Photosensitized Cationic Polymerization of Cyclohexene Oxide Using a Phenacylanilinium Salt

The photoinitiated cationic polymerization of cyclohexene oxide with N‐phenacyl‐N,N‐dimethylanilinium hexafluoroantimonate (PDA⁺SbF₆^–) and a polynuclear aromatic compound, such as perylene, anthracene or phenothiazine, or an aromatic carbonyl compound, such as benzophenone or thioxanthone, was studied at λ_inc > 340 nm. All the aromatic sensitizers except benzophenone and thioxanthone are effective in initiating the polymerization at wavelengths where PDA⁺SbF₆^– is transparent. An initiation mechanism is proposed that involves electron transfer from the excited sensitizer to PDA⁺SbF₆^–.     

Selective Reactions with Organoaluminum Compounds

With the aid of selected examples an overview is given of the development trends in highly discriminative reactions using organoaluminum compounds. (1) Isomerization of substituted oxiranes into allyl alcohols has been effected both stereo- and regioselectively by means of a new organoaluminum reagent, diethylaluminum 2,2,6,6-tetramethylpiperidide (DATMP); this reaction which provides a new route for the regiospecific transformation of allyl alcohols into 1,3-dienes. (2) A novel nonenzymic heterolysis of allylic phosphates of terpenoids has been effected by organoaluminum compounds and has enabled development of a new method for the selective synthesis of cyclic terpenes. (3) The reductive condensation of α-haloketones with carbonyl compounds in the presence of diethylaluminum chloride and zinc affords β-hydroxy-carbonyl derivatives in good yields with exclusion of undesired self-condensations products.     

Thermodynamics and Thermochemistry of Organoaluminum Compounds

The accuracy and reliability of thermodynamic data on vaporization of trialkylaluminum, alkylaluminum hydrides, and alkylaluminum chlorides and of thermochemical data for these compounds were estimated on the basis of author's and published data. A unified system of consistent thermodynamic characteristics of the organoaluminum compounds was proposed, and the enthalpies of vaporization of a number of unstudied compounds and the dissociation energies of Al-R bonds were estimated.     

Complexing of Organoaluminum Compounds with Polyethers and Polyacetals

This work is concerned with the study of the complexing reaction between the low molecular weight V-acceptor, diethylaluminum chloride (DC), and polymeric donors containing oxygen, such as poly(ethylene oxide) (PEO), polypropylene oxide) (PPO), polytetrahydrofuran (PTHF), polyformal-dehyde (PF), poly(phenylene oxide) (PPO), polydioxolan (PDO), and polytrioxocan (PTO). Three types of complexes, 1:1, 2:1, and 1:2, were detected in solution. In the case of PEO, the thermodynamical parameters of the 1:1 complex formation are ΔH₁ = ?23.3 ± 0.5 kcal/mole, K¹ = (5 ± 2) × 105 liter/mole, ASi = ?51.5 ± 2.4 eu, while those of the 1:2 complex formation (0.2A1) from the 1:1 adduct are AH = -18.5 ± 0.6 kcal/mole, K = 0.9 ± 0.3 liter/mole, AS = ?62.3 ± 2.9 eu. Two structures were found in the case of 1:1 polymer-acceptor complexes.     

Organoaluminum Compounds as Catalysts for Monohydroboration of Carbodiimides

The effective catalytic activity of organoaluminum compounds for the monohydroboration of carbodiimides has been demonstrated. Two aluminum complexes, 2 and 3 , were synthesized and characterized. The efficient catalytic performances of four aluminum hydride complexes L¹AlH₂ (L¹=HC(CMeNAr)₂, Ar=2,6-Et₂C₆H₃; 1 ), L²AlH₂(NMe₃) (L²=o-C₆H₄F(CH=N-Ar), Ar=2,6-Et₂C₆H₃; 2 ), L³AlH (L³=2,6-bis(1-methylethyl)-N-(2-pyridinylmethylene)phenylamine; 3 ), and L⁴AlH(NMe₃) (L⁴=o-C₆H₄(N-Dipp)(CH=N-Dipp), Dipp=2,6-iPr₂C₆H₃; 4 ), and an aluminum alkyl complex L¹AlMe₂ ( 5 ) were used for the monohydroboration of carbodiimides investigated under solvent-free and mild conditions. Compounds 1 – 3 and 5 can produce monohydroborated N-borylformamidine, whereas 4 can afford the C-borylformamidine product. A suggested mechanism of this reaction was explored, and the aluminum formamidinate compound 6 was characterized by single-crystal X-ray, also a stoichiometric reaction was investigated.     

