Oxidation of 2,2'-Dihydroxy-3,3'-di-tert-buty-5,5'-dimethoxyl-biphenyl to 3,3'-Di-tert-butylbiphenyl-2,5,2',5'-diquinone with Copper(Ⅱ)Chloride as Catalyst:Synthesis,Structure and Spectral Properties of Diquinone

Use of free air as oxidant and copper（II）chloride as catalyst,3,3＇-di-tert-butylbi-phenyl-2,5,2＇,5＇-diquinone（BBDQ）was prepared via catalytic oxidation of 2,2＇-dihydroxy-3,3＇-di-tert-butyl-5,5＇-dimethoxy-biphenyl（di-BHA）.The yield of reaction attained 95% and the selectivity for BBDQ was 100%.The single-crystal X-ray diffraction analysis reveals that the dihedral angle between two rings（benzene rings for di-BHA and quinone rings for BBDQ）changes from 89.8 to 45.3o,indicating the steric hindrance effects of methyl disappear in the oxidation process.The crystal structures of di-BHA and BBDQ are further confirmed by their spectral characterizations.The probable mechanism for this oxidation process is also discussed.

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether （MTBE） to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high （2.00×10^4 mg/L） to low （2 mg/L）. The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00× 10^4-2.00× 10^4 mg/L （the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5）. Low concentrations （2-500 rag/L） stimulated algal growth up to the greatest effect of 85%-200% when the concentration of MTBE was 50-100 mg/L during day 3-5. The toxicity of MTBE （72-120 h EC50） was 6.65×10^3-9.58×10^3 mg/L for C. ellipsoidea and that is 1.14× 10^4-2.00× 10^4 mg/L for A. floc-aquae. We found that the toxicity and ecological risk of MTBE for the algal community structure were low and the toxicity was influenced by the duration time of the test.

Aerobic degradation of methyl tert-butyl ether by a Proteobacteria strain in a closed culture system

The contamination of methyl ten-butyl ether （MTBE） in underground waters has become a widely concerned problem all over the world. In this study, a novel dosed culture system with oxygen supplied by H2O2 was introduced for MTBE aerobic biodegradation. After 7 d, almost all MTBE was degraded by a pure culture, a member of β-Proteobacteria named as PMI, in a closed system with oxygen supply, while only 40% MTBE was degraded in one without oxygen supply. Dissolved oxygen （DO） levels of the broth in closed systems respectively with and without H2O2 were about 5-6 and 4 mg/L. Higher DO may improve the activity of monooxygemase, which is the key enzyme of metabolic pathway from MTBE to tert-butyl alcohol and finally to CO2, and may result in the increase of the degrading activity of PM1 cell. The purge and trap GC-MS result of the broth in closed systems showed that tea-butyl alcohol, isopronol and acetone were the main intermediate products.

The Inhibition Effect of Tert-Butyl Alcohol on the TiO_2 Nano Assays Photoelectrocatalytic Degradation of Different Organics and Its Mechanism

The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was reported. The adsorption performance of these organics on the TNA photoelectrode was investigated by using the instantaneous photocurrent value, and the degradation property was examined by using the exhausted reaction. The results showed that glucose exhibited the poor adsorption and easy degradation performance, phthalate showed the strong adsorption and harddegradation, but TBA showed the weak adsorption and was the most difficult to be degraded. The degradation of both glucose and phthalate could be inhibited evidently by TBA. But the effect on glucose was more obvious. The different inhibition effects of TBA on different organics could be attributed to the differences in the adsorption and the degradation property. For instance, phthalate of the strong adsorption property could avoid from the capture of·OH radicals by TBA in TNA photoelectrocatalytic process.

Determination of methyl tert-butyl ether(MTBE) in Chinese fuels by gas chromatography/mass spectrometry and gas chromatography/flame ionization detector

A method was developed to determine the concentration of methyl tert-butyl ether(MTBE) in gasoline, diesel and heating oil by gas chromatography(GC) with mass spectrometry(GC-MS) or flame ionization detection(FID). The diluted gasoline was directly injected into the GC, and the complete separation of MTBE from co-eluting hydrocarbons was not required. GC/MS or GC/FID method can be used to analyze MTBE in different concentration range and have good consistency.

