Reaction of 5-Amino-2,3-dicyano-1,4-naphthoquinone with Arylamines

The reaction of 5-amino-2,3-dicyano-1,4-naphthoquinone (1) with arylamines gave 5-amino-8-arylamino- (2), 5,8-bis(arylamino)- (3), and 5-hydroxy-8-arylamino-2,3-dicyano-1,4-naphthoquinone (4) together with 5-amino-2-arylamino-3-cyano- (5) and 5-amino-2-cyano-3-aryl-amino-1,4-naphthoquinone (6). It is proposed that the initial quinone-quinoneimine tautomerism of 1 to 4-hydroxy-2,3-dicyano-5-imino-1,5-naphthoquinone 7 facilitates the 8-arylamination. Some derivatives of 2 have good properties as dyes for optical information-recording media for semiconductor lasers.     

The chlorination of 1,4-dihydroxyanthraquinone with thionyl chloride

The chlorination of 1,4-dihydroxyanthraquinone (quinizarin) using thionyl chloride yielded three different products, depending on the purity of the starting material and catalysts used. The compounds isolated were 9-chloro-10-hydroxy-1,4-anthraquinone (3a), 2,4-dichloro-1-hydroxy-anthraquinone (2) and the new compound 1-hydroxy-4-(4-hydroxy-anthraquinone-1-oxy)-anthraquinone (4a). Some acylated derivatives of 3a and of 4a are reported.     

Design,synthesis, antibacterial and antifungal activity of novel spiro-isoxazolyl bis-[5,5′]thiazolidin-4-ones and spiro-isoxazolyl thiazolidin-4-one-[5,5′]-1,2-4 oxdiazolines

The synthesis of novel isoxazolyl 1,6-dithia-4,9-diazaspiro[4.4]nonane-3,8-diones (4a–h) and isoxazolyl 1-oxa-6-thia-2,4,9-triazaspiro[4.4]non-2-ene-8-ones (5a–h) analogs is described. Reaction of N-1-\{3-methyl-5-[(E)-2-aryl-1-ethenyl]-4-isoxazolyl}-2-chloroacetamide (2) with aryl isothiocyanates yielded 3,3-methyl-5-[(E)-2-aryl-1-ethenyl]-4-isoxazolyl-2-(arylimino)-1,3-thiazolan-4-ones (3). Cyclocondensation of 3 with mercaptoacetic acid furnished novel isoxazolyl-1,6-dithia-4,9-diazaspiro[4.4]nonane-3,8-diones (4a–h). Cycloaddition of 3 with benzonitrile oxides afforded novel isoxazolyl 1-oxa-6-thia-2,4,9-triazaspiro[4.4]non-2-ene-8-ones (5a–h). Compounds 4a–h and 5a–h showed significant biological activity against all the standard strains.     

Synthesis and structure of new alkynyl derivatives of phenothiazine and phenoxazine

New alkynyl derivatives of phenothiazine and phenoxazine were obtained via Sonogashira cross-coupling reactions. This was achieved by first synthesizing the intermediates 6-chloro-5H-benzo[a]phenothiazin-5-one, 6-chloro-5H-benzo[a]phenoxazin-5-one and 6-chloro-5H-naphtho[2,1-b]pyrido[2,3-e][1,4]oxazin-5-one by anhydrous base-catalyzed condensations between 2,3-dichloro-1,4-naphthoquinone and 2-aminothiophenol, 2-aminophenol and 2-aminopyridinol, respectively .The cross-couplings of these electron-rich chlorophenothiazine and chlorophenoxazine intermediates with terminal alkynes, employing 4?mol% Pd and 7?mol% XPhos in the presence of base in acetonitrile at 80°C, afforded the highly colored alkynylated derivatives in good yields. These reaction conditions allowed the incorporation of both unprotected N-H and carbonyl groups. Structural assignments were established by spectroscopic (UV, IR, ¹H and ¹³Cnmr), ms and elemental analytical data.     

