Enhanced solid-state metathesis routes to carbon nanotubes

Ignition of three solids creates multiwalled carbon nanotubes in seconds. A solid-state metathesis (exchange) reaction between hexachloroethane (C2Cl6) and lithium acetylide (Li2C2) with 5% cobalt dichloride (CoCl2) added as an initiator produces up to 7% carbon nanotubes, as observed via transmission electron microscopy. Using the concept that sulfur can promote nanotube growth, the reaction yield can be increased to 15% by switching to CoS as the initiator. The more readily available, inexpensive calcium carbide (CaC2) can be substituted for lithium acetylide while maintaining comparable yields. Switching initiators to FeS can be used to further enhance the yield. A systematic study of the C2Cl6/CaC2 reaction system indicates that a yield up to 25% can be realized by using 6% FeS as the initiator. Reaction temperatures for the C(2)Cl6/CaC2 system of up to 3550 degrees C are calculated using thermodynamic data assuming quantitative yield and adiabatic conditions.     

Structure reassignment and synthesis of Jenamidines A1/A2, synthesis of (+)-NP25302, and formal synthesis of SB-311009 analogues

The proposed structures of jenamidines A, B, and C (1-3) were revised to jenamidines A1/A2, B1/B2, and C (8-10). Jenamidines A1/A2 (8) were synthesized from activated proline derivative 43 by conversion to 26 in two steps and 50% overall yield. Acylation of 26 with acid chloride 38d gave 39d, which was deprotected with TFA and then mild base to give 8 in 45% yield from 26. (-)-trans-2,5-Dimethylproline ethyl ester (49) was prepared by the enantioselective Michael reaction of ethyl 2-nitropropionate (51) and methyl vinyl ketone (50) using modified dihydroquinine 60 as the catalyst. Further elaboration converted 49 to natural (+)-NP25302 (12). A Wittig reaction of proline NCA (76) with ylide 79 gave 72 as a 9/1 E/Z mixture in 27% yield, completing a one-step formal synthesis of SB-311009 analogues.     

Sterically encumbered systems for two low-coordinate phosphorus centers

Tetraarylphenyls of the form 2,3,5,6-Ar4C6 (Ar = p-tert-butylphenyl) are investigated as sterically demanding ligands for the syntheses of compounds having two p-phenylene-bridged phosphorus centers. The precursor to such materials, 1,4-diiodo-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (1), is readily obtained via a one-pot procedure in 68% yield. Compound 1 is then used to provide the bis(dichlorophosphine) 1,4-bis(dichlorophosphino)-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (2) and the derived bis(phosphine) 1,4-bis(phosphino)-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (3) in yields of 56 and 94% respectively. These materials provide access to novel materials containing two low-coordinate phosphorus centers bridged by a sterically encumbered phenylene unit. Compound 2 reacts with benzaldehyde and 2,6-dichlorobenzaldehyde in the presence of excess trimethylphosphine and zinc to produce the new pale yellow crystalline bis(phosphaalkenes) (E,E)-PhC(H)=PAr4C6P=C(H)Ph (4a; 42%) and (E,E)-Ar'C(H)=PAr4C6P=C(H)Ar' (4b; 46%; Ar' = 2,6-dichlorophenyl). The crystal structure of 4a shows a P=C bond length of 1.676(5) A. Compound 2 is also used to provide the unusual red-orange bis(diphosphene) DmpP=PAr4C6P=PDmp (5; 55%; Dmp = 2,6-Mes2C6H3). Compound 5 is structurally characterized, and a P=P bond length of 2.008(2) A is ascertained.     

