1,4-Dihydroxyanthraquinone-2-carboxamides and 2,3-dicarboximides. Orange dyes for synthetic polymer fibres

Hydrolysis of 1,4-dihydroxy-2,3-dicyanoanthraquinone gives 1,4-dihydroxyanthraquinone-2,3-dicarboxylic anhydride, reaction of which with alkylamines and arylamines gives either the 2-carboxamide or 2,3-dicarboximide derivatives. These compounds colour polyester in brownish-orange hues having good light fastness. The colour of the dyes is discussed in relation to other 2-substituted derivatives of 1,4-dihydroxyanthraquinone.     

Synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans

The synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans was undertaken because these compounds incorportae the essential structural features of certain 2,3-diphenyl-benzofurans and 1,2,3-triphenylalkanones reported earlier to have marked antifertility activity. The synthesis of the 2 tetrahydrofurans was achieved by the cyclization of corresponding 2,3,4-triphenylbutane-1,4-diols upon heating with dimethyl sulfoxide (DMSO). The butane 1,4-diols were in turn prepared either by direct litium aluminum hydride (LAH) reduction of methyl 3-benzoyl-2,3-diphenylpropionates or by conversion of these propionates to delta-3,4-butryrolactones followed by LAH reduction. The propionates were prepared from the Fiedel-Crafts reaction of 2,3-diphenylsuccinic anhydride with benzene. Tetrahydrofurans were tested for their antiimplantation activity in rats. 2,3-trans-3,4-cis-2,4-diphenyl-3-p -(beta-pyrrolidinoethoxy) phenyltetrahydrofuran oxalate was found to inhibit implantation completely at 50 mg/kg, but was inefective at a lower dose.     

An unusual route to 1,4-diphenyl-2,3-dimethylbutadiene-1,3

Summary Treatment of 2,3-dimethyl-2,3-diphenylbutanediol-1,4-ditosylate with tetra-n-butylammonium bromide in dimethyl-acetamide did not give the expected 2,3-dimethyl-2,3-diphenyl-1,4-dibromobutane but, rather, by a double phenonium ion rearrangement, 1,4-diphenyl-2,3-dimethylbutadiene-1,3. 2,3-Dimethyl-2, 3-diphenyl-1,4-dibromobutane was required as starting material for the synthesis of head to head poly(-methyl-styrene) by Grignard coupling.This communication is Part XXX of Head to Head Polymers. Part XXIX: M.Malanga and O. Vogl, Acta Polymerica, in press.     

Syntheses of Cyclic Hydroxamic Acids and Lactams with 2,3-dioxo-1,4-benzoxazine skeleton

Ethyl 2-nitrophenyl oxalate ( 1 a ) and its 5-methoxy derivative ( 1b ) were subjected to catalytic hydrogenations over 3% Pt (S) on carbon in different solvents. Thus, hydrogenation in acetic acid yielded 4-hydroxy-2,3-dioxo-1,4-benzoxazine ( 2a ) and its 7-methoxy derivative ( 2b ) by reductive cyclization, the dehydro forms of the naturally occurring cyclic hydroxamic acids DIBOA and DIMBOA from Gramineae. In contrast, hydrogenation of esters 1 in methanol results in the formation of amides 3 by acyl group migration. On heating, amides 3 undergo lactonization to form lactone-lactames 4 , which in turn undergo ring opening to give amides 3 when refluxed in ethanol.     

Untersuchungen zur Chemie von 3-Chlormethyl-3-methyl-2,3-dihydro-1,4-benzoxathiinen

Investigations on the Chemistry of 3-Chloromethyl-3-methyl-2,3-dihydro-1,4-benzoxathiines A series of 3-chloromethyl-2,3-dihydro-1,4-benzoxathiines 3 were prepared by the reaction of several β-methallylphenylethers 1 with sulfur dichloride. In some cases intermediate sulfenyl chlorides 2 were isolated and characterized as substituted thiazolidin-2-ones. The thermal regioisomerization of selected sulfenyl chlorides and one of the thiazolidinone products was achieved. Starting from 3-chloromethyl-2,3-dihydro-1,4-benzoxathiine 3o several derivatives were obtained by nucleophilic displacement at the 3-chloromethyl position, activated by S-3-neighboring group partizipation. The structure of the 3-acetoxymethyl derivative was determined by x-ray crystal structure analysis. Further special derivation with selected chiral reagents led to diastereomeric compounds. The separation of the diastereomers by crystallization and chromatography was attempted. HPLC-separation was achieved in one case.     

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.     