Measurements and correlation of liquid–liquid equilibrium data for the ternary(methyl tert-butyl ketone + o, m, p-benzenediol + water)system at(333.2, 343.2 and 353.2) K

In this work, liquid–liquid equilibria(LLE) data for the ternary system methyl tert-butyl ketone(MTBK)+ o, m,p-benzenediol + water were investigated at 333.2 K, 343.2 K and 353.2 K under 101.3 kPa. The performance of MTBK to extract o, m, p-benzenediol from wastewaters was estimated by partition coefficients and separation factors. The Hand and Bachman equations were both applied to check the reliability of the experimental LLE data. Furthermore, the Non-Random Two-Liquid(NRTL) and Universal Quasi Chemical(UNIQUAC) models were applied to correlate the measured LLE data. The results showed a good agreement with the determined ternary LLE data with the root-mean-square error(RMSE) values below 0.71%. MTBK was proved to be a promising extracting agent in extracting benzenediols from effluents.

Synthesis, Crystal Structure and Antitumor Activity of (E)-4-tert-Butyl-N-(2,4-dichlorobenzylidene)-5-(1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound （E）-4-tert-butyl-N-（2,4-dichlorobenzylidene）-5-（1,2,4-triazol-1-yl）-thiazol-2-amine was synthesized by the reaction of 4-tert-butyl-5-（1,2,4-triazol-1-yl）-thiazol-2-amine with 2,4-dichlorobenzaldehyde, and its crystal structure was determined by singlecrystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.9748（4）, b = 10.1803（5）, c = 11.4603（6）, α = 102.882（1）, β = 100.253（1）, γ = 104.457（1）°, V = 850.95（7）3, Z = 2, F（000） = 392, C16H15Cl2N5S, Mr = 380.29, Dc = 1.484 g/cm3, S = 1.095, μ = 0.512 mm-1, the final R = 0.0301 and wR = 0.0965 for 3334 observed reflections （I 〉 2σ（I））. The preliminary antitumor activity shows that for the title compound the IC50 of Hela is 0.175 μmol/mL and that of Bel7402 is 0.156 μmol/mL.

Synthesis and phosphorescent properties of two novel iridium (Ⅲ) complexes bearing bulky tert-butyl substituents

The synthesis and phosphorescence properties of two novel Ir(Ⅲ)complexes bearing tert-butyl substituents,bis(4-tert-butyl-2- phenylbenzothiozolato-N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tbt)_2Ir(acac)]and bis(4-tert-butyl-1-phenyl-1H-benzimidazolato- N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tpbi)_2Ir(acac)],are reported,their molecular structures are confirmed by^1H NMR,ESI-MS and elementary analysis.Photoluminescence(PL)studies revealed that they can emit strong green and orange phosphorescence in high quantum yields.Compared to their prototypes lacking of tert-butyl substituents,the two novel iridium(Ⅲ)complexes both have shorter lifetimes and improved or nearly similar PL quantum efficiencies,implying that the exciton quenching is inhibited effectively when molecular steric hindrance increases.The two chelates have great potential to be used as electrophosphorescent materials.

Synthesis,Crystal Structure and Antitumor Activity of N-(4-tert-butyl-5-(4-chlorobenzyl)thiazol-2-yl)-2,6-difluorobenzamide

The title compound was synthesized by the reaction of 4-tert-butyl-5-（4-chlorobenzyl）-2-aminothiazole with 2,6-difluorobenzoic acid. The crystal structure of the title compound, C21H19ClF2N2OS, was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group Pbca with a = 12.6479（13）, b = 13.1204（13）, c = 14.1341（15）, Z = 4, V = 2011.5（4）3, Mr = 420.89, Dc = 1.390 g/cm3, S = 1.023, μ = 0.326 mm-1, F（000） = 872, the final R = 0.0365 and wR = 0.0880 for 6101 observed reflections（I 〉 2σ（I））, and R = 0.0507, wR = 0.0978 for 7779 independent reflections. X-ray crystal structure displays that the hydrogen bonding interactions observed link the molecules to form a dimeric unit. The preliminary biological test of the title compound shows good antitumor activity, with IC50 of 0.046 μmol/mL against the Hela cell line.

Polymerization of n-Hexyl Isocyanate Initiated by Novel Rare Earth Tris(2,6-di-tert-butyl-4-methylphenolate)

The polymerization of n-hexyl isocyanate(HNCO) was carried out in the presence of a novel single initiator, rare earth tris(2,6-di-tert-butyl-4-methylphenolate)[Ln(OAr)_3]. The influences of reaction conditions such as the monomer concentration, the polymerization temperature and time, and the types of solvents on the polymerization of HNCO were studied. Polymerizations of phenyl, i-propyl, p-tolyl, n-butyl and n-octyl isocyanates with La(OAr)_3 were also examined.

