4–Hydroxy–3–arylamino–l, 8–naphthalimides and 3–(and 4–) hydroxy–2–(and 5–) arylamino–7H–bcnzimidazo–(2, l–a)benz(d,e)isoquinolin–7–ones. Red dyes for synthetic–polymer fibres

4–Hydroxy–1, 8–naphthalimides and the isomer mixtures of'3–and 4–hydroxy–7 H–benzimidazo–(2, l–a)–benz(d, e)–isoquinolin–7–ones were coupled with diazotised arylamines to yield orange–red to bluish–red dyes having good coloration properties and excellent fastness to light on polyester fibres. Structure–property relationships in the dyes are discussed with respect to the nature of the substituents in the imide, imidazole and arylazo moieties.     

1,4-Dihydroxyanthraquinone-2-ethers and 2-sulphones — yellow to orange dyes for synthetic-polymer fibres

Condensation of 2-bromo-1,4-dihydroxyanthraquinone with alcohols and phenols affords the 2-ether derivatives, which colour synthetic-polymer fibres, particularly polyester, in yellow-orange hues of good build-up and light fastness. The influence of the 2-ether substituent on the colour of these 1,2,4-tri-donor-substituted anthraquinones is discussed, together with the relative influence of the electron acceptor 2-sulphone substituent.     

New Intermediates and Dyes for Synthetic–polymer Fibres 4–(4–Methoxyanilino)–3–nitro–l, 8–naphthalimides

The synthesis of a series of 4–(4–methoxyanilinoj–3–nitro–1, 8–naphthalimides by condensation of amines with 4–(4–methoxyanilino)–3–nitronaphthalene–l, 8–dicarboxylic anhydride, and also by condensation of 4–halogeno–3–nitro–1, 8–naphthalimides with 4–methoxyaniline is described. They dye synthetic–polymer fibres, particularly polyesters, deep orange of excellent fastness properties. In presence of strong bases, e. g. 3–aminopropan–l–ol, the 4–arylamino group is replaced, giving a series of yellow dyes. A method is described for preparing the dyes without isolation of intermediate stages.     

Novel yellow azo–anthraquinone dyes for polylactide fibres: effects of alkyl chain length

1‐(4′‐Alkylaminosulphurylphenyl)‐3‐methyl‐5‐pyrazolonyl azo–anthraquinone dyes were prepared in four steps from 1‐aminoanthraquinone, as an approach to enhancing the exhaustion levels of disperse dyes on polylactide fibres. Their structures were confirmed from combustion analysis and mass spectrometry, infrared and proton nuclear magnetic resonance spectroscopy. Results from artificial intelligence‐based molecular modelling studies showed that increasing alkyl chain length gave an increase in LogP, molecular volume and aplanar shape. Their application to polylactide fibres led to both good per cent exhaustion values and good light fastness ratings. It was also found that the nature of the alkyl chains attached to the phenyl ring had little influence on dye colour, but clearly influenced per cent exhaustion and wash fastness.     

Derivatives of 4-amino-2-nitrodiphenylamine as dyes for synthetic polymer fibres

The synthesis of a series of substituted 4-amino-2-nitrodiphenylamines is described. These compounds dye synthetic polymer fibres in bordeaux to violet-blue shades of moderate to poor light fastness. Light fastness properties are enhanced by the use of substituents which decrease the basicity of the 4-amino group; such substitution, however, results in colour shifts into the yellow to orange region.     

Synthesis and application of yellow azo‐anthraquinone disperse dyes for polylactide fibres

1‐Phenyl‐3‐methyl‐5‐pyrazolonyl azo‐anthraquinone dyes having high light fastness on polylactide fibres were synthesised from 1‐aminoanthraquinone via a diazotisation‐coupling reaction with 1‐phenyl‐3‐methyl‐5‐pyrazolones. The structures of these new dyes were confirmed using mass spectrometry, infrared and proton nuclear magnetic resonance spectroscopy and combustion analyses. Their dyeing behaviour on polylactide fibres was also determined, whereupon it was found that the title dyes could be applied at a relatively low dyeing temperature and that the corresponding dyed fabrics had good fastness properties.     

7H-pyrazolo[5, 1-a]benz[d,e]isoquinolin-7-ones: Yellow to orange dyes for synthetic-polymer fibres

N-Amino-1,8-naphthalimides were condensed with ketones containing an α-methylene group and the resulting hydrazones ring closed to afford derivatives of 7H-pyrazolo(5,1-a)benz(d,e)isoquinolin-7-one. These compounds coloured synthetic-polymer fibres, particularly polyester, in brilliant fluorescent greenish-yellow to orange hues of good fastness to light and sublimation. The colour of the dyes is discussed with respect to substituent effects in the pyrazole and naphthalene rings, and in relation to analogous 7H-benzimidazo(2,1-a)benz(d,e)isoquinolin-7-ones.     

