14)(PiPr3)2] with aryl ketones C6H5C(O)R (R = Me, Ph), aryl ketoximes C6H5C(NOH)R (R = Me, Ph) and benzaloxime C6H5C(NOH)H resulted in the formation of six-coordinate aryl(hydrido) iridium(III) compounds 21-25 with the aryl ligand coordinated in a bidentate kappa2-C,O or kappa2-C,N fashion. With C6H5C(O)NH2 as the substrate, the two isomers [IrH[kappa2-N,O-NHC(O)C6H5](Cl)(PiPr3)2] 26 and [IrH[kappa2-C,O-C6H4C(O)NH2](Cl)(PiPr3)2] 27 were prepared stepwise. Treatment of trans-[IrCl(C8H14)(PiPr3)2] with benzoic acid gave the benzoato(hydrido) complex [IrH[kappa2-O,O-O2CC6H5](Cl)(PiPr3)2] 29 which did not rearrange to the kappa2-C,O isomer.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

The structures, morphologies, and photophysical properties of multiluminescent layered lanthanide-phosphono-carboxylate nanoparticles

A new family of layered metal(III)-phosphono-carboxylate nanostructures (M=Y, Eu, Tb, Er, and Yb) was hydrothermally synthesized and their structures and morphologies were characterized by X-ray powder diffraction and TEM. 4-[Bis(phosphonomethyl)amino]caproic acid and 4- [bis(phosphonomethyl)amino]undecanoic acid, with general formula (H(2)O(3)PCH(2))(2)NR (R=C(5)H(10)COOH(P2CAPR) and C(10)H(22)COOH(P2UND), respectively) were used as building blocks for the preparation of novel layered hybrid materials in which the inorganic layers were composed of MO(7) or MO(8) polyhedra and PO(3)C tetrahedra. The interlayer region was occupied by carboxyalkyl chains. These layered compounds were easily dispersed as stable solutions in alkylamine/water upon ultrasonication. These dispersions were constituted of rectangular elongated nanoparticles (NPs), which showed a distribution of sizes ranging from 20-500 nm. These new materials had interesting photophysical properties because they were multiluminescent compounds. These properties gave rise to several emission bands, which were spread over the broad spectroscopic region, from the near-UV up to the near-IR regions. Each emission band had a specific lifetime, which ranged from the sub-ps to the ms scale.