氧化环己烯连续进料下二氧化碳-环氧丙烷-氧化环己烯三元共聚物的合成

由于氧化环己烯（CHO）与二氧化碳的共聚反应速度比其与环氧丙烷（PO）快,这种竞聚率的差异导致一锅法所得的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的组成难以稳定控制。 为此本文在稀土三元催化剂下,采用氧化环己烯单体连续进料的方法合成了二氧化碳-环氧丙烷-氧化环己烯三元共聚物,催化效率可达575 g/(mol Zn h)。 三元共聚物的玻璃化转变温度随CHO含量升高而增大,当CHO的摩尔投料比从0.19增加到0.59时,玻璃化温度从44.3 ℃提高到70.1 ℃。 CHO连续进料合成的三元共聚物的组成与投料比基本相近,且连续进料法所合成的三元共聚物只有一个玻璃化转变温度,而普通的一锅法所得的三元共聚物通常存在两个玻璃化转变温度,因此连续进料法是制备组成稳定的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的有效方法。     

Cationic Copolymerization of Epichlorohydrin with Styrene Oxide and with Cyclohexene Oxide

Cationic copolymerizations of epichlorohydrin (ECH) (chloro-methyl oxirane) with styrene oxide (SO) (phenyl oxirane) and with 1,2-cyclohexene oxide (CO) (7-oxabicyclo [410] heptane) were carried out at 50°C by employing the salt triphenylmethyl hexachloro-antimonate (HC) (Ph₃CSbCl₆) as initiator. NMR spectra before and after attempted extractions of the polymeric products indicated that the resulting polymeric products were true copolymers and not mixtures of the respective homopolymers. Monomer reactivity ratios for both pairs of comonomers were determined; for one pair the values were r ₁(ECH) = 3.29, r ₂(CO) = 0.16 and for the second pair r ₁(ECH) = 0.57, r ₂(SO) = 0.16.     

铜盐催化氧化环己烯的开环加成反应

研究了一系列铜盐催化的氧化环己烯与苯基氯化镁的开环加成反应。发现Cu(OTf)2[三-氟甲磺酸铜(Ⅱ)]为催化剂时,反应能够以95％的产率得到反式-2-苯基环己醇。应用了多种代表性的手性双齿配体与Cu(OTf)2形成的配合物,催化氧化环己烯与苯基氯化镁的开环加成反应,得到很低的对映选择性。根据实验的结果建议了反应的催化循环机理。     

Photopolymerization of Cyclohexene Oxide Initiated with Iron-arene Complex

Two iron-arene complex photoinitiators with different substituents in arene ligands were synthesized, their activities in initiating photopolymerization of cyclohexene oxide (CHO) were compared with that of IRGACURE 261, a commercialized photoinitiator from Ciba-Geigy. A higher activity was found when the arene ligand was substituted with a stronger electron donating group. For the system initiated by IRGACURE 261 the concentration of active centers in CHO polymerization was determined and it was found that the concentration is maximum at around 35℃. The post (dark) polymerization was significant, the polymerization yield decreased with the increase of irradiation temperature and increased with the increase of post polymerization temperature. The results are interpreted based on the mechanism proposed by Lohse, et al..     

Polymerization of Fluorothiocarbonyl Compounds

Recently it was shown that the C[dbnd]S group in fluorothiocarbonyl compounds readily undergoes addition polymerization. This review describes polymers obtainable from such compounds as CF₂[dbnd]S, CF₃CF[dbnd]S, ClCF₂CF[dbnd]S, HCFClCF[dbnd]S, and hexafluorothioacetone. The polymerization of CF₂[dbnd]S is readily brought about in anionic systems at low temperatures, giving a high-molecular-weight poly(thiocarbonyl fluoride) with a number-average molecular weight in the range of 300,000 to 400,000. It is believed that the major portion of this polymer is composed of chains of CF₃–-S—(—CF₂S—)_n–CF[dbnd]S. Poly(thiocarbonyl fluoride) is a highly resilient elastomer in the amorphous form but suffers the disadvantage of slow crystallization at temperatures below 35°C and concomitant loss of rubbery properties. Above 175°C it depolymerizes. Fluorothioacyl fluorides also undergo anionic polymerization, but the products are logy elastomers. Copolymers of fluorothioacyl fluorides with CF₂[dbnd]S have better thermal stability but poorer resilience than poly(thiocarbonyl fluoride). Hexafluorothioacetone has been polymerized at—110°C to give a white elastomer that slowly depolymerizes at room temperature to regenerate monomer. Thiocarbonyl fluoride is also susceptible to free-radical polymerization, and in free-radical systems it copolymerizes with conventional vinyl monomers, giving a wide variety of new elastomeric products.     