Heterocyclic hansa yellow analogues: Synthesis of novel azodisperse dyes from 3-oxo-N-(pyrazol-4-yl) butanamide as possible dyes for polyester fibres

Different heterocyclic Hansa Yellow analogues were synthesized from 3-oxo-N-(pyrazol-4-yl)butanamide for possible use as azodisperse dyes for dyeing polyester fibres. The free energy relationship between the position of absorption of these dyes-λ-and substituent Hammett sigma constants was investigated.     

1-Amino-4-hydroxyanthraquinone-β-ethers and thioethers: Red dyes for synthetic-polymer fibres

Condensation of 1-amino-2-bromo-4-hydroxyanthraquinone and of 1-amino-3-bromo-4-hydroxyanthraquinone with alcohols, phenols and thiols yields the corresponding β-ethers and thioethers. These compounds colour polyester in deep rose-red to violet-red hues of excellent build-up and good fastness to light and sublimation. The colour of the dyes is discussed with respect to the nature and orientation of the β-substituents.     

Properties of Monoazo Disperse Dyes,Derivatives of 3– and 4–Aminophthalimide

The synthesis of several disperse dyes, from 3–amino–12–phthalimide and its N–methyl derivative as diazo component and N, N–dialky lanilines as coupling component is described. The dyeing behaviour and some physical properties of these dyes are investigated and compared with those of isomeric dyes containing azo groups in the 4–position, previously studied [5]. These properties were found to be considerably affected by the presence of an alkyl sub–stituent on the nitrogen atom of imide group. Further, dyes containing unsubstituted –NH groups showed somewhat better thermal properties (higher melting points and dyeings of better fastness to sublimation), but at the same time their dyeability was worse for all the known processes of dyeing polyester fibres. Based on the i. r. and visible spectra of the dyes under investigation, it was concluded that the dyes containing unsubstituted –NH groups are highly associated; dyes containing azo groups in the 4–position associate to give one product, whereas association of the dyes with azo groups in the 3–position leads to two different products.     

Substituent Effects on the Colour,Dyeing and Fastness Properties of Trisubstituted 4–N–β–Hydroxyethyl–N–β–Cyanoethylaminoazobenzenes

School of Chemistry and Chemical Technology University of Bradford Bradford West Yorkshire BD7 1DP The synthesis of a series of 2′, 4′, 6′-trisubstituted derivatives of 4–N–β–hydroxyethyl–4– N–β–cyanoeth ylaminoazobenzene is reported, and the effect of the nature of the substituents on the colour, dyeing and fastness properties of these dyes is described. The dyes coloured synthetic–polymer fibres well, with the exception of those containing a methylsulphonyl group, which gave weaker dyeings on polyester. Dyes substituted by 2′-nitro groups tended to have poor light fastness, and reasons for the variations in the light fastness of monoazo dyes of this type are discussed.     

Laser Raman studies of α–bromoacrylamide reactive dyes and wool

The use of laser Raman spectroscopy in the investigation of interactions in α–bromoacrylamide reactive dye–wool fibre systems has been established. The spectra obtained (in particular using C. I. Reactive Red 84) provide some evidence to support the proposal that the dye reacts via addition at the double bond of the reactive group, followed by ring closure through nucleophilic substitution. Furthermore, preliminary studies of the effect of the commercial levelling assistant Albegal B on the aqueous dye environment have been made using C. I. Reactive Yellow 39. The results show that, whilst the primary interaction between the dye and auxiliary may be via the water–solubilising sulphonate groups of the dye, hydrophobic interactions are also important.     

Tangentially Coupled π Systems and their Through-Space Interaction – trichromophoric perylene dyes

Three perylene tetracarboxylic bisimide chromophores have been attached to a benzene ring in m-position ( 3 ). In this way steric and through-bond interactions of the chromophores are minimized and their through-space-interactions can be studied for which an unusually high bathochromic shift has been found. This indicates a destabilization. No exciton coupling has been observed in the trichromophoric dyes.     

Synthesis of pyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles and pyrazolo[4′,3′:5,6]pyrazino[2,3-d]pyrimidines and their application to polyester fibres

4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied.     

Oxidative Gold Catalysis Meets Photochemistry – Synthesis of Benzo[a]fluorenones from Diynes

Diynes bearing one terminal and one triarylmethyl‐substituted alkyne were converted into complex benzofluorenone derivatives via a one‐pot process involving a gold‐catalyzed step followed by a photocyclization/oxidation. In the first step an N‐oxide was used to position‐selectively generate an α‐oxo carbenoid at the terminal alkyne which after a regioselective 1,6‐carbene transfer along the tethered tritylalkyne and a subsequent aryl 1,2‐shift furnished tetraphenylethylene‐like derivatives. These intermediates were successfully transformed to fluorenones via oxidative photocyclization.

