Acetyl chloride-ethanol brings about a remarkably efficient conversion of allyl acetates into allyl chlorides

AcCl-EtOH transforms primary and secondary allyl acetates into allyl chlorides that retain the olefinic bond in the more stable position. Whereas secondary allyl alcohols also react with almost the same efficacy as the acetates, the reactions of primary allyl alcohols that possess 1,2-disubstituted alkenes are very slow. The products are isolated in high state of purity simply by removal of the volatiles.     

Synthesis and characterization of cationic and zwitterionic allyl zirconium complexes derived from trimethylenemethane (TMM) cyclopentadienylzirconium acetamidinates

Protonation of the trimethylenemethane derivatives, Cp*Zr(σ²,π-C₄H₆)[N(R¹)C(Me)N(R²)] (1a: R¹=R²=i-Pr and 1b: R¹=Et, R²=t-Bu) (Cp*=η⁵-C₅Me₅), by [PhNMe₂H][B(C₆F₅)₄] in chlorobenzene at −10 °C provides the cationic methallyl complexes, Cp*Zr(η³-C₄H₇)[N(R¹)C(Me)N(R²)] (2a: R¹=R²=i-Pr and 2b: R¹=Et, R²=t-Bu), which are thermally robust in solution at elevated temperatures as determined by ¹H NMR spectroscopy. Addition of B(C₆F₅)₃ to 1a and 1b provides the zwitterionic allyl complexes, Cp*Zr{η³-CH₂C[CH₂B(C₆F₅)₃]CH₂}[N(R¹)C(Me)N(R²)] (3a: R¹=R²=i-Pr and 3b: R¹=Et, R²=t-Bu). The crystal structures of 2b and 3a have been determined. Neither the cationic complexes 2 or the zwitterionic complexes 3 are active initiators for the Ziegler-Natta polymerization of ethylene and α-olefins.     

Carbonate derivatives of 14β-hydroxycodeine

Carbonate derivatives of 14β-hydroxycodeine, viz., 14β-hydroxy-6-O-(methoxycarbonyl)codeine, 6-O-methoxycarbonyl-14β-(methoxycarbonyloxy)codeine, and 14β-acetoxy-6-O-methoxy-carbonylcodeine, potential substrates for ring C modification in morphinane alkaloids, were synthesized for the first time Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1739–1740, August, 2008.     

Electrochemical Synthesis of gem-Difluoro- and γ-Fluoro-Allyl Boronates and Silanes

The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α-trifluoromethyl or α-difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem-difluoro and γ-fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L⁻¹.h⁻¹ and 496 g.L⁻¹.h⁻¹). Moreover, the synthetic utility of these building blocks was highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested to explain the formation of the products.     

铬酸氢根季铵树脂对烯丙醇的选择性氧化

合成了铬酸氢根季铵盐树脂,以它作为一种选择性氧化剂应用于烯丙醇的氧化反应,考察了温度、时间、溶剂、树脂与醇的物料比对氧化反应的影响。在优化的反应条件下,即以苯为溶剂,n（树脂）：n（醇）=3．5：1,回流12h,丙烯醛产率达60．65％。实验表明,该季铵盐树脂能有效地将烯丙醇选择性地氧化为丙烯醛。     

烯丙基锂四氢呋喃配合物的合成

在四氢呋喃存在下,将丙烯和丁基锂直接反应合成了未见文献报道的烯丙基锂四氢呋喃配合物。对产物组成进行了鉴定,并用红外光谱讨论了烯丙基的结构。对反应条件进行了较为详细的研究。     

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization

Allyl halides with triflamide under oxidative conditions form halogen-substituted amidines. Allyl cyanide reacts with triflamide in acetonitrile or THF solutions in the presence of NBS to give the products of bromotriflamidation with a solvent interception, whereas in CH₂Cl₂ two regioisomers of the bromotriflamidation product without a solvent interception were obtained. The formed products undergo base-induced dehydrobromination to give linear isomers with the new C=C bond conjugated either with the nitrile group or the amidine moiety or alkoxy group. Under the same conditions, the reaction of allyl alcohol with triflamide gives rise to amidine, which was prepared earlier by the reaction of diallyl formal with triflamide. Unlike their iodo-substituted analogs, bromo-substituted amidines successfully transform into imidazolidines under the action of potassium carbonate.     