铁-芳烃络合物引发氧化环己烯阳离子光聚合反应动力学研究

以环戊二烯异丙苯铁六氟磷酸盐为引发剂,用示差扫描量热法研究了氧化环己烯(CHO)阳离子聚合反应动力学.实验结果表明,温度对CHO聚合反应影响很大.CHO在一系列温度下等温聚合时,放热量和转化率均在40℃左右最高,而聚合反应速率则随着温度的升高而降低.CHO聚合反应属一级反应,活化能为-9.87kJ/mol,并对聚合反应历程进行了理论推导,其结果与实验结果相符合.     

钯催化环己烯氧化合成环己酮

考察了由不同金属酞菁（ＭＰｃ，Ｍ＝Ｆｅ，Ｃｏ，Ｃｕ）氯代金属卟啉（ＭＴＰＰＣ．，Ｍ＝Ｆｅ，Ｃｒ，Ｍｎ）和Ｐｄ（ＯＡｃ）２（醋酸钯）／ＨＱ（氢醌）组成的催化体系对环己烯氧化成环己酮的催化活性。表明，在乙腈酸性水溶液中，Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ催化体系对环己烯氧化合成环己酮显示出较高的催化活性，在３０ｍｉｎ内环己酮收率可达８４％，选择性＞９８％，研究了各种因素对体系催化活性的影响。     

Radiation-Induced Polymerization of Styrene Oxide

Radiation-induced polymerization of styrene oxide in the liquid and solid states was carried out by initiating with γ-rays from ⁶⁰Co and electrons from a Van de Graaff accelerator.

Effects of dose rate, a radical inhibitor, and temperature on the polymerization were examined. Infrared spectra and viscosities of polymers obtained were measured.

From these experiments, the following results were obtained:

1. Apparent activation energies are 6.2 kcal/mole for the liquid-state polymerization and 0.17 kcal/mole for the solid-state polymerization, respectively.

2. The polymerization in liquid state is inhibited and retarded by p-ben-zoquinone.

3. The rate of polymerization is approximately proportional to the dose rate.

4. The viscosity of polymers obtained increases with irradiation dose.

5. Infrared spectrum of polymers obtained varies with the polymerization temperature.

It is emphasized in this paper that the chain-transfer and isomerization reactions are rapid and play an important role in the polymerization of styrene oxide, and that the polymer-forming process is not so rapid, owing to a step-by-step type of growing.     

Catalytic Oxidation of Cyclohexene with Molecular Oxygen on Hydrotalcite－like Compounds

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Noncatalyzed Addition of Trimethylsilyl Isothiocyanate to Aziridines and Cyclohexene Oxide

Ring opening of N-substituted aziridines and cyclohexene oxide with trimethylsilyl isothiocyanate proceeds without the use of any catalyst under mild conditions to give N-substituted trans-2-amino-1-isothiocyanates, trans-2-amino-1-thiocyanates, or trans-2-hydroxy-1-isothiocyanates.     

稀土三元催化剂催化二氧化碳/环氧丙烷/环氧环己烷的三元共聚合研究

在稀土三元催化剂(三氯乙酸稀土配合物/二乙基锌/甘油)催化下实现了二氧化碳、环氧丙烷及环氧环己烷的三元共聚合.该催化剂对二氧化碳与环氧环己烷共聚的催化活性比对二氧化碳与环氧丙烷共聚的高.增加反应单体中环氧环己烷的比例可提高共聚物中环己撑碳酸酯的含量,大幅度改善共聚物的耐热性.     

环氧乙烷环氧丙烷开环聚合反应动力学研究

环氧乙烷和环氧丙烷由于具有较高的环张力,因而容易发生开环聚合。本文综述了环氧乙烷合环氧丙烷开环聚合反应的动力学研究进展,考察了环氧乙烷和环氧丙烷开环聚合反应的机理,分别讨论了各类催化剂体系中环氧乙烷和环氧丙烷开环聚合的动力学常数、两者的竞聚率及开环聚合产物的分子量分布,并指出了开环聚合反应动力学研究对于环氧乙烷和环氧丙烷的开环聚合研究及工业应用的重要性。     

A New Cyclohexene Oxide from Uvaria tonkinensis var. subglabra

A new compound, subglain B, was isolated from the stems of Uvaria tonkinensis var.subglabra and its structure was identified as 1S, 2R, 3S, 6R-1-benzoyloxymethylene-1,2-dihydroxy-3-benzoyloxy-6-chlorocyclohex-4-ene (1), by spectral evidences.