Syntheses, Structures and Characteristics of Two New Cu(II) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu（Ⅱ） coordination polymers, [Cu2（tbph）2（btb）2]n （1） and {[Cu2（tbph）2- （bth）2]·H2O}n （2）, （H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis（1,2,4-triazol-1- yl）butane, bth = 1,6-bis（1,2,4-triazol-l-yl）hexane）, have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a （3,4）-connected 2D sheet with a （4.6^4.8）（4.8^2） topology. The thermal behavior of the two cor- responding complexes has briefly been investigated.

Synthesis,Crystal Structure and Fungicidal Activity of(E)-2-[(4-tert-Butyl-5-(4-methoxybenzyl)thiazol-2-ylimino)methyl]phenol

The title compound （E）-2-[（4-tert-butyl-5-（4-methoxybenzyl）thiazol-2-ylimino）methyl]phenol was synthesized by the reaction of 5-（4-methoxybenzyl）-4-tert- butylthiazol-2-amine with salicylaldehyde, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 5.9362（8）, b = 11.5070（15）, c = 29.460（4）A, β= 97.326（3）°, V = 1995.9（5） A^3, Z = 4, F（000） = 808, C22H24N2O2S, Mr= 380.49, De= 1.266 g/cm^3, S = 1.031,μ = 0.181 mm^-1, the final R = 0.0474 and wR = 0.1441 for 4327 observed reflections （I 〉 2σ（I））. Intramolecular O-H…N hydrogen bond is observed in the crystal. The preliminary bioassay showed that the title compound exhibits 95% inhibition rate against Rhizoctonia solani at the test concentration of 500 mg/L.

Synthesis and Crystal Structure of N-tert-butyl-N′-(2,4-dichlorobenzoyl)-N- [1-(4-chlorophenyl)-1, 4-dihydro-6-methylpyridazine-4-oxo-3-carbonyl] hydrazine

The title compound N-tert-butyl-N(-(2,4-dichlorobenzoyl)-N-[1-(4-chlorophenyl)- 1,4-dihydro-6-methylpyridazine-4-oxo-3-carbonyl]hydrazine [(C23H_21N4O3Cl3)2·1.5H_2O, Mr = 1042.60] was prepared by the reaction of 1-(4-chlorophenyl)-1,4-dihydro-4-oxo-6- methylpyridazine-3-carboxylic acid with chloroformate ethyl ester, then with N′-tert-butyl-N- (2,4-dichlorobenzoyl) hydrazine in the present of triethylamine. The crystal structure has been determined by X-ray diffraction. The crystal belongs to Monoclinic, space group P21/c, with unit cell constants a =11.4948(9), b=12.7495(10), c=35.854(3) ?, β =92.964(2)°, Z=4, V=5247.6(7) ?3, Dc = 1.320 Mg/m3, F(000) = 2156 , μ (MoKa)= 0.385, R = 0.0661, wR = 0.1875, for 9151 observed reflections( I >2σ(I)). The structure is a dimer linked by intermolecular hydrogen bond which can be observed between N(1)- H...O(6), N(5)- H...O(3). The distances are 2.068 and 2.027? respectively.

RING-OPENING POLYMERIZATION OF l,4-DIOXAN-2-ONE INITIATED BY LANTHANUM TRIS(2,6-DI-TERT-BUTYL-4-METHYLPHENOLATE)

The ring-opening polymerization of 1,4-dioxan-2-one （PDO） was carried out by lanthanum tris（2,6-di-tert-butyl-4- methylphenolate） （La（OAr）3） as novel single component initiaLor. The influences of polymerization reaction temperature and the molar ratio of monomer to initiator on the monomer conversion and molecular weight of poly（1,4-dioxan-2-one） （PPDO） were explored. PPDO with high viscosity average molecular weight of 1.95×10^5 can be prepared at 40℃ when [PDO]/ [La（OAr）3] molar ratio was 800. Mechanism investigation shows that the polymerization proceeds through a ＂coordination- insertion＂ mechanism with selective rupture of acyl-oxygen be,nd of PDO.

Syntheses and Crystal Structures of One-dimensional Ni(Ⅱ) Complexes with 5-Tert-butyl Isophthalic Acid

Two new Ni（ Ⅱ） coordination polymers, {[Ni（tbip）（bipy）（H2O）]-0.5H2O}n 1 and [Ni（tbip）（phen）（H2O）]n 2 （Hatbip = 5-tert-butyl isophthalic acid, bipy = 2,2＇-bipyridine, phen = 1,10-phenanthroline）, have been synthesized under hydrothermal conditions and characterized by elemental analysis, X-ray diffraction, and IR spectroscopy. In the two polymers, H2tbip acts as a tridentate ligand. Compound 1 has a tbip bridged 1-D linear chain which is extended by hydrogen bonds into a 1-D double chain, while compound 2 exhibits a 1-D zigzag chain.