Formation of organopalladium complexes on SiO2 and Al2O3 as a result of the reaction of allyl alcohol with supported PdCl2; thermal decomposition of these complexes

It was established by electronic spectroscopy in the UV and visible regions and mass spectrometry that when allyl alcohol reacts from the gas phase with palladium chloride supported on SiO₂ and Al₂O₃ a complex similar in characteristics to a bis--allylpalladium chloride complex that is fixed on the surface of the support is formed. Decomposition of this complex in vacuo occurs at 135°C with the formation of allyl chloride and zero-valence supported palladium.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1536–1539, July, 1992.     

共聚类吸水树脂综合应用性能研究

以丙烯酸烯丙酯为交联剂合成了丙烯酸和丙烯酰胺共聚类吸水树脂,并对该吸水树脂的综合稳定性（耐热性、耐寒性、耐光性）进行了研究.对树脂凝胶溶胶含量、土壤保水性、树脂对去离子水、生理盐水、人工血、人工尿的吸收能力及树脂的膨胀动力学和热分解动力学作了较为全面的研究.确定了膨胀动力学参数及热分解反应动力学参数, 结果表明：所合成树脂吸水膨胀过程中膨胀指数0.5〈n〈1,属于non-Fikian扩散,吸水树脂的热解过程分为两个阶段,都属于一级反应,以丙烯酸烯丙酯作为交联剂合成的丙烯酸和丙烯酰胺共聚类吸水树脂具有良好的综合应用性能.     

人造芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯的气相色谱分析

采用２ｍ×３ｍｍ玻璃柱，涂布０．５％ＥＧＡ的８０～１００目ＧａｓｃｈｒｏｍＱ为固定相，以异辛醇为内标物，分析芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯异构体。该方法既可用于人造芥子油的含量分析，也可用于市售芥子油的质量鉴定。     

希土烯丙基化合物的研究——Ⅷ.镝、钬、铒、镱和镥的2-甲基烯丙基化合物的合成

用无水希土氯化物与2-甲基烯丙基氯化镁及四甲基乙二胺,0℃下,在四氢呋喃中反应,加乙醚后可得到五个含2-甲基烯丙基的重希土元素的化合物。经元素分析、红外光谱和质谱分析的鉴定,确定该化合物的组成为Ln(C_4H_7)_2Cl_5Mg_2(tmed)_2。     

烯丙基缩水甘油醚的合成

烯丙醇和环氧氯丙烷在三氟化硼乙醚络合物的催化作用下进行加成和环化反应制得标题化合物。研究了催化剂用量、反应原料配比及碱用量对产物收率的影响。     

Electrochemical study of allylbenzene and allylcyclohexadienyl complexes of ruthenium

Cyclic voltammetry has been used to study the electrochemical behavior of RuCl(³-C₃H₅)(⁶-C₆H₆) (1), [Ru(PPh₃) · (³-C₃H₅)(⁶-C₆H₆)]BF₄ (2), and Ru(PPh₃)· (³-C₃H₅)(⁵-C₆H₇) (3); the latter was prepared by reacting2 with LiAlH₄. The reduction of1 and2 gives the 19-electron complexes1 ^–. and 2^·, whereas oxidation of3 gives the 17-electron complex3 ^+·. The reactivities of1 ^–·,2 ^·, and3 ^+· are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1126–1128, June, 1993.     

Dicobalt octacarbonyl-catalyzed cationic polymerization of allylic and enolic ethers

In the presence of silanes bearing Si H groups, dicobalt octacarbonyl [Co₂(CO)₈] efficiently catalyzes the cationic polymerization of a wide variety of enol ether and other related monomers including vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, ketene acetals, and allene ethers. In addition, this catalyst system is also effective for the polymerization of complimentary allylic and propargylic ethers by a process involving tandem isomerization and cationic polymerization. This latter process occurs by a stepwise mechanism in which the allylic or propargylic ether is first isomerized, respectively, to the corresponding enol ether or allenic ether and then this latter compound is rapidly cationically polymerized in the presence of the catalyst. In accord with this mechanism, it has been shown that the structure of the polymers prepared from related enol and allyl ethers using the above catalyst system are identical. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1579–1591, 1997     

