High refractive index materials: A structural property comparison of sulfide‐ and sulfoxide‐containing polyamides

High‐refractive‐index polyamides (PAs) are developed by incorporation of sulfide‐ or sulfoxide linkages and chlorine substituents. The PAs are synthesized through the polycondensation of two novel diamine monomers, 2,2′‐sulfide‐bis(4‐chloro‐1‐(4‐aminophenoxy) phenyl ether (3a) and 2,2′‐sulfoxide‐bis(4‐chloro‐1‐(4‐aminophenoxy) phenyl ether (3b), with various aromatic diacids (a–e). The ortho‐sulfide or sulfoxide units, pendant chlorine groups, and flexible ether linkages in the diamine monomers endowed the obtained PAs with excellent solubilities in organic solvents. The resulting PAs showed high thermal stability, with 10% weight loss temperatures exceeding 415 °C under nitrogen and 399 °C in air atmosphere. The combination of chlorine substituents, sulfide or sulfoxide linkages, and ortho‐catenated structures provided polymers with high transparency along with high refractive index values of up to 1.7401 at 632.8 nm and low birefringences (<0.0075). The structure–property relationships of the analogous PAs containing sulfide or sulfoxide linkages were also studied in detail by comparing the results. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2867–2877     

Polylithiumorganic compounds. Part 29: C,C Bond cleavage of phenyl substituted and strained carbocycles using lithium metal

The reaction of phenyl substituted cyclopropanes phenylcyclopropane and 1,1-diphenylcyclopropane, phenyl substituted bicyclobutanes 1-phenylbicyclobutane, 1-methyl-3-phenylbicyclobutane, 1-methyl-2,2-diphenylbicyclobutane, as well as phenyl substituted spiropentanes phenylspiropentane and 1,1-diphenylspiropentane with lithium metal or lithium di-t-butylbiphenyl (LiDBB) was investigated. Under suitable reaction conditions and choice of solvent in all cases cleavage of the single bond next to the activating phenyl group was observed. The dilithiumorganic compounds thus obtained are sufficiently stable and can be trapped with electrophiles. Lithium hydride elimination is observed as follow-up reaction only in a few cases. The corresponding anions of the strained ring systems 1-lithio-2,2-diphenylcyclopropane, 1-lithio-3-phenylbicyclobutane, 1-lithio-3-methyl-2,2-diphenylbicyclobutane, and 1-lithio-4-phenylspiropentane, which can be obtained by lithium bromine exchange or by metalation of the unsubstituted carbocycle, do not show any cleavage upon reaction with lithium metal.     

A novel photoinitiator of cationic polymerization: Preparation and characterization of bis [4-(diphenylsulfonio)phenyl]sulfide–bis-hexafluorophosphate

Efforts to prepare triphenylsulfonium hexafluorophosphate by metathesis between commercially available “triphenylsulfonium chloride” and potassium hexafluorophosphate failed to yield the expected product but gave, instead, in approximately 50% yield, a crystalline substance with well-defined properties readily distinguishable from triphenylsulfonium hexafluorophosphate. The unexpected substance is identified as bis-[4(diphenylsulfonio)phenyl]sulfide–bis-hexafluorophosphate, for which no previous reference has been found in the literature. Its identification is based on elemental analysis, NMR, mass spectrometry, and infrared analysis. Bis-[4-(diphenylsulfonio)phenyl]sulfide–bis-hexafluorophosphate was also prepared by the reaction of benzene with sulfur monochloride in the presence of aluminum chloride and chlorine, followed by addition of potassium hexafluorophosphate. The product is an effective photonitiator for the crosslinking of epoxide resins.     

Reactions of tris(2-pyridyl)phosphines and tris(2-pyridyl)phosphine oxides with some electrophiles

Treatment of tris(2-pyridyl)phosphine or tris(2-pyridyl)phosphine oxide with electrophiles such as chlorine, bromine, deuterium chloride, or benzenediazonium chloride gave unusual coupling products, i.e., 5-chloro-, 5-bromo-, 5-deuterio-, or 5-phenylazo-2,2′-bipyridyls, respectively, as a major coupling product in each case. This is considered to be the result of electrophilic substitution on a pyridyl ring in a pentacovalent phosphorane intermediate formed in each reaction. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 439–449, 1997     