Dyes for synthetic-polymer fibres: 14H-naphtho[2,3-a]phenothiazine-8,13-diones I72 I72 V 3 and 1H-2,3-dihydroanthra[2,1-b][1,4]-thiazine-7,12-diones I72 I72 V 3

Condensation of 1-amino- or 1-hydroxy-2-bromoanthraquinones with 2-amino-benzenethiol, or of 1-amino-2-bromoanthraquinones with 2-nitrobenzenethiol I72 I72 V 3 gives 14H-naphtho[2,3-a]-phenothiazine-8,13-diones. The related 1H-2,3- I72 I72 V 3 dihydroanthra[2,1-b][1,4]thiazine-7,12-diones result from interaction of 1- I72 I72 V 3 amino-2-mercaptoanthraquinones with 1,2-dibromoethane or of 1-hydroxy-2- I72 I72 V 3 bromoanthraquinones with 2-aminoethanethiol. The colour, dyeing and fastness I72 I72 V 3 properties of these compounds on synthetic-polymer fibres are described. I72 I72 V 3     

Dyes for synthetic-polymer fibres: I72 I72 V 2 14H-naphtho[2,3-a]phenothiazine-8,13-diones I72 I72 V 3 and 1H-2,3-dihydroanthra[2,1-b][1,4]-thiazine-7,12-diones I72 I72 V 3

Condensation of 1-amino- or 1-hydroxy-2-bromoanthraquinones with 2-amino-benzenethiol, I72 I72 V 2 or of 1-amino-2-bromoanthraquinones with 2-nitrobenzenethiol I72 I72 V 3 gives 14H-naphtho[2,3-a]-phenothiazine-8,13-diones. The related 1H-2,3- I72 I72 V 3 dihydroanthra[2,1-b][1,4]thiazine-7,12-diones result from interaction of 1- I72 I72 V 3 amino-2-mercaptoanthraquinones with 1,2-dibromoethane or of 1-hydroxy-2- I72 I72 V 3 bromoanthraquinones with 2-aminoethanethiol. The colour, dyeing and fastness I72 I72 V 3 properties of these compounds on synthetic-polymer fibres are described. I72 I72 V 3     

Heterocyclic quinones. XVI. The Reaction of acid Amides with 2,3- Dichloro-1,4-naphthoquinone,a novel route to naphth[2,3-d]oxazole-4,9-diones

Heating acid amides 2 with 2,3-dichloro-1,4-naphthoquinone 1 in solvents like glycerol or ethylene glycol gave readily naphth [2,3-d] oxazole-4,9-diones 4 . The reaction was enhanced by addition of catalytic amounts of sodium hydrogencarbonate, but failed to proceed at all when attempted in low boiling polar or nonpolar solvents. 2-Amido-3-chloro-1,4-naphthoquinones 3 were produced as intermediates in these reactions.     

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.     

GLYCEROL CONDENSATION PRODUCTS OF AMINOANTHRAQUINONES

Glycerol condensation reaction of 2- and 1-aminoanthraquinones was reexamined. 2-Aminoanthraquinone gave phenaleno[3,2-f]quinolin-7-one (10,11-pyridinobenzanthrone), 9H- phenanthro[10,1-gh]quinolin-9-one (4,5-pyridinobenzanthrone) and phenaleno[2,3-g]quinolin-7-one (10,9-pyridinobenzanthrone) besides phenaleno[2,3-f]quinolin-13-one (9,8-pyridinobenzanthrone) hitherto reported. 1-Aminoanthraquinone gave phenaleno[3,2-h]quinolin-13-one (8,9-pyridinobenzanthrone) along with a small amount of phenaleno[2,3-h]quinolin-7-one (11,10-pyridinobenzanthrone), but not 13H-phenanthro[1,10-gh]quinolin-13-one (6,5-pyridinobenzanthrone) as hitherto reported. NMR spectra of these six compounds were assigned and they supported the assigned isomeric structures.     

