Cycloaddition Reactions and Dendritic Polymer Architectures – A Perfect Match

Summery: The potential of cycloaddition (CA) reactions for the synthesis of dendritic polymers is pointed out. The [4 + 2] Diels Alder cycloaddition as well as 1,3-dipolar CA reactions including “click chemistry” are addressed, and the advantages of these reactions like high selectivity, thus high tolerance towards additional functionalities, high yields and synthesis under mild reaction conditions are highlighted. New perfectly branched dendrimers as well as hyperbranched polymers have been prepared and modified using the 1,3-dipolar cycloaddition reaction of azines with alkynes. The 1,3-dipolar CA reaction of bisazine with maleimides results in hyperbranched and thus, irregular and broadly distributed polymers though with a degree of branching of 100% due to special intermediate formation. The [4 + 2] Diels Alder cycloaddition was successfully applied for the synthesis of highly branched polyphenylene structures using the AB₂ + AB and the A₂ + B₃ approach. CA reactions are also very suitable for highly efficient polymer analogous reactions and thus, they can also be used to prepare complex polymer architectures like dendronized polymers.     

Characterization of a poly(ethersulphone) by on-line coupling of size exclusion chromatography with NMR and FTIR spectroscopy

An on-line detection „on the flow”︁ during the size exclusion chromatography run using FTIR and NMR spectrometers was applied to investigate the liquid chromatographic separation process of oligomers and to identify the separated chromatographic compounds. The FTIR and NMR detectors give real-time information about the chemical structure and functional groups of the eluated species. The preferences and limits of the on-line coupling were discussed using an oligomeric hydroxyl terminated poly(ethersulphone) as an example. Molecular weights could be calculated from the ¹H-NMR spectra of the separated species using the intensities of end-group and main-chain signals. Residues of N-methylpyrrolidone which was used as solvent in the oligomer synthesis were identified by the FTIR detector.     

Tannin-Mordant Coloration with Matcha (camelia sinensis) and Iron(II)-Lactate on Human Hair Tresses

The aim of this work was to optimize our natural hair dyeing system which we described in our previous work and to compare with other dyeing systems. Therefore, we investigated concentration limits of matcha and mordant and compared this new dyeing method with commercial permanent systems on the market. Completely unpigmented hair tresses were dyed with matcha powder (camelia sinensis) and iron(II)-lactate. To investigate the wash fastness and concentration limits, the differently dyed hair tresses were spectrophotometrically measured. The comparison of the damage potential for which cysteic acid is an indicator was measured by NIR. The concentration of matcha and mordant are responsible for the intensity of the color results. The higher the matcha or the mordant concentration, the darker the color results of the dyed hair tresses. Hair damage of matcha mordant dyeing is comparable with results of commercial permanent hair coloration systems. Moreover, the results of wash fastness of matcha mordant dyed hair tresses is comparable and even better by tendency to permanent colored hair tresses.     

Phosphine-Stabilized Pnictinidenes

The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh₂)C₆H₄GeAr* ( 1 ) with Group 15 element trichlorides ECl₃ (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh₂)C₆H₄(Ar*)Ge(Cl)ECl₂ ( 2 : E=P, 3 : E=As, 4 : E=Sb) were reduced by using sodium metal or LiHBEt₃. The molecular structures of the phosphine-stabilized phosphinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)P ( 5 ), arsinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)As ( 6 ) and stibinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)Sb ( 7 ) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh₂)C₆H₄(Ar*)GeP] [B(C₆H₃(CF₃)₂)₄] ( 8 ) was isolated. The ³¹P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu₂AlH]₂, and the product of an Al−H addition to the low-valent phosphorus atom (o-PPh₂)C₆H₄(Ar*)Ge(H)P(H)Al(C₄H₉)₂ ( 9 ) was characterized.     

Germaborenes: Borylene Transfer Agents for the Synthesis of Iminoboranes

Halide and phenyl substituted germaborenes were shown to react with azides at room temperature and transfer a borylene moiety to give iminoboranes. This iminoborane synthesis based on a borylene transfer route was investigated computationally in the case of the phenyl substituted germaborene.