Palladium‐catalysed cyclocarbonylation reactions in dimethyl carbonate,an eco‐friendly solvent and ring‐opening reagent

Dimethyl carbonate (DMC) is used as an alternative and eco‐friendly solvent for selective cyclocarbonylation reactions of allyl phenol derivatives for the synthesis of lactones; in some cases, depending on the reaction condition, DMC behaves as a ring‐opening reagent producing methoxycarbonyl compounds. Copyright © 2003 John Wiley & Sons, Ltd.     

Spectral Studies of Palladium(II)-Allyl Thiourea System

Abstract

Palladium(II) forms 1:1 and 1:4 complexes with allyl thiourea. The molar composition of the complexes was determined by molar-ratio and continuous variation methods and confirmed by means of elemental analysis of the compounds isolated from solution.

Conformity to Beer's law was observed for up to 12 μg ml^?1 of 4 palladium in strongly acidic medium (molar absorptivity 2.28×10⁴ 1 mol^?1 cm^?1 at 292 nm);the Sandell's sensitivity of the reaction for palladium is 0.0047 μg cm^?2 per 0.001 absorbance unit.

The tolerance of the system to platinum metals and other common cations is satisfactory.

A statistical evaluation of the analytical procedure of palladium determination has been undertaken.

The infrared spectra of allyl thiourea and of its 1:1 and 1:4 palladium complexes have been measured in the 2.5–50μ region. The absorption bands have been assigned. The spectra reveal that allyl thiourea forms sulphur-to-metal bonds only, rather than nitrogen-to-metal bonds in the complexes studied.     

光诱导的二芳基烯丙醇氰甲基化合成δ-酮腈的反应研究

以二芳基烯丙醇与溴乙腈为原料,开发了一种可见光诱导的合成δ-酮腈的方法.控制实验的结果表明,该反应可能是通过自由基机理进行的,溴乙腈作为氰甲基自由基源参与到反应中.     

Thermal behaviour of poly(allyl azide)

The paper describes the synthesis of low molecular mass poly(allyl chloride) (PAC) (M _n= 856-3834 g mol^-1) using Lewis acid (ALCL₃, FeCL₃, TiCL₄) and al powder. Branching in PAC was indicated on the basis of elemental analysis and ¹H-NMR spectroscopy. azidation of pac could be carried out at 100°C by using NaN₃ and DMSO as solvent. Curing of poly(allyl azide) (PAA) by cyclic dipolar addition reaction with EGDMA (ethylene glycol dimethacrylate, 5-45 phr) was investigated by differential scanning calorimetry and structure of cured polymer was confirmed by FTIR. A two-step mass loss was exhibited by uncured and cured PAA in nitrogen atmosphere. A mass loss of 20-28% (155-274°C) and 50-61% (330-550°C) was observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Transition metal-catalyzed tandem isomerization and cationic polymerization of allyl ethers. II. Structural and mechanistic studies

In the presence of organosilanes, dicobalt octacarbonyl catalyzes the polymerization of alkyl allyl ethers to give high molecular weight polymers. This article reports the results of a detailed mechanistic study of this new polymerization reaction. The evidence obtained in this study supports a stepwise process involving first, the reaction of dicobalt octacarbonyl with an organosilane to form HCo(CO)₄ and R₃SiCo(CO)₄. In subsequent steps, HCo(CO)₄ isomerizes the allyl ether to a 1-propenyl ether and then this compound is polymerized by the formal transfer of a silyl cation from R₃SiCo(CO)₄. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1985–1997, 1997     

A mechanism of the hydrogenation of the double bond in the synthesis of allyl chalcogenides in the hydrazine hydrate-potassium hydroxide system

Allyl halides react with elemental selenium in the N₂H₄·H₂O−KOH system to give diallyl chalcogenides and allyl propyl chalcogenides. The latter form only in the presence of oxygen when unsaturated intermediates CH₂=CHCH₂YK (Y=S and Se), which are soluble in hydrazine hydrate, are hydrogenated with diimide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1874–1876, September, 1998.