Gauging the significance of atomic oxygen [O(3P)] in sulfoxide photochemistry. A method for hydrocarbon oxidation

A liquid-phase photolysis of 1,2-benzodiphenylene sulfoxide, 1, and dibenzothiophene sulfoxide, 2, was used to generate atomic oxygen [O(3P)] or an equivalent active oxygen species. The reaction for sulfoxide photodeoxygenation was similar to a microwave discharge method for generating O(3P) atoms in the condensed phase (Zadok, E.; Rubinraut, S.; Mazur, Y. J. Org. Chem. 1987, 52, 385-90). Sulfoxide photodeoxygenation is a potentially clean method for O(3P) production compared to the microwave discharge method. With Argon purging of the sulfoxide sample before photolysis, the method can preclude a secondary oxidation process involving molecular oxygen. Our study focused on the results of oxidation products in the reaction of styrene, 3, and on the dependence of substrates that provided an opportunity to vary the electronic and steric effects. The sulfoxide photochemistry is rationalized with the primary formation of O(3P) in which a charge-transfer interaction between O(3P) and substrate precedes oxidation. Functionalization of hydrocarbons takes place under mild photolysis conditions of 1 and 2, which leads to an interesting possibility for the synthetic use of atomic oxygen, O(3P). Alkanes give principally alcohols. Alkenes give principally epoxides and ketones. For comparison, hydroxyl radicals are more reactive and less selective toward hydrocarbons compared to O(3P) atoms. On the other hand, O(3P) atoms balance reactivity and selectivity and involve the oxidation of inert alkanes typically inaccessible to peracid, dioxirane, ozone, and singlet molecular oxygen chemistry. The findings from this study may be useful to those interested in generating high-value oxygenated compounds from readily available petroleum components.     

The reaction of atomic oxygen O(3P) with isobutane

The reaction of O(³P) atoms with isobutane has been studied by using the discharge-flow system described previously [1]. The rate constant was measured from determinations of the isobutane concentration in the presence of an excess of O atoms and is given by k₁ = (7.9 ± 1.4) × 10⁷ dm³/mol·s at 307 K. In order to explain the observed reaction products, the mechanism requires that the principal process be the successive abstraction of H atoms from isobutane and from the t-butyl radical to give isobutene. A minor part of the reaction between O(³P) and the t-butyl radical gives the t-butoxy radical, which decomposes to acetone. The branching ratios are .     

The reaction of atomic oxygen O(3P) with propane

The reaction of O(³P) atoms with propanehas been studied at temperatures near 300 K by using a discharge flow system. Oxygen atoms were generated in the absence of molecular oxygen by the reaction N + NO → N₂ + O, nitrogen atoms having been generated in a microwave discharge. Rate constants for the reaction were measured in two ways, either by measurement of O-atom decay in the presence of excess propane or by measuring the change in propane concentration after an appropriate time in the presence of an excess of oxygen atoms. The two methods were in good agreement, and the mean rate constant at 306 K is given by A study of the products of the reaction under conditions corresponding to complete removal of oxygen atoms has shown that an important product of the reaction in the early stages is propene. This is difficult to explain interms of a mechanism involving alkoxy radicals similar to that which has been proposed for some other O(³P)–hydrocarbon reactions. An alternative mechanism is proposed in terms of successive hydrogen abstraction reactions.     

Reactions of 3-[N-chloroacetylamino-N-(4-nitrophenyl)]-2-formylindole with alkylamines

The reactions of 3-[N-chloracetylamino-N-(4-nitrophenyl)]-2-formylindole (1a) with 2-(N, N-dialkylamino)ethylamines afford complex condensation products 7b,c consisting of two similar but not identical diazepinoindole fragments. For the reaction of compound 1a with 3-(N,N-diethylamino)propylamine, the process occurs in a different manner, and the predominant product is 4-ethylaminopropyl-1-(4-nitrophenyl)-2-oxo-1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole hydrocloride (14). Two routes of these unexpected transformations were proposed. The structures of the synthesized products were proved by the ¹sH and ¹³C NMR, HMBC, and HSQC (direct proton-carbon correlation) spectra. Dedicated to Academician V. A. Tartakovsky on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1536–1542, August, 2007.     

