Phosphorylation of 1,4-bis(hydroxymethyl)benzene

1,4-Bis(hydroxymethyl)benzene undergoes bisphosphorylation with P(NEt₂)₃ at room temperature. The reaction produces no cyclic structures.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 440–442, February, 2005.     

Synthesis and characterization of soluble polyamides based on 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane and diacid chlorides

Aromatic soluble polyamides and copolyamides having hexafluoroisopropylidene and isopropylidene moieties in the molecular structure of polymer chain were prepared by reacting the aromatic diacid chlorides and fluorine or nonfluorine containing aromatic diamines using low-temperature polycondensation process. Polymers were produced with high yield and moderate to high inherent viscosity. All polyimides and copolyamides showed thermal stability above 440°C and glass transition temperature above 200°C. Some of the polyamides were cast into transparent bulk films which were further characterized by mechanical, x-ray, and water absorption analysis. Fluoro polyamides showed superior structural properties as compared to nonfluoro polyamides. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of new aromatic polyesters and a polyether derived from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone

New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71–0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200–240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229–2235, 1998     

Preparation and characterization of fluorine-containing aromatic condensation polymers. II. Preparation and characterization of fluorine-containing aromatic polyformal and copolyformals by solution polycondensation of 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and/or 2,2-bis-(4-hydroxyphenyl)propane with dichloromethane

A series of fluorine-containing aromatic homopolyformal and copolyformals with a wide range of unit ratio were synthesized by the solution polycondensation of 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (Bisphenol AF) and/or 2,2-bis (4-hydroxyphenyl)propane (Bisphenol A) with dichloromethane, and the effect of the fluorine substitution on the preparation and properties of these polymers was investigated by comparing with those of Bisphenol-A-based homopolyformal without fluorine. Irrespective of the ratio of Bisphenol AF, high-molecular-weight, fluorine-containing polyformals with reduced viscosities of 1.4–5.3 dL/g were obtained in high yields by using dichloromethane as both comonomer and solvent, potassium hydroxide as a base, and N-methyl-2-pyrrolidone as a comedium at 75°C for 4 h. Their solubility increased markedly by the introduction of fluorine atom. Colorless, transparent, and tough films were cast from chloroform solution irrespective of fluorine content. These films had good mechanical properties comparable to that of Bisphenol-A-based homopolyformal. The contact angles by water were larger than 90°, regardless of their fluorine contents, at 25°C. The glass transition temperature and thermal stability increased monotonically with increasing fluorine content. © 1994 John Wiley & Sons, Inc.     

Preparative Method of Synthesis of Phosphoramidite Macroheterorings Derived from 2,2-Bis(4-hydroxyphenyl)propane and Related Phenols

Russian Journal of General Chemistry -     

Synthesis and some properties of 2,2-bis(difluoroamino)propanol

Conclusions Geminal bis(difluoroamino) alcohols were obtained by reacting difluoroamine with the trifluoroacetates of acetylenic alcohols and subsequent saponification. Some of the chemical properties of 2,2-bis(difluoroamino)-propanol were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 458–460, February, 1982.     

Synthesis and characterization of soluble polyimides from 2,2-bis(4-aminophenyl)cycloalkane derivatives

New aromatic diamines [(1) and (2)] containing polycycloalkane structures between two benzene rings were synthesized by HCl-catalyzed condensation reaction of aniline hydrochloride and corresponding polycycloalkanone derivatives. The structures of diamines were identified by ¹H-NMR, ¹³C-NMR, FTIR spectroscopy, and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The inherent viscosities of the resulting polyimides were in the range of 0.34–1.02 dL/g. The polyimides showed good thermal stabilities and solubility. All the polymers were readily soluble in N-methyl-2-pyrrolidone, m-cresol, tetrachloroethane, etc. Some of them were soluble even in chloroform at room temperature. The glass transition temperatures were observed in the range of 323–363°C, and all of the polymers were stable up to 400°C under nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3449–3454, 1999     

Synthesis of 1,4-bis(4-pyridyl)butadiyne

2-Methyl-4-(4-pyridyl)-3-butyn-2-ol ( 2 ) was prepared in 70% yield by the reaction of 4-bromopyridine with 2-methyl-3-butyn-2-ol in diethylamine in the presence of bis(triphenylphosphine)palladium(II) chloride and copper(I) iodide. Removal of the protective group in 2 by refluxing with sodium hydroxide in toluene yields (90%) 4-ethynylpyridine ( 3 ). Oxidative coupling of 3 in pyridine by dioxygen in the presence of copper(I) chloride produces a 92% yield of 1,4-bis(4-pyridyl)butadiyne.     