Sonochemical synthesis and properties of nanoparticles of FeSbO4

A sonochemical method was employed to prepare reactive nanoparticles of FeSbO(4) at 300 °C, which is the lowest calcination temperature reported so far for preparing FeSbO(4). A systematic evolution of the FeSbO(4) phase formation as a function of temperature was monitored by in situ synchrotron X-ray measurements. The 300 and 450 °C calcined powders exhibited specific surface areas of 116 and 75 m(2)/g, respectively. The X-ray photoelectron spectra analysis confirmed the presence of mainly Fe(3+) and Sb(5+) in the calcined powder. The response of the fabricated sensors (using both 300 and 450 °C calcined powders) toward 1000 ppm and 1, 2, 4, and 8% hydrogen, respectively, has been monitored at various operating temperatures. The sensors fabricated using 300 °C calcined powder exhibited a response of 76% toward 4% H(2) gas at an operating temperature of 300 °C, while those fabricated using 450 °C calcined powder exhibited a higher response of 91% with a quick recovery toward 4% H(2) gas at 300 °C. The results confirmed that a higher calcination temperature was preferred to achieve better sensitivity and selectivity toward hydrogen in comparison to other reducing gases such as butane and methane. The experimental results confirmed that the sonochemical process can be easily used to prepare FeSbO(4) nanoparticles for various catalytic applications as demonstrated. Here, we project FeSbO(4) as a new class of material exhibiting high sensitivity toward a wide range of hydrogen gas. Such sensors that could detect high concentrations of hydrogen may find application in nuclear reactors where there will be a leakage of hydrogen.     

Kinetics of the deprotonation of methylnitroacetate by amines: unusually high intrinsic rate constants for a nitroalkane

A kinetic study of the reversible deprotonation of methylnitroacetate (4H) by primary aliphatic amines, secondary alicyclic amines, hydroxide ion, and water in water at 25 degrees C and in 50% DMSO/50% water (v/v) at 20 degrees C is reported. Intrinsic rate constants, k0, determined by extrapolation or interpolation of Br?nsted plots have been determined. In comparison to proton transfers involving other nitroalkanes, the intrinsic rate constants for 4H are exceptionally high; for example, log k0 for the reaction of 4H with secondary alicyclic amines in water (1.22) is 1.81 log units higher than log k0 for nitromethane (-0.59), while in 50% DMSO/50% water, log k0 for 4H (2.44) is 1.71 log units higher than that for nitromethane (0.73). A general discussion of the factors affecting intrinsic rate constants of proton transfer from nitroalkanes is presented; it provides the context for an understanding as to why k0 is so high for the proton transfers from 4H. The correlation between intrinsic rate constants for the addition of nucleophiles to alkenes of the type R'R' 'C=CXY and the intrinsic rate constants of proton transfers from carbon acids of the type H2CXY is also discussed as a general proposition as well as with specific reference to the Ph(SMe)C=C(NO2)CO2Me/H2C(NO2)CO2Me pair.     

含有Mo--Mo四重键的双钼络合物Mo_2(C_8H_8)_3的合成和晶体结构

Mo_2(C_8H_8)_3是由Mo(CO)_6和环辛四烯在正癸烷中回流而制得。它的晶体属单斜晶系,空间群为P2_1,单胞参数为:a=7.772(3),b=11.964(5),c=10.445(2),β=100.33(2)°,V=955(1)~3,根据Z=2和fw=504.31计算密度Dc=1.75g/cm~3。在Enraf-Nonius CAD4衍射仪上用MoKα射线收集了I>2σ(I)的独立衍射点2393个。晶体结构用直接法(MULTAN)程序解出,所有非氢原子的位置参数和各向异性热振动参数经全矩阵最小二乘法修正,最后的偏离因子R_1(F)=0.030,R_2(F)=0.035。分子中钼—钼的距离为2.293(1),形成了Mo-Mo四重键。Mo_2(C_8H_8)_3存在两种晶型;一是与W_2(C_8H_8)_3同晶;另一是与Cr_2(C_8H_8)_3同晶。     

十二烷基磺酸钠微乳状液结构转变的电化学研究

制备了C12H25SO3Na-C4H9OH-C7H16-H2O四组分体系在km=W(C4H9OH)/W(C12H25SO3Na)=2时的拟三元相图。使用二茂铁和铁氰化钾作为电化学探针用循环伏安法测定了起始含油量为21％的无水混合物在滴加水过程中所形成的微太液的扩散系数。从扩散系数随含水量的变化确定微乳液的结构转变。含水量为20％－45％时生成油包水型微液;含水量大于65％时生成水包油型微乳液。当含水量在45％－65％之间时形成的是二连续型微乳液。电导率数据证实了循环伏安法的测定结果。     

Pyrolysis of 2-(2-azidobenzoyl)pyridine and 3-(2-Pyridyl)-2,1- benzisixazoles. Prepration and chemistry of some pyrido[1,2-b]cinnolin-6-ium hydroxide inner salts