Synthesis, Crystal Structure and Antitumor Activity of 4-tert-Butyl-N-(2-fluorophenyl)-5- (1H-1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound has been synthesized by the reaction of 1-bromo-3,3-dime- thyl- 1 - （1 H- 1,2,4-triazol- 1 -yl）butan-2-one with 1 -（2-fluorophenyl）thiourea, and its crystal struc- ture was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a = 15.2568（6）, b = 12.1533（5）, c = 16.7307（7） A, Z = 8, V = 3102.2（2） A3, Mr = 317.39, Dc = 1.359 g/cm3, S = 1.05, μ = 0.223 mm-1, F（000） = 1328, the final R = 0.034 and wR = 0.097 for 2590 observed reflections （I 〉 2σ（I））. X-ray crystal structure presents the intramolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. In addition, the preliminary biological test on the title compound shows good antitumor activity, with IC50 of 0.122 μmol/mL against the Hela cell line.

A Cu(Ⅱ) Coordination Polymer with 5-Tert-butyl Isophthalate Linker:Synthesis,Crystal Structure,and Magnetic Properties

A new Cu（Ⅱ） metal-organic coordination polymer, {[Cu2（tbip）2（bie）2]·H2O}n （1, H2tbip = 5-tert-butyl isophthalic acid, bie = 1,2-bis（imidazol-1 ＇-yl）ethane）, was assembled under hydrothermal conditions by the reactions of Cu（Ⅱ） acetate with H2tbip and bie. Complex 1 was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in triclinic, space group P1, with a = 9.9145（10）, b = 13.2211（13）, c = 15.4363（15） nm, a = 87.0250（10）, β = 88.3220（10）, γ = 83.8240（10）°, V= 2008.4（3） nm3, Z = 2, Dc = 1.505 Mg/m3, F（000） = 944, g = 1.125 mm^-1, S = 1.030, the final R = 0.0336 and wR = 0.0790. The results reveal that complex 1 is a two-dimensional layered structure. In addition, magnetic properties of I were also investigated.

Synthesis and Crystal Structure of 4-tert-Butyl-6-(4-chlorophenyl)-3,6-dihydro-2H-1,3-thiazin-2-iminium Chloride

The title compound, 4-tert-butyl-6-（4-chlorophenyl）-3,6-dihydro-2H-1,3-thiazin- 2-iminium chloride （C14H18C12N2S）, has been synthesized by the reaction of 1-（4-chlorophenyl）- 4,4-dimethylpent-1-en-3-one with thiourea, and its crystal structure was determined by single- crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c with a = 16.3064（11）, b = 9.4471（6）, c = 11.2626 （8）A, β = 108.400（1）°, Z = 4, V = 1646.28（19） A^3, Mr = 317.26, Dc = 1.280 g/cm^3, S = 1.078,μ = 0.510 mm^-1, F（000） = 664, the final R = 0.0514 and wR = 0.1412 for 3210 observed reflections （I 〉 2σ（I））. The thiazine ring system displays a twisted boat conformation, and three N-H,..Cl hydrogen bonds exist in the crystal. The combination of two N-H...Cl hydrogen bonds generate an R2^1 （6） ring.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

Synthesis, Crystal Structure and Antitumor Activity of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)-thiazol-2-amine

The title compound, 4-（tert-butyl）-5-（1 H- 1,2,4-triazol- 1 -yl）-N-（2-hydroxy-3,5-diio- dinebenzyl）thiazol-2-amine, was synthesized via the reduction of 4-（tert-butyl）-5-（1H-l,2,4- triazol-l-yl）-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 7.91944（19）, b = 10.5250（3）, c = 24.4985（6） A, Z = 4, V = 2041.66（9） A3, Mr = 599.22, Dc = 1,949 Mg/m3, S = 1.120, p = 3.203 mm-1, F（000） = 1152, the final R = 0.0283 and wR = 0.0592 for 3490 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O（2）-H（2A）…O（1）, O（2）-H（2B）…N（I） and N（5）-H（5）…O（2）, and an octatomic ring R^（8） is formed via intramolecular hydrogen bond of O（I）-H（IA）…N（4）. Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.