气相色谱-质谱联用法对3-氯亚氨基二苄中杂质的研究

应用气相色谱-质谱联用方法研究3-氯亚氨基二苄中的杂质。在30.0m×0.25mm,0.5μm的ZB-5MS毛细管柱上,柱温100°C保持3min,后以20°C/min的速率程序升温至250°C,气化室温度270°C,载气氦气流量0.8mL/min的条件下,3-氯亚氨基二苄及其中杂质获得很好分离。通过对各组分质谱图分析,并结合反应过程确定了3-氯亚氨基二苄中的四种杂质分别为亚氨基二苄,甲基亚氨基二苄酮,10-氯-5H-二苯并[b,f]氮杂和3,7-二氯-10,11-二氢-二苯并[b,f]氮杂。     

Novel magnesium and zinc porphyrazines containing galactose moieties: Synthesis via click reaction and characterization

In this study, galactose conjugated new magnesium and zinc porphyrazines were synthesized by the cyclotetramerization reaction of 2,3-bis[1-(2,2,7,7-tetramethyltetra-hydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5,methyl)-1H-[1,2,3]triazol-4-yl methylsulfanyl]-but 2-enedinitrile. This substituted dicyano compound was prepared via two different routes. One started from cis-1,2-dicyano-1,2-ethylenedithiolate disodium, [1-(2, 2, 7,7-tetramethyltetrahydrobis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5-yl-methyl)-1H-[1,2,3]triazo-l-4-yl]methanol and ended in a multi-step reaction sequence via Click procedures. The other reaction was between 5-azidomethyl-2,2,7,7-tetramethyltetrahydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran and (2Z)-2,3-bis(prop-2-yl-1-yl-thio)but-2-enedinitrile. A very soluble galactose linked magnesium porphyrazine derivative in common polar solvents and water was achieved by the deprotected isopropylidene groups in TFA and water media. It is first time, zinc porphyrazine complex has been achieved at one-step reaction by using Zn(BuO)₂ as template agent. The new compounds have been characterized by a combination of elemental analysis, ¹H, ¹³C NMR, IR, UV–vis and MS spectral data.     

Synthesis of Thiazolo(4,5-b)-quinoxalines and related compounds

The reaction of 2,3,7-trichloroquinoxaline ( 1 ) or 2,3-dichloro-7-bromoquinoxaline ( 2 ) with thiourea in DMSO gave 6,6′-dichloro- or 6,6′-dibromodiquinoxalino[2,3-b:2′:3′-e]1,4-dithiien ( 3 or 4 ). However, 1 or 2 reacts with thiourea in ethanol to give ( 3 or 4 ) beside 7-chloro- or 7-bromo-2-imino-2,3-dihydrothiazolo[4,5-b] quinoxaline ( 5 or 6 ) respectively. Interaction of 1 or 2 with acetone thiosemicarbazone gave 7-chloro- or 7-bromo-3-amino-2-imino-2,3-dihydro-thiazolo[4,5-b] quinoxaline hydrochloride ( 13 or 14 ) respectively. Cyclization of 7-chloro- or 7-bromo-3-amino-2-imino-2,3-dihydrothiazolo[4,5-b]quinoxaline ( 15 or 16 ) on treatment with aromatic acid chlorides or isothiocyanates succeeded to give 19—21 or 28 and 29 .     

The synthesis and characterization of novel metalloporphyrazine containing crown ether linked calix[4]arene moieties

The synthesis and characterization of novel magnesium porphyrazine, peripherally symmetrically derived from 1,3-alternate 26,28-[35,36-dicyano-34,37-dithia-29,32,40,43-tetraoxa-35-en]calix[4]arene-crown-5, were carried out. This compound was prepared starting from cis-1,2-dicyano-1,2-ethylenedithiolate and 1,3-alternate 26,28-bis(5′-chloro-3′-oxapentyloxy)calix[4]arene-crown-5. The new macrocycle was characterized using the techniques of UV–vis, ¹H, ¹³C NMR, IR, MS and elemental analysis.     