The pyrolysis of 3-(2-pyridyl)-2,1-benzisoxazoles 5A, 5B, and 5C (A : unsubstituted; B : 5-bromo; C : 5,7-dibromo) at about 215° afforded 5,11-dihydro-11-oxopyrido [1,2-b] cinnolin-6-ium hydroxide inner salt 6A , the 2-bromo ( 6B ) and the 2,4-dibromo ( 6C ) compounds respectively in high yields. X-ray crystallographic analysis of 6B unambiguously confirmed the structure. The benzisoxazoles 5A-5C were obtained from the pyrolysis of the corresponding 2-(2-azidobenzoyl) pyridines 2A-2C at about 112°. While 2A and 2B afforded the corresponding benzisoxazoles 5a and 5B in 82% and 51% yields respectively, 2-(2-azido-3,5-dibromobenzoyl)pyridine ( 2C ) afforded a mixture of the benzisoxazole 5C and the tricyclic compound 6C , isolated 43% and 41% yields respectively. The properties of the novel mesoionic compounds of type 6 , their oxidative and reductive ring cleavage products together with alkylation and catalytic hydrogenation products are described. Electrophilic substitutions, substitutions in position 11 via the 11-thiones 11 and other miscellaneous trans of 6 are also presented.     

Reduction features of NO over a potassium-doped C12A7-O- catalyst

The NO reduction features over a noble-metal-free NO(x) storage/reduction catalyst ([Ca24Al28O64](4+*)4O-/K, defined as C12A7-O-/K), including the NO conversion, the N2 selectivity, and sulfur tolerance, were investigated with hydrogen and C3H6 as the reducing agents in a fixed-bed continuous flow reactor. The NO conversion and the N2 selectivity on the C12A7-O-/K catalyst mainly depends on the sample temperature, the percentage of potassium, the reducing agents, and the composition of the mixture of gases. The C12A7-O-/10%K catalyst possessed the highest selective reduction ability (to N2) among the catalysts C12A7-O-/x%K. Over 50% of NO can be reduced to N2 with H2 as the reduction agent at 550-700 degrees C. The C12A7-O-/K catalyst also shows higher NO(x) storage capacity (183.9 micromol/g at about 550 degrees C) as well as sulfur tolerance for both the NO(x) storage and the reduction processes. The catalyst characteristics and the intermediate species formed in the NO storage and reduction processes were investigated by the X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight mass spectrometry. The mechanism of NO(x) reduction was addressed according to the above investigations.     

Use of a single trajectory to study product energy partitioning in unimolecular dissociation: mass effects for halogenated alkanes

A single trajectory (ST) direct dynamics approach is compared with quasiclassical trajectory (QCT) direct dynamics calculations for determining product energy partitioning in unimolecular dissociation. Three comparisons are made by simulating C(2)H(5)F-->HF + C(2)H(4) product energy partitioning for the MP26-31G(*) and MP26-311 + + G(**) potential energy surfaces (PESs) and using the MP26-31G(*) PES for C(2)H(5)F dissociation as a model to simulate CHCl(2)CCl(3)-->HCl + C(2)Cl(4) dissociation and its product energy partitioning. The trajectories are initiated at the transition state with fixed energy in reaction-coordinate translation E(t) (double dagger). The QCT simulations have zero-point energy (ZPE) in the vibrational modes orthogonal to the reaction coordinate, while there is no ZPE for the STs. A semiquantitative agreement is obtained between the ST and QCT average percent product energy partitionings. The ST approach is used to study mass effects for product energy partitioning in HX(X = F or Cl) elimination from halogenated alkanes by using the MP26-31G(*) PES for C(2)H(5)F dissociation and varying the masses of the C, H, and F atoms. There is, at most, only a small mass effect for partitioning of energy to HX vibration and rotation. In contrast, there are substantial mass effects for partitioning to relative translation and the polyatomic product's vibration and rotation. If the center of mass of the polyatomic product is located away from the C atom from which HX recoils, the polyatomic has substantial rotation energy. Polyatomic products, with heavy atoms such as Cl atoms replacing the H atoms, receive substantial vibration energy that is primarily transferred to the wag-bend motions. For E(t) (double dagger) of 1.0 kcalmol, the ST calculations give average percent partitionings to relative translation, polyatomic vibration, polyatomic rotation, HX vibration, and HX rotation of 74.9%, 6.8%, 1.5%, 14.4%, and 2.4% for C(2)H(5)F dissociation and 39.7%, 38.1%, 0.2%, 16.1%, and 5.9% for a model of CHCl(2)CCl(3) dissociation.     