     

Preparation and electrorheological characteristics of β‐cyclodextrin–epichlorohydrin–starch polymer suspensions

Three environment friendly β‐cyclodextrin polymer electrorheological (ER) particles (NS‐β‐CDP, WSS‐β‐CDP, and CLS‐β‐CDP) were synthesized by copolymerization through a mixture of β‐cyclodextrin (β‐CD) and epichlorohydrin in the absence of starch or in the presence of water‐soluble and water‐insoluble starch, respectively. The electrorheological properties of suspensions in silicone oil were then investigated under direct current (dc) electric fields. It was found that the yield stress of the typical WSS‐β‐CDP ER fluid was 6.2 kPa in 4 kV/mm, which is 35% higher than that of NS‐β‐CDP and similar to that of CLS‐β‐CDP. In the meantime, it can display a high ER performance even over a range of 65–95°C. The structures of these polymers were characterized by FT‐IR and Raman spectrometry, respectively. The results demonstrated that all of these polymers keep the original structural character of β‐CD and the copolymerizations between starch and β‐CD indeed occur. Furthermore, it was found that there was some relationship between the characteristic strength of polymers and their dielectric properties. Hence, the improvement of copolymer dielectric properties resulted in the enhancement of ER effects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1681–1686, 2004     

Intermediates and dyes for synthetic-polymer fibres. Benzo [b]naphtho [3,2-d]thiophene-6,7-dicarboxylic acid imides and benzimidazo dibenzothio

Benzo[b]naphtho[2,3-d]thiophene-6,7-dicarboxylic anhydride (I) is obtained y Pschorr intramolecular cyclisation of 2-(2-aminophenylthio)-1,8-naphthalic anhydride. Condensation with alkylamines and arylamines gives the corresponding imides, which colour synthetic-polymer fibres in greenish-yellow hues, and reaction with o-phenylenediamines affords the isomer mixtures of derivatives of benzimidazo[1,2-b]-dibenzothiopheno-[4,3,2-d,e] isoquinolin-10-one and of benzimidazo-[2,1-a] dibenzothiopheno-[4,3,2-d,e]isoqumolin-10-one, which dye polyester fibres bright reddish-orange. Both series of dyes have excellent fastness to light and sublimation. The colour of the dyes is discussed in relation to the isomeric compounds derived from benzo[k,1]thioxanthene-3,4-dicarboxylic anhydride (III) and from benzo[d]naphtho[1,2-b]thiophene-9,10-dicarboxylic anhydride (II). The synthesis of the individual isomers resulting from reaction of I with o-phenylenediamine is reported and their absorption maxima related to polar factors operative within each isomer.     

Thermodynamic Analysis on the Codeposition of SiC–Si3N4 Composite Ceramics by Chemical Vapor Deposition using SiCl4–NH3–CH4–H2–Ar Mixture Gases

A thermodynamic calculation on the chemical vapor deposition of the SiCl₄–NH₃–CH₄–H₂–Ar system was performed using the FactSage thermochemical software databases. Predominant condensed phases at equilibrium were SiC, Si₃N₄, graphite, and Si. The equilibrium conditions for the deposition of condensed phases in this system were determined as a function of the deposition temperature, dilution ratio (δ), and reactant ratios of CH₄/SiCl₄ and NH₃/SiCl₄. The CVD phase diagrams were used to understand the reactions occurring during the formation of Si–C–N from the gas species and determine the area of SiC–Si₃N₄. The concentration of condensed‐phase products was used to determine the deposition conditions of CVD SiC–Si₃N₄. The present work was helpful for further experimental investigation on CVD Si–C–N.     

Operational Inhomogeneities in La0.9Sr0.1Ga0.8Mg0.2O3–δ Electrolytes and La0.8Sr0.2Cr0.82Ru0.18O3–δ–Ce0.9Gd0.1O2–δ Composite Anodes for Solid Oxide Fuel Cells

The electrolyte/anode interface in solid oxide fuel cells with La_0.9Sr_0.1Ga_0.8Mg_0.2O_3–δ electrolytes and composite anodes containing La_0.8Sr_0.2Cr_0.82Ru_0.18O_3–δ and Ce_0.9Gd_0.1O_2–δ (GDC) was studied using transmission electron microscope Z‐contrast imaging and energy dispersive X‐ray spectroscopy. The anode/electrolyte interface of an operated cell had numerous defective regions in the electrolyte, immediately adjacent to anode GDC particles. These areas had a different chemical composition than other electrolyte regions and were crystallographically inhomogeneous. These regions were not observed in a cell reduced in hydrogen that was not operated, suggesting that they were the result of combined electrical and chemical potential gradients present during cell operation. Ru nanoparticles were observed on the chromite surfaces of the operated.     

1,5-Dihydroxy-4,8-diamino- and 1,8-dihydroxy-4,5-diaminoanthraquinone-β-ethers and thioethers. Blue dyes for synthetic polymer fibres

Condensation of mono- and di-bromo-derivatives of 1,5-dihydroxy-4,8-diaminoanthraquinone and of 1,8-dihydroxy-4,5-diaminoanthraquinone with phenols and thiols afforded the corresponding β-ethers and thioethers. These compounds coloured polyester in bright reddish-blue to greenish-blue hues of generally good fastness to light and sublimation. The colour of the dyes is discussed with respect to the nature and orientation of the β-substituent.