表皮生长因子受体酪氨酸激酶抑制剂的药效团研究

根据一系列表皮生长因子受体酪氨酸激酶抑制剂的三维定量构效关系研究，得 到了该类抑制剂的药效团，研究结果与Novartis的药效团模型相当类似．药效团包 括一个氢键受体，一个氢键给体，一个疏水区和一个带有氯或溴原子药效团对于研 究表皮生长因子受体酪氨酸激酶抑制剂结构与活性的关系具有重要的意义．通过三 维数据库搜索可能会得到新的先导化合物．     

An application of HPLC and ion chromatography to study intramolecular charge transfer in polyhalogenated systems

Reaction of hydrated electrons with aromatics substituted with both bromine and chlorine results in the production of significant yields of chloride ion and the complementary bromine substituted phenyl radical. The total yields show that in all cases the reduction is essentially quantitative. For the dihalogenated benzenes and phenols the relative yields for C-Br and C-Cl bond rupture (0.86:0.14) reflect the relative rates for electron attachment at the Br and Cl positions, suggesting that there is little intramolecular charge transfer on the time scale of dissociation of the initial anion. In the case of dihalogenated benzoates about 40% of the reduction results in C-Cl bond rupture. In this case the added charge initially localized on the carboxyl group is transferred preferentially to the chlorine atom indicating that solvation of the intermediate radical anion must play an extremely important role in controlling the overall reduction process.     

Nucleophilic substitution reactions of 1,4-dichlorobenzene chromium tricarbonyl with mono- and diphenoxides

The nucleophilic substitution reactions of 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) with the phenoxide anion were investigated. The substitution of the first chlorine was very fast and gave the mono-substituted product in high yield. The substitution of the second chlorine group was significantly retarded by the presence of the phenoxy group incorporated during the first reaction and also due to the competing decomplexation reaction. The application of 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) to the synthesis of new monomers was demonstrated by the preparation of 2,2′-bis[4-(4-chlorophenoxy)phenyl]propane ( 9 ). 2,2′-Bis[4-(4-chlorophenoxyl)phenyl]propane ( 9 ) was synthesized by a nucleophilic substitution reaction of 4,4′-isopropylidenediphenolate with 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) followed by decomplexation with I₂. 2,2′-Bis[4-(4-chlorophenoxy)-phenyl]propane ( 9 ) was also synthesized via a three-step reaction starting from the nucleophilic substitution reaction of 4,4′-isopropylidenediphenol ( 7a ) with 1-chloro-4-nitrobenzene ( 10 ). 2,2′-Bis[4-(4-chlorophenoxy)phenyl]propane ( 9 ) was polymerized by a Ni(0)-catalyzed reaction to yield amorphous aromatic polyethers with number-average molecular weights of up to 11,200 g/mol. © 1993 John Wiley & Sons, Inc.     

The carbonylation of phenyl bromide and its derivatives under visible light irradiation

The carbonylation of phenyl bromide catalyzed by Co（OAc）₂ has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH₃ONa,PhCOOCH₃ is produced in 70%yield with 100%selectivity,the similar results are also obtained with a stronger base（CH₃）₃CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or（n-C₄H₉）₃N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC₆H₄CH₃ are similar to phenyl bromide, while the activities of o,m,p-BrC₆H₄Cl are higher with the high yields（≥93%） of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.     

Reactivity of main grouptransmittion metal bonds : III. Reactions of halogens with Ph3SiMn(CO)5 and Ph3SnMn(CO)5

The products of the reaction of Ph₃MMn(CO)₅ (M = Si or Sn) with chlorine, bromine and iodine in tetrachloromethane, have been determined.Ph₃SiMn(CO)₅ does not react with iodine, and the SiMn bond is cleaved by chlorine and by bromine.Ph₃SnMn(CO)₅ reacts in a much more complex manner, PhSn bond cleavage occurring with all three halogens to give mono-, di-, and, with the exception of iodine, tri-halogenated derivatives. Bromine, in high concentration, and iodine also cleave the SnMn bond.     

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene was studied. Unexpectedly, 3-bromo-1-methyl-1-azoniatricyclo[2.2.1.0^2,6]heptane tribromide was isolated rather than the product of bromine addition to the double bond. The former reacted with the starting alkene in a polar solvent to form the corresponding monobromide.     