A new low-voltage-driven polymeric electrochromic

Design, synthesis, and properties of a novel donor-acceptor-donor type low-voltage-driven green polymeric electrochrome, P1, which is based on 8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-11-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)acenaphtho[1,2-b]quinoxaline (1) are highlighted. It is noted that P1 has an ambipolar (n- and p-doping processes) character in 0.1 M tetrabutylammonium hexafluorophosphate/dichloromethane solution and switches to a transmissive blue state upon oxidation. Furthermore, this new polymeric electrochromic candidate exhibits high redox stability, high coloration efficiency and/or contrast ratio, high percent transmittance (%T) and low response time (1.0 s) with a band gap of 1.10 eV-1.25 eV.     

Ring closure reaction of 5-hydroxy-pyrido[2,3-d]pyrimidine-2,4,7-triones to benzo[b]pyrimido[4,5-h]1,6-naphthyridine-1,3,6-triones

N-Substituted aminouracils ( 1 ) react with malonates by cyclocondensation to 5-hydroxy-pyrido[2,3-d]pyrimidine-2,4,7-triones ( 2 ), which give with triethylorthoformate and aniline 6-(phenylaminomethylene)-pyrido[2,3-d]pyrimidine-tetraone ( 3 ). Halogenation of 2a - d (with R² = Me) with phosphorylchloride leads to 5,7-dichloro-pyrido[2,3-d]pyrimidine-2,4-diones ( 4 ) by cleavage of the methyl group at N-8, whereas Vilsmeier reaction of 2 affords 5-chloro-6-formyl derivatives ( 6 ), which cyclize with arylamines to give benzo[b]pyrimido[4,5-h] 1,6-naphthyridines ( 9 ). Compounds 9 were obtained independently by amination of the tosylates 5 to the 5-arylamino compounds 8 , and Vilsmeier formylation to yield 9 .     

Synthesis of bispiroheterocyclic systems as antimicrobial agents via the reaction of 2-(cycloalkylidene)-1-thia-4-azaspiro[4.4]-nonan-3-one and/or [4.5] decan-3-one with hydrazines,hydroxylamine, urea and thiourea derivatives

1-Oxa-4-thiaspiro[4.4]nonan-2-one ( 1 ) and/or 1-oxa-4-thiaspiro[4.5]-decan-2-one ( 2 ) reacted with 1-naphthylamine to afford 1-thia-4-(1-naphthyl)-4-azaspiro[4.4]nonan-3-one ( 3 ) and/or 1-thia-4-(1-naphthyl)-4-azaspiro[4.5]decan-3-one (4). Reactions of 3 and/or 4 with cyclopentanone or cyclohexanone gave the corresponding 2-cycloalkylidene-4-(1-naphthyl)-1-thia-4-azaspiro[4.4]nonan-3-ones ( 5 and 6 ) and 2-cycloalkylidene-4-(1-napthyl)-1-thia-4-azaspiro[4.5]-decan-3-ones ( 7 and 8 ). Reaction of compounds 5 – 8 with hydrazine hydrate, phenylhydrazine, hydroxylamine hydrochloride, urea and thiourea afforded the corresponding bispirothiazolopyrazolines ( 9 – 16 ), bispirothiazoloisoxazolines ( 17 – 20 ), bispirothiazolopyrimidinones ( 21 – 24 ) and bispirothiazolothiopyrimidinones ( 25 – 28 ) respectively. All the synthesized bispiroheterocyclic derivatives were identified by conventional methods (IR, ¹H-NMR) and elemental analyses. All the prepared compounds were tested for their antimicrobial activities in comparison with tetracycline as a reference compound.     