Three-dimensional structures of cyclic 2,2-bis(hydroxymethyl)-tetrahydrofuran acetals

2-Substituted spiro[1,3-dioxane-5,2-tetrahydrofurans] were obtained from 2,2-bis (hydroxymethyl) tetrahydrofuran, and their three-dimensional structures were investigated by ¹H and ¹³C NMR spectroscopy. The tetrahydrofuran ring lies in the plane of symmetry of the 1,3-dioxane ring with an equatorial orientation of the oxygen atom.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 162–166, February, 1984.     

Synthesis of aromatic polyethers by Scholl reaction. VII. Oxidative polymerization of 2,2-bis[4-(1-naphthoxy)phenyl]propane and 2,2-bis [4-(1-naphthyl)phenyl]propane

The synthesis and the mechanism of oxidative polymerization of 2,2-bis[4-(1-naphthoxy)phenyl]propane ( 4 ) and 2,2-bis[4-(1-naphthyl)phenyl]propane ( 9 ) are presented. Both monomers polymerize by two different propagation steps. The first one represents a cation-radical dimerization of the naphthyl groups to dinaphthyl structure. H⁺[FeCl₄]^? generated from the first propagation step initiates a transalkylation reaction which provides structural units containing isopropylidenic groups inserted between phenyl and naphthyl, and between two naphthyl groups, respectively. Since the phenyl groups resulted from the second propagation reaction are unreactive in both the oxidative coupling and the transalkylation steps this polymerization reaction leads to polymers with low molecular weights containing phenyl chain ends.     

季戊四醇双缩醛的合成

以苯为溶剂，ＴｓＯＨ为催化剂合成了几种长直链的季戊四醇双缩醛。     

Sulfur-containing polymers. Synthesis and properties of novel poly(arylene thioether)s based on 2,2-bis(4-mercaptophenyl)propane

Novel poly(arylene thioether)s were synthesised using the one pot polymerisation method from the bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane and activated difluoro aromatic compounds. Each of the polymers, obtained in good yields and with fairly high molecular weights, were characterised by IR, GPC and NMR analyses. In particular, the NMR characterisation was performed using ¹H NMR, ¹³C NMR, DEPT, 2D COSY and 2D HSQC experiments. To study the effect on the thermal properties of replacing the ethereal oxygen atoms with sulfur atoms, we have synthesised the counterparts, the poly(arylene ether)s, with similar molecular weights. We observed that the substitution of the ethereal oxygen atoms with sulfur atoms results in a slightly lower thermal stability for the poly(thioether ketone)s, both under nitrogen and in air, and does not modify the T_g values. For the poly(thioether sulfone), on the other hand, the thermal stability is equal to that of the poly(ether sulfone), while the T_g is 10 °C lower. Furthermore, each sample is completely amorphous, with the exception of one of the poly(thioether ketone)s (sample 1b), which shows the capacity to crystallise, even if with a very slow crystallisation kinetics.     

Polymorphs of 1,1-bis(4-hydroxyphenyl)cyclohexane and multiple Z' crystal structures by melt and sublimation crystallization

Close packing conflict in a metastable polymorph of the pure title host (Z' = 2, melt crystal m) is resolved in the stable form (Z' = 1, sublimed crystal s) as O-H...O hydrogen bond changes to O-H...pi interaction. Melt crystallization and sublimation show a greater percentage of high Z' structures in CSD statistics.     

Synthesis and structures of 1,4-bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes

1,4-Bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes were synthesized by the reactions of triphenylphosphine with CCl4 and NBS, respectively. The structures of the compounds were studied by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1399–1401, August, 2006.     

2,2’-二(4-羟基苯基)丙烷与四丁基铵包合物([(n-C4H9)4N]＋• [(C15H15O2)2H]－)的两种同质异晶体

合成了2,2’-二(4-羟基苯基)丙烷为主体分子的四丁基铵包合物, [(n-C4H9)4N]＋•[(C15H15O2)2H]－, 并通过单晶Ｘ射线衍射法对其进行了晶体结构测定, 发现该包合物的晶体存在两种同质异晶体. 结果表明, 晶型1属单斜晶系, C2/c空间群, 晶胞参数a＝2.8199(2) nm, b＝0.92730(8) nm, c＝2.1450(3) nm, β＝130.050(1)°, Z＝4, R1＝0.0771, wR2＝0.2452; 晶型2属三斜晶系, P`1空间群, 晶胞参数a＝1.0895(1) nm, b＝1.2331(2) nm, c＝1.7244(2) nm, α＝108.137(2)°, β＝94.458(2)°, γ＝100.172(2)°, Z＝2, R1＝0.0697, wR2＝0.2176. 晶型1中2,2’-二(4-羟基苯基)丙烷阴离子的氢键链构成管道式主体晶格, 正四丁基铵阳离子被包合在这些管道中; 晶型2中2个独立的2,2’-二(4-羟基苯基)丙烷阴离子分别形成氢键主体层, 它们交替排列并与夹在其间的正四丁基铵阳离子形成类三明治层状包合物.