5,6-Bis(dimethylamino)acenaphthylene as an activated alkene and ‘proton sponge’ in halogenation reactions

It has been shown that 5,6-bis(dimethylamino)acenaphthylene in its reactions with X₂ (X=Cl, Br, I) and N-X-succinimides behaves simultaneously as an electron-rich alkene or arene and proton sponge. Thus, addition of bromine or iodine to the C(1)C(2) bond is followed by immediate dehydrohalogenation leading to the formation of the corresponding 1(2)-(di)halogenoacenaphthylenes in good yields. Reaction with chlorine enables isolation of only 1,4,7-trichloro-5,6-bis(dimethylamino)acenaphthylene. With N-halosuccinimides, the halogenation is directed mainly by the steric bulk of the entering halogen and then by solvent polarity thus allowing the regioselective preparation of 1(2)- or 4(7)-(di)halides. Introduction of the third and fourth bromine atoms, but not chlorine, is accomplished by mono-N-demethylation. The pK_a values of some new derivatives of acenaphthene and acenaphthylene proton sponges were measured by competitive transprotonation ¹H NMR spectroscopy technique in DMSO. The X-ray molecular structures of 4,7-dichloro-5,6-bis(dimethylamino)acenaphthylene and its monoprotonated form are reported.     

Photoreaction of 2-halo-N-pyridinylbenzamide: intramolecular cyclization mechanism of phenyl radical assisted with n-complexation of chlorine radical

The photochemical behavior of 2-halo-N-pyridinylbenzamide (1-4 in Chart 1) was studied. The photoreaction of 2-chloro-N-pyridinylbenzamides 1a, 2a, 3a, and 4 afforded photocyclized products, benzo[c]naphthyridinones (6-9 and 16), in high yield, whereas the bromo analogues 1b, 2b, and 3b produced extensively photoreduced products, N-pyridinylbenzamides (1c, 10, and 11), with minor photocyclized product. Since the photocyclization reaction of 2-chloro-N-pyridinylbenzamide is retarded by the presence of oxygen and sensitized by the presence of a triplet sensitizer, acetone or acetophenone, a triplet state of the chloro analogue is involved in the reaction. Since several radical intermediates, particularly n-complexes of chlorine radical, are identified in the laser flash photolysis of 2-chloro-N-pyridinylbenzamide, an intramolecular cyclization mechanism of phenyl radical assisted with n-complexation of chlorine radical for the cyclization reaction is proposed: the triplet state (78 kcal/mol) of the chloro analogue (1a), which is populated by the excitation of 1a undergoes a homolytic cleavage of the C-Cl bond to give phenyl and chlorine radicals; while chlorine radical holds the neighbor pyridinyl ring with its n-complexation, the intramolecular arylation of the phenyl radical with the pyridinyl ring proceeds to produce a conjugated 2,3-dihydropyridinyl radical and then the conjugated radical aromatizes to afford a cyclized product, benzo[c]naphthyridinone by ejecting a hydrogen. The photoreduction product can be formed by hydrogen atom abstraction of the phenyl sigma radical from the environment.     

Synthesis, Fourier transform infrared and Raman spectra, assignments and analysis of N-(phenyl)- and N-(chloro substituted phenyl)-2,2-dichloroacetamides

N-(phenyl)-2,2-dichloroacetamide (NPA) and N-(chloro substituted phenyl)-2,2-dichloroacetamides of the configuration XyC6H(5-y)-NHCO-CHCl2 (where, X = Cl and y = 1, 2 and 3) were synthesised and the Fourier transform infrared (FTIR) and Fourier transform Raman (FT-Raman) spectra of the compounds were recorded and analysed. The FTIR spectra of all the compounds were recorded in a Bruker IFS 66V spectrometer in the range of 4000-400 cm(-1) and the FT-Raman spectra were also recorded in the same instrument in the region 3500-100 cm(-1). The variation of an amide bond (-NHCO-) parameters with the substitution of the chlorine atom in the phenyl group and the mixing of different normal modes are discussed with the help of potential energy distribution (PED) calculated through normal co-ordinate analysis.     

四溴双酚A-双(2,3-二溴丙基醚)的绿色合成

本文探索了水相中烯烃与溴的加成反应,以四溴双酚A双烯丙基醚为原料,在水相中合成四溴双酚A-双(2,3-二溴丙基)醚,通过考察助剂类型及用量、溴的用量、反应时间、反应温度等因素,优化反应条件,产品收率可达到93.6%,通过HPLC检测纯度达到91.7%。本文借助十二烷基硫酸钠不仅解决了原料不溶于水导致产品团聚的问题,而且此方法后处理简单,无废液产生,简化了工艺路线,可有效降低成本。     