Simultaneous LC?CMS?CMS Determination of HM30181A, [2-(2-{4-[2-(6,7-Dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-ethyl]-phenyl}-2H-tetrazol-5-yl)-4,5-dimethoxyphenyl]amide, as a new P-Glycoprotein Inhibitor and Its Two Metabolites, M1 and M2, in Human Plasma: Application to a Pharmacokinetic Study

A simultaneous simple, rapid, and sensitive LC?CMS?CMS method was developed and validated for the determination of HM30181A, [2-(2-{4-[2-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-ethyl]-phenyl}-2H-tetrazol-5-yl]-4,5-dimethoxy-phenyl]amide, as a P-glycoprotein inhibitor and its two metabolites, M1 and M2, in human plasma using docetaxel as an internal standard (IS). The analytes were extracted from 200???L of biological sample by liquid?Cliquid extraction using 1?mL of methyl-t-butyl ether. Chromatographic separation was carried on a Luna C8 column at 30???C with mobile phase consisting of distilled water with 0.1% formic acid and acetonitrile (75:25, v/v) at a flow rate of 0.7?mL?min^?1 for human plasma samples. The method was linear over concentration ranges of 0.5?C50, 0.1?C10, and 0.1?C10?ng?mL^?1 for HM30181A, M1, and M2, respectively, in human plasma. The values of coefficient variation for the assay precision were <12.5, <9.10, and <9.96% for HM30181A, M1, and M2, respectively, in human plasma. The values of accuracy were 93.0?C108, 94.7?C104%, and 95.7?C105% for HM30181A, M1, and M2, respectively, in human plasma. This method is simple, sensitive, and applicable for the pharmacokinetic studies of HM30181A and its metabolites in humans.     

Syntheses and structural characterization of luminescent platinum(II) complexes containing di-tert-butylbipyridine and new 1,1-dithiolate ligands

Three new di-tert-butylbipyridine (dbbpy) complexes of platinum(II) (1-3) containing 1,1-dithiolate ligands have been synthesized and characterized. The 1,1-dithiolates are 2,2-diacetylethylene-1,1-dithiolate (S(2)C=C(C(O)Me)2) (1), 2-cyano-2-p-bromophenylethylene-1,1-dithiolate (S(2)C=C(CN)(p-C(6)H(4)Br)) (2), and p-bromophenyl-2-cyano-3,3-dithiolatoacrylate (S(2)C=C(CN)(COO-p-C(6)H(4)Br)) (3). Complex 1 exhibits a solvatochromic charge-transfer absorption in the 430-488 nm region of the spectrum and a luminescence around 635 nm in ambient temperature CH(2)Cl(2) solution. These observations are consistent with what has been seen previously in related Pt diimine 1,1-dithiolate complexes. The nature of the emissive state is assigned as a (3)(mixed metal/dithiolate-to-diimine) charge transfer, while the solvatochromic absorption band corresponds to the singlet transition of similar orbital character. The other complexes also exhibit a low-energy solvatochromic absorption. The crystal structures of two of the complexes have been determined, representing the first time that Pt(diimine)(1,1-dithiolate) complexes have been crystallographically studied. The structures confirm the expected square planar coordination geometry with distortions in bond angles dictated by the constraints of the chelating ligands. The Pt-S and Pt-N bond lengths and S-Pt-S and N-Pt-N bond angles for the two structures are identical within experimental error (2.283(2) and 2.278(2) A; 2.053(6) and 2.050(8) A; 75.01(8) degrees and 75.40(8) degrees; 79.2(2) degrees and 79.0(2) degrees, respectively). Crystal data for 1: monoclinic, space group P2(1)/n (No. 14), with a = 7.20480(10) A, b = 20.53880(10) A, c = 19.1072(2) A, beta = 93.83 degrees, V = A(3), Z = 4, R1 = 3.34% (I > 2sigma(I)), wR2 = 9.88% (I > 2sigma(I)) for 3922 unique reflections. Crystal data for 2: monoclinic, space group P2(1)/n (No. 14), with a = 15.0940(5) A, b = 9.5182(3) A, c = 20.4772(7) A, beta = 111.151(1) degrees, V = A(3), Z = 4, R1 = 4.07% (I > 2sigma(I)), wR2 = 8.64% (I > 2sigma(I)) for 3859 unique reflections.     