Reactions of O(3 P) with aromatic compounds in the liquid phase

The oxidation of 12 aromatic compounds using either high voltage or radio frequency glow discharges has been studied. The reactions have been carried out by making the oxygen plasma reach the low vapor pressure substrate. This (1.5-3 ml) was placed into a double-walled glass vessel that was cooled down to temperatures close to its freeing point. Oxygen pressure was of the order of 0.05-0.30 torr, the ratio p(Oa) / (vapor pressure of the liquid) being in the range 10–120. The results obtained in the plasma-liquid interactions of this work considerably differ from those in the homogeneous gas phase. Neither fragmentation products in the traps nor polymers on the reactor walls have been detected. Product formation has proved to be more selective as well. For anisole and five monoalkylben:enes o-, m-, and p-alkvlphenols amounted to 65–86% of the total yield, ortho derivatives being the most important products. The oxidation of the alkyl side chain was observed at a lower level than the aromatic hydroxylation. No ipso substitution was detected. Diand trimethylbenzenes were also studied, di- and trirnethylphenols being the major products. For all substrates dihydroxy derivatives were the most important byproducts. Total conversion, i.e., mass transformed against initial mass of substrate, has been studied as a Junction of temperature of the liquid and oxygen fog, rate in the reactor, this ranging from 10 to 20 mMol/h. The optimum conversions were 7 to 40%. A correlation between these results and the behavior of the O(3P) population in the discharge has been /bund.     

Ion recognition properties of poly[Cu(3-MeOsalpd)] films

Poly[Cu(3-MeOsalpd)] films with good physical, chemical and electrochemical stability may be potentiodynamically electrodeposited with high deposition efficiency from acetonitrile solutions of the monomer. Comparative coulometric assays with the Ni-based analogue show that the metal in the salen motif does play a role in the electronic structure of the polymer, but that the electroactive response is ligand (not metal) based. The dynamics of redox switching are ultimately limited by coupled electron/counter ion diffusion, but this process is sufficiently rapid that it influences the voltammetric response only for thick films (Γ >420?nmol?cm^?2) at high scan rates. Redox cycling in monomer-free electrolyte shows a voltammetric signature that responds, via interaction with the pseudo-crown ether receptor sites, to the presence of Li⁺, K⁺, Mg²⁺ and Ba²⁺ ions in solution. The most prominent change is associated with the first anodic peak in the i-E signature. For each of the metal ions considered, this peak potential responds logarithmically to concentration in a manner that varies with individual complexed cation and film thickness and to an extent greater than predicted by the Nernst equation. The film characteristics offer some analytical promise, including a trade-off between sensitivity and dynamic range and signal amplification, possibly due to supramolecular effects.     

A layered tin(II) phosphonate, [Sn(C6H5O3P)]n

Poly­[tin(II)‐μ‐phenyl­phospho­nato], [Sn(C₆H₅O₃P)]_n, was synthesized solvothermally at 423 K and crystallized in the monoclinic system, space group Cc. The inorganic layers consist of alternating pyramidal Sn and tetrahedral P centers, joined by doubly bridging O atoms. The corner‐sharing SnO₃ and PO₃C₆H₅ polyhedra define a corrugated layer of six‐membered rings. The layers are connected along the unique b axis by interdigitated phenyl rings of the phenyl­phospho­nate groups.     