蒎酮酸的卤代反应

国外对蒎酮酸的制备、反应及其衍生物的应用报道颇多。为了开发利用我国丰富的松节油资源,我们对顺式蒎酮酸(1)的卤代反应进行了研究。关于蒎酮酸的溴代反应已有研究,而氯代反应还未见报道。我们选用了氯气和氯化硫酰作为氯代反应试剂。在酸性条件下1与氯反应时,得到顺式-2,2-二甲基-3-氯乙酰基环     

Conjugate halo- and mercuroazidation of 1-phenyltricyclo-[4.1.0.0<Superscript>2.7</Superscript>]heptane. Synthesis of a conformationally rigid α-amino acid with a bicyclo[3.1.1]heptane skeleton

1-Phenyltricyclo[4.1.0.0^2.7]heptane reacted with N-bromo-, N-chloro-, and N-iodosuccinimides and with mercury(II) acetate in the presence of sodium azide as external nucleophile to give conjugate addition products to the central C¹–C⁷ bicyclobutane bond with a norpinane structure, where the azido group and the phenyl were attached to the same carbon atom (C⁶). The bromo- and chloroazidation showed anti-stereo-selectivity, and the iodoazidation, moderate syn-stereoselectivity; the mercuroazidation afforded exclusively the corresponding syn-addition product. Hydro-, bromo- and chlorodemercuration of the mercury adduct with sodium tetrahydridoborate and elemental bromine and chlorine, respectively, did not involve the azido group, and the original configuration was retained. The reduction of the hydrodemercuration product with LiAlH₄ gave 6-exo-phenylbicyclo[3.1.1]heptan-6-amine which was transformed in three steps into conformationally rigid 6-endo-(acetamido)bicyclo[3.1.1]heptane-6-carboxylic acid.     

Reactions of group IV organometallic compounds : XXIX. Insertion reactions of (trimethylsilylmethylene)phosphorane with heterocumulenes. Inhibition of Wittig type reactions

A reaction of (trimethylsilylmethylene)dimethylphenylphosphorane, PhMe₂PCHSiMe₃ (I), with phenyl isocyanate affords a 2/1 insertion product, which results from insertion of phenyl isocyanate into both the CSi and CH bonds of I. By way of contrast, a reaction of isothiocyanate and carbon disulfide with I affords 1/1 products by insertion of these heterocumulenes into the CSi bond of I. In these reactions, Wittig-type elimination of dimethylphenylphosphine oxide or sulfide did not occur because of irreversible migrations of the trimethylsilyl group to the anionic centers of the Zwitterionic intermediates.     

Synthesis of new haloderivatives of benzo[<Emphasis Type="Italic">f</Emphasis>]quinoline and 4,7-phenanthroline

By condensations of 2-naphthylamine and 6-aminoquinoline with halogen-substituted benzaldehydes, 3-acetylpyridine and acetophenone derivatives new 1,3-diaryl(heteryl)benzo-[f]quinolines and 4,7-phenanthrolines were synthesized containing atoms of fluorine, bromine, and chlorine in the phenyl rings.     

Ionic and radical addition of chlorine,bromine and some halogen systems of butadiene monoxide (4)

Ionic reactions of bromine, chlorine, methyl hypochlorite or N-bromosuccinimide with butadiene monoxide ( 4 ) give only 1,2-addition products. The Markownikoff (1-halo-2-methoxy-3,4-epoxybutane) and anti-Markownikoff (2-halo-1-methoxy-3,4-epoxybutane) product ratios for ionic reaction of methyl hypochlorite and N-bromosuccinimide in methanol with 4 are similar to those obtained with 1-hexene. These data indicate that a rather symmetrical halonium ion is formed in the ionic halogenation of 4 . Free radical reaction of bromine, chlorine, or trichloramine to 4 does not give ring-opened products as one might expect for formation of an epoxy carbonyl intermediate. The mechanistic implications from these observations are discussed.     

Chalcogenation of 1,3-dichloropropene with elemental chalcogens in the system hydrazine hydrate–base

Sulfur reacts with 1,3-dichloropropene in the system hydrazine hydrate–KOH to form bis(1-chloroprop-1-en-3-yl) sulfide, and in the system hydrazine hydrate–monoethanolamine, bis(1-chloroprop-1-en- 3-yl) disulfide. The reaction of tellurium in the system hydrazine hydrate–KOH leads to diallyl telluride, the product of nucleophilic substitution of the allylic chlorine atom and reductive cleavage of the С_sp2–Cl bond. The reaction of selenium with 1,3-dichloropropene gives a complex mixture of products. At excess KOH (Se: KOH = 1: 5) bis(1-chloroprop-1-en-3-yl) selenide was isolated.