6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌的合成

6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌对肿瘤细胞有一定的抑制作用,研究其新的合成方法具有较重要的理论和实践意义。本文以6-(4-甲基-3-戊烯基)萘-1,4-二醌为原料,过氧化氢为氧化剂,通过环氧化反应制备了目标产物6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌。采用FT-IR、GC-MS和¹H NMR等手段对产物进行了表征,确定了产物结构。探讨了氧化剂用量、反应时间、溶剂种类和无水碳酸钠用量对反应转化率和得率的影响,得到适宜的工艺条件为:以过氧化氢为氧化剂,n(萘二醌):n(过氧化氢):n(无水碳酸钠)=1:8:0.5,溶剂为乙醇,反应温度为30℃,反应时间为2h。在上述条件下,产物得率为83.9%。     

Zur Molekülverknüpfung mit Schwefelchloriden. IX. Reaktion von Schwefeldichlorid mit N-Allyl-anilinen. Eine Synthese für 2-Chlormethyl-2,3-dihydro-1,4-benzothiazine

Molecule Linkage by Sulfur Chlorides. IX. The Addition Reaction of Sulfur Dichlorides with N-Allyl-anilines. A Synthesis for 2-Chloromethyl-2,3-dihydrobenzo-1,4-thiazines Reactions of different substituted N-allyl-anilines 1 with sulfur dichloride yield 2-chloromethyl-2,3-dihydrobenzo-1,4-thiazines 3a – i . The identification of the products was carried out by mass spectroscopy and ¹H-n.m.r.-spectroscopy. The seven-membered cyclic isomers of the S, N-heterocycles 3 , dihydro-benzo-1,5-thiazepanes 5 were not obtained.     

8种新型7胺-基取代的1,4二-氢-3H-2,3苯-并噁嗪-3甲-酸乙酯衍生物的合成

1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯经过硝化、还原和重氮化溴代得到了7溴--1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯(C)。以Pd(OAc)2/R(+)B INAP(2,2′-二苯膦-1,1′-联萘)为催化体系,C与苯胺、N-甲基苯胺、对氟苯胺、对乙氧基苯胺、环己胺、吗啡、四氢吡咯及六氢吡啶等8种有机胺类化合物(Am ine1~8),在氮气保护下,以碳酸铯为碱于干燥的甲苯中100℃反应16~24 h,生成了相应的8种新的7胺-基取代的1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯类化合物(D1~8),反应收率分别为83%、85%、71%、90%、72%、63%、75%和83%。通过1HNMR、质谱和元素分析对这些化合物的结构进行了表征。     

Bisaxially Substituted 2,3-Naphthalocyaninatoiron Compounds

2,3-Naphthalocyaninatoiron(II) (2,3-NcFe) ( 1 ) is reacted with L = 1,4-diisocyanobenzene (dib), tert-butylisocyanide (t-buNC), cyclohexylisocyanide (c-hxNC), benzylisocyanide (bzNC), pyrazine (pyz), 4,4′-bipyridine (bpy) and pyridine (py) to form the corresponding bis-axially coordinated 2,3-naphthalocyaninatoiron(II) compounds, 2,3-NcFeL₂ 3, 4, 5, 6, 7, 8, 9. All 2,3-NcFeL₂-complexes are characterized by IR-, and if soluble enough by ¹H-NMR- and UV/VIS-spectroscopy, TG/DTA-measurements and elemental analyses. The dc-room temperature conductivities of the 2,3-NcFeL₂-complexes are measured and found to be several orders of magnitude higher than the corresponding phthalocyaninato-iron-complexes PcFeL₂.     

Synthesis of highly fluorescent coumarinyl chalcones derived from 8-acetyl-1,4-diethyl-1,2,3,4-tetrahydro-7H-pyrano[2,3-g]quinoxalin-7-one and their spectral characteristics

A series of novel coumarin based chalcones were synthesized by the classical crossed aldol condensation reaction of 8-acetyl-1,4-diethyl-1,2,3,4-tetrahydro-7H-pyrano[2,3-g]quinoxalin-7-one and various substituted benzaldehydes. These novel ketocoumarin derivatives having a 1,4-diethyl-1,2,3,4-tetrahydroquinoxaline framework exhibited brilliant fluorescence. The novel chalcones absorbed in the range of 458-523 nm in various solvents. The wavelength of maximum absorption of these chalcones was found to be significantly longer than their simple acyl derivative known in the literature. The dyes displayed longer wavelength of absorption in the high polarity solvents compared to non-polar solvents. Thermogravimetric analysis of the chalcones revealed that the chalcones possess good thermal stability.     

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     

Derivate des 2-Phenyl- und 2-Methyl-2,3-dihydro-1,4-dithiin-5,6-dicarbonsäureimids

Derivatives of 2-Phenyl- and 2-Methyl-2,3-dihydro-1,4-dithiine-5,6-dicarboxylic Acid Imide The reaction between 2-phenyl- ( A ) and 2-methyl-2,3-dihydro-1,4-dithiine-5,6-dicarboxylic acid imide ( B ), respectively, and primary aromatic amines or diamines in the presence of formaldehyde or acetaldehyde yields the α-aminoalkyl- and bis-α-aminoalkyl derivatives 1—26 . Interaction of A and B with disulfides, sulfochlorides, sulfuryl chloride, acetanhydride, acid chlorides and chloroformic acid esters affords the N-substituted compounds 27—32, 33—38, 39—40 and 41—48 , respectively. The IR spectra of the products are discussed.     

Zur Molekülverknüpfung mit Schwefelchloriden. V. Die Reaktion von Dichlorsulfan mit Allyl-phenyl-äthern. Eine Synthese für 3-