Reactions of 2,5-pyrrolediylbis[N-(o-hydroxyphenylaldimine)] with some metal ions

The novel Schiff-base 2,5-pyrrolediylbis[N-(o-hydroxyphenylaldimine)] (SBH₂) has been synthesized by the condensation of 2,5-pyrroledicarboxaldehyde and o-amino-phenol. The reactions of the Schiff-base with several transition- and post-transition-metal ions have been investigated. The Schiff-base reacts as a tetradentate dianion without deprotonation of the pyrrole. The complexes M(SB)·nH₂O have been isolated and characterized with n = 1, 2 or 3; SB is the dianion of the Schiff-base; and M = divalent Mn, Co, Ni, Cu, Zn, Pd, Cd, Pb or UO₂. The binuclear complexes M(SB)MX₂ for M = Cu, X = NO₃, and M = Ni or Pd, X = Cl, have also been isolated.     

Cs[Si3O6(OH)] and Rb[Si2O4(OH)]: two novel phyl­losilicates

The crystal structures of two novel phyl­losilicates with compositions Cs[Si₃O₆(OH)] (caesium hydroxo­hexa­oxotetra­otri­silicate) and Rb[Si₂O₄(OH)] (rubidium hydroxo­hexa­oxotetrao­di­silicate) have been characterized by X‐ray diffraction. The topology of the caesium phyl­losilicate silica sheet consists of interconnected four‐ and six‐membered rings and thus differs from all of the previously reported phyl­losilicates. The topology of the rubidium phyl­losilicate silica sheet consists of six‐membered rings only, in boat conformations, resulting in a corrugated sheet similar to that observed in δ‐Na₂Si₂O₅. Both of the title compounds exhibit the characteristic sandwich structure of sheet silicates, with the Cs atom ninefold coordinated and the Rb atom eightfold coordinated to the framework O atoms.     

[Cu(en)2]0.5[Al3P3O12(OH)]-aluminophosphate with zeotype AWO: Synthesis, crystal structure and phase transformation

A new aluminophosphate [Cu(en)₂]_0.5[Al₃P₃O₁₂(OH)] (denoted as AlPO-CJ53; en = ethylenediamine) with zeotype AWO topology has been synthesized under hydrothermal conditions in which the self-assembled Cu(en) ₂ ²⁺ cations in the reaction system act as the template. AlPO-CJ53 crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 0.85547(11) nm, b = 1.7671(2) nm, c = 0.90500(12) nm, β = 107.725(2)°, V = 1.3031(3) nm³. Its framework consists of AlO₄(OH)/AlO₄ and PO₄ units forming 8-ring channels along the c direction, where the copper complex cations Cu(en) ₂ ²⁺ are located to neutralize the negative charges of the framework. AlPO-CJ53 transforms to AlPO₄-25 with zeotype ATV upon calcination at 400 °C.     

Reactions of O2(1Δg) with atomic nitrogen and hydrogen

The reactions of electrically dicharged nitrogen and hydrogen with O₂(¹Δ_g) is probabnly slower than with ground state O₂. ON the other hand, the reaction of H-atoms with O₂(¹Δ_g) was found to occur with a rate constant k=(2,5±0.5)× 10^?14 cm³ molecule^?1 sec^?1, although it was not posible to establish whether the reaction produced OH radicals or simply represented physical quenching.     

Reactions of O(3P) with secondary C-H bonds of saturated hydrocarbons in nonequilibrium plasmas

The functionalization of three n-alkanes by means of a low-pressure oxygen plasma has been achieved. The plasma was generated by applying a low-Frequency high-voltage glow discharge through an oxygen flow. bit, activated species so produced have been allowed to interact with the surface of each one of the liquid compounds at a time. The hydrocarbon has been cooled down to a temperature low enough so that its vapor pressure is about 20–100 times lower than the O₂ pressure, this heing of the order of 0.1–0.4 torr. Under these conditions the main products of the reactions have been the alcohols, except for the primary ones, and the corresponding ketones. A remarkable result we have arrived at is that for the first time secondary carbon hydrogen bonds have shown to possess different reactivities withO(³P). The latter has proved to he the most relevant active species of the plasma. A discussion is given to explain this novel result under two theoretical bases recently published: (i) a conformational analysis of the hydrocarbons according to molecular mechanics calculations, and (ii) an analysis of properties of the molecules based on calculations with charge distributions derived from 6–31G^* wave functions.     