Synthesis of oligoethylene glycol ethers from the seed oil of Vernonia anthelmintica

The seed oil of Vernonia anthelmintica on reaction with diols (mono-, di-, tri-, or tetraethylene glycols) in the presence of boron trifluoride etherate, followed by saponification and esterification (methanol/H⁺), gives the oligoethylene glycol ethers: methyl 12(13)-hydroxy-13(12) [2-hydroxy-ethyl-1-oxy]-octadec-9-enoate; methyl 12(13)-hydroxy-13(12)-[5-hydroxy-3-oxapentyl-1-oxy]-octadec-9-enoate; methyl 12(13)-hydroxy-13(12)-[8-hydroxy-3,6-dioxaoctyl-1-oxy]-octadec-9-enoate; and methyl 12(13)-hydroxy-13(12)-[11-hydroxy-3,6,9-trioxaundecyl-1-oxy]-octadec-9-enoate. Methyl 12,13-dihydroxyoctadec-9-enoate is a co-product in all reactions.     

Tuning of the neutral state color of the π-conjugated donor-acceptor-donor type polymer from blue to green via changing the donor strength on the polymer

Two donor-acceptor-donor types of π-conjugated monomers were synthesized using Stille coupling reaction. Both monomers were found to produce electroactive polymers upon electrochemical oxidation. The effects of different donor substituents on the polymers' electrochemical and spectroelectrochemical properties were examined. Optical characterization revealed that the band gaps of poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5,8-di(thiophen-2-yl)quinoxaline) (PDBQTh) and poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)quinoxaline) (PDBQEd) were 1.5 eV and 1.3 eV, respectively. PDBQEd reveals two distinct absorption bands as expected for this type of donor-acceptor-donor polymer at 423 and 738 nm, while PDBQTh has a single absorption band at 630 nm. The colorimetry analysis revealed that while PDBQTh has a blue color, PDBQEd showed a green color in the neutral state. PDBQEd revealed reversible n-doping.     

Synthesis and antimicrobial activity of fatty 2-morpholinones prepared from epoxy fatty acid methyl esters

Reactions of methyl 10,11-epoxyundecanoate (I), methyl 9,10-epoxyoctadecanoate (II) methyl 12,13-epoxy-cis-9-octadecenoate (III) and methyltrans-2,3-epoxyhexadecenoate (IV) with glycine in dimethylformamide (DMF) in the presence of anhydrous AlCl₃ as catalyst have yielded 5(6)-[8′-carbomethoxyoctyl]-2-morpholinone (V); 5(6)-[7′'-carbomethoxyheptyl]-6(5)-octyl-2-morpholinone (VI);5(6)-[10′-carbomethoxydec-cis-2-enyl)-6(5)-pentyl-2-morpholinone (VII), and 5-tridecyl-6-carbomethoxy 2-morpholinone (VIII), respectively in excellent yield. The products have been characterized with the help of spectral data and microanalysis. Antifungal and antibacterial screening of (V–VIII) showed pronounced activity against four bacteria and seven fungal species. Presented in part at the 43rd Annual Convention of the Oil Technologists' Association of India (OTAI) held in Bombay, India In February 1988.     

Quinoxaline derivatives as long wavelength photosensitizers in photoinitiated cationic polymerization of diaryliodonium salts

The present paper is focused on visible light initiated cationic polymerizations. Photoinitiated polymerization of representative vinyl ether and oxirane monomers using two quinoxaline derivatives; namely (2-(2,3-dihydrobenzo [b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b]-[1,4]dioxin-7-yl)-5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7yl) quinoxaline) (DBQEd) and 2,3,5,8-tetra(thiophen-2-yl)quinoxaline (TTQ) are studied. Novel dyes based on the quinoxaline skeleton are employed as efficient photosensitizers in cationic photopolymerizations. Polymerizations were initiated at room temperature upon irradiation with long-wavelength UV and visible lights in the presence of diphenyliodonium hexafluorophosphate (Ph₂I⁺PF₆^?). The progress of the polymerizations was monitored by optical pyrometry (OP). Solar irradiation is also employed to carry out the cationic polymerization of a diepoxide monomer in the presence of air.