Practical synthesis of an open geodesic polyarene with a fullerene-type 6:6-double bond at the center: diindeno[1,2,3,4-defg;1',2',3',4'-mnop]chrysene

Diindeno[1,2,3,4-defg;1',2',3',4'-mnop]chrysene (1), the smallest possible alkene-centered C60 substructure with a curved pi-system, is obtained in 25-35% yield by flash vacuum pyrolysis of the twisted 1,1'-dibromobifluorenylidene (2) on a 100 mg scale at 1050 degrees C. At 1200 degrees C, the bowl-shaped hydrocarbon 1 rearranges to the planar isomer diindeno[5,6,7,1-defg;5',6',7',1'-lmnop]chrysene (14) by a double 5/6 ring-expansion/ring-contraction. X-ray crystallography establishes that the central carbon atoms of 1 are nearly 80% as pyramidalized as the carbon atoms of C60 (POAV angles = 9.0 degrees and 11.6 degrees for 1 and C60, respectively). A four-step synthesis has been developed to prepare the pyrolysis precursor (2) as a mixture of (E)- and (Z)-isomers in 39% overall yield from commercially available 9-fluorenone-1-carboxylic acid (10).     

DFT study on the reed diethylaluminum cation-like system: structure and bonding in Et(2)Al(CB(11)H(6)X(6)) (X = Cl, Br)

Electronic and molecular structure has been investigated in the diethylaluminum cation-like system Et(2)Al(CB(11)H(6)X(6)) (1, X = Cl; 2, X = Br) and neutral compounds AlX(3) (X = Cl, Br, Me, C(6)H(5)) with DFT B3LYP and BP86 levels of theory. The calculated geometries of Et(2)Al(CB(11)H(6)X(6)) (1, X = Cl; 2, X = Br) are in excellent agreement with those determined experimentally by X-ray crystallography. The Al-X bond distances 2.442, 2.445 A in 1 and 2.579, 2.589 A in 2 are longer than those expected for single bonds based on covalent radius predictions (Al-Cl = 2.15 A and Al-Br = 2.32 A) and those observed for bridged Al-X-Al bonds (2.21 A in Al(2)Cl(6), 2.33 A in Al(2)Br(6)) and are close to sum of ionic radii of Al(3+) and X(-) (Al-Cl = 2.35 A and Al-Br = 2.50 A). The optimized geometries of the neutral compounds AlX(3) (X = Cl, Br, Me(3), C(6)H(5)) at BP86/TZ2P show Al-Cl = 2.088 A in AlCl(3), Al-Br = 2.234 A in AlBr(3), Al-C = 1.973 A in AlMe(3), Al-C = 2.255 A in Al(C(6)F(5))(3). These bond distances are similar to those expected for single bonds based on covalent radius predictions. The calculated charge distribution indicates that the aluminum atom carries a significant positive charge while the ethyl and carborane groups are negatively charged. The Cl and Br atoms in compounds 1 and 2 are slightly positive while, in neutral compounds AlX(3) (X = Cl, Br, Me(3), C(6)H(5)), X is negatively charged. Energy decomposition analysis of Et(2)Al(delta)(+)(carborane)(delta)(-) shows that the bonding between the fragments is more than half electrostatic. The ionic character of the Al...Cl bonds in compound 1(59.8%) is greater than the Al.Br bonds in the compound 2 (57.9%). This quantifies and gives legitimacy to the designation of these types of compounds as "ion-like". The Al-X bonding in AlX(3) is mainly covalent with percentage ionic character 28.2% in AlCl(3), 31.5% in AlBr(3), 25.6% in AlMe(3), 18.4% in Al(C(6)F(5))(3).     