多通道反应O(3P)＋CH2F的理论研究

用密度泛函理论研究了氧原子与氟代甲基自由基的反应.反应中出现的所有物种的平衡构型用B3LYP方法在6-311＋＋G（2d, 2p）基组水平上进行了优化，同时对各物种进行了频率分析；在同一理论水平上计算了各反应通道的势能面变化，分析了反应物、中间体、过渡态、产物的振动模式随反应途径的变化关系，阐明了该多通道反应的反应机理.     

Li+ cation coordination in [Li2(CF3SO3)2(diglyme)] and [Li3(C2F3O2)3(diglyme)]

The title compounds, poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­methanesulfonato‐lithium(I)], [Li₂(CF₃SO₃)₂(C₆H₁₄O₃)]_n, and poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­acetato‐dilithium(I)‐μ₃‐tri­fluoro­acetato], [Li₃(C₂F₃O₂)₃(C₆H₁₄O₃)]_n, consist of one‐dimensional polymer chains. Both structures contain five‐coordinate Li⁺ cations coordinated by a tridentate diglyme [bis(2‐methoxy­ethyl) ether] mol­ecule and two O atoms, each from separate anions. In both structures, the [Li(diglyme)X₂]^? (X is CF₃SO₃ or CF₃CO₂) fragments are further connected by other Li⁺ cations and anions, creating one‐dimensional chains. These connecting Li⁺ cations are coordinated by four separate anions in both compounds. The CF₃SO₃^? and CF₃CO₂^? anions, however, adopt different forms of cation coordination, resulting in differences in the connectivity of the structures and solvate stoichiometries.     

[Gd(3-HPYA)3(H2O)]n的合成及其晶体结构

3-(3-吡啶基)丙烯酸(3-HPYA)配体与稀土金属离子钆(Gd)通过水热法合成了一种新的一维链状配位聚合物[Gd(3-HPYA)3(H2O)]n(1),其结构经IR,热重分析,元素分析和x-射衍单晶衍射仪表征.1属于三斜晶系,空间群P-1,晶胞参数为:a=0.61943(15)nm,b=1.27000(3)nm,c=1.563 40(4)nm,α=111.728(4)°,β=90.330(4)°,γ=95.202(4)°,Z=2.1通过分子间的氢键堆积为三维网状结构.对1的热稳定性进行了研究.     

Catalytic Reactions with Hydrosilane and Carbon Monoxide [New synthetic methods (30)]

The reagent hydrosilane/carbon monoxide opens up new possibilities for organic synthesis. Four cases will be discussed: 1. The reaction of olefins with hydrosilane (trialkylsilane) and carbon monoxide in the presence of Co, Ru, and Rh complexes leads to enol silyl ethers having one more carbon atom that the olefins. 2. Cyclic ethers underto carbonylative ring opening to ω-siloxyaldehydes when reacted with hydrosilane and carbon monoxide in the presence of Co₂(CO)₈ as catalysts 3. Aldehydes are catalytically converted into the next higher α-siloxyaldehydes or 1,2-bis(siloxy)alkenes depending on the reaction conditions used. 4. The reaction of alkyl acetates proceeds in various ways depending on the nature of the alkyl group; enol silyl ethers or alkenes are optained.–Mechanisms of these Co₂(CO)₈ catalyzed reactions using hydrosilane and carbon monoxide are discussed in which HCo(CO)_n or R₃SiCo(CO)_nL function as catalytically active agents. With these species there are four types of catalytic cycles.–The synthetic possibilities of these catalytic reactions have still not been fully explored.