Gas-liquid chromatographic determination of fatty acid composition of cholesteryl esters in human serum using silica Sep-Pak cartridges

A simple and fast analytical procedure for separation and purification of cholesteryl esters of human serum is described. A single lipid extract, together with spiked cholesteryl pentadecanoate, as an internal standard, was passed through a Silica Sep-Pak cartridge. 1.5% diethyl ester in light petroleum was used to elute cholesteryl esters from the column. The separation was verified with thin-layer chromatography on silica gel using light petroleum-diethyl ether-glacial acetic acid (80:20:1) as a solvent. A very clean thin-layer chromatogram of cholesteryl esters without any additional spots of other lipids was obtained. The cholesteryl esters were quantitated by analyzing their fatty acid composition as methyl esters by gas-liquid chromatography. The coefficients of variation were 0.8--4.9% for the major fatty acids (C16:0, C16:1, C18:1, C18:2, C20:4) and 6.7--30.8% for the minor fatty acids (C18:0 and C20:0). The recoveries for cholesteryl palmitate, cholesteryl oleate and cholesteryl linoleate were 90.7, 92.3 and 91.0%, respectively.     

N-alkenyl indoles as useful intermediates for alkaloid synthesis

A mild cross-coupling reaction to access several N-alkenyl-substituted indoles has been developed. The coupling procedure involves treating a NH-indole with various alkenyl bromides using a combination of 10 mol % of copper(I) iodide and 20 mol % of ethylenediamine as the catalyst in dioxane at 110 °C in the presence of K(3)PO(4) as the base. When treated with acid, these unique enamines produce a dimeric product derived from a preferred protonation reaction at the enamine π-bond. A cationic cyclization reaction of the readily available 2-(2-(1H-indol-1-yl)allyl)cyclopentanol was utilized to construct tetracyclic indole derivatives with a quaternary stereocenter attached to the C(2)-position of the indole ring. An alternative strategy for selective functionalization at the C(2)-position of a N-alkenyl-substituted indole derivative that was also studied involves a radical cyclization of a xanthate derivative. The work described provides an attractive route to the tetracyclic core of some vinca alkaloids, including the tetrahydroisoquinocarbazole RS-2135.     

The use of nonendcapped C18 columns in the cleanup of clenbuterol and a new adrenergic agonist from bovine liver by gas chromatography-tandem mass spectrometry analysis

More specific official methodology is needed to survey the illegal use of clenbuterol in animal production plus the synthesis of new compounds that currently elude routine analytical methods. The identification of a new adrenergic agonist, N1-(2-(4-amino-3,5-dichlorophenyl)-2-hydroxyethyl)-N1-isopropyl-propanamide (known as compound A) in animal feed has prompted studies to verify if the existing cleanup procedures developed for clenbuterol are really effective. This study considers the ion-exchange mechanism on cyanopropyl (CN), sulfonic cation exchange (SCX), mixed phase (MPH) (C8 + SCX), and nonendcapped C18 (C18NE) solid-phase extraction (SPE) columns. Results indicate that compound A (by contrast with clenbuterol) is not efficiently retained on the CN, SCX, and MPH SPE columns (recovery <10%). This finding thus leads to the development of a gas chromatography-tandem mass spectrometry procedure based on C18NE SPE that is able to purify both agonists from bovine livers spiked at 0.5, 1.0, and 2.0 ppb with a mean recovery of 93% for clenbuterol and 92% for compound A.     

A Novel synthesis of 2-functionalized benzofurans by palladium-catalyzed cycloisomerization of 2-(1-hydroxyprop-2-ynyl)phenols followed by acid-catalyzed allylic isomerization or allylic nucleophilic substitution

A novel two-step synthesis of 2-hydroxymethylbenzofurans 3 and 2-alkoxymethylbenzofurans 4-6, based on palladium-catalyzed cycloisomerization of 2-(1-hydroxyprop-2-ynyl)phenols 1 under basic conditions to give 2-methylene-2,3-dihydrobenzofuran-3-ols 2, followed by acid-catalyzed isomerization or allylic nucleophilic substitution with alcohols as nucleophiles, is reported. Cycloisomerization reactions leading to 2 (80-98% yields) were carried out at 40 degrees C in MeOH as the solvent, in the presence of a base and catalytic amounts of PdX2 + 2KX (X = Cl, I). Isomerization reactions of 2 readily occurred at 25-60 degrees C in DME as the solvent, with H2SO4 as the proton source, to give 2-hydroxymethylbenzofurans 3 in 65-90% yields. In a similar manner, allylic nucleophilic substitution reactions of 2 with ROH as nucleophiles [carried out at 25-40 degrees C in ROH (R = Me) or ROH-DME mixtures (R = Bu, Bn) in the presence of H2SO4] afforded 2-alkoxymethylbenzofurans 4, 5, and 6 (R = Me, Bu, and Bn, respectively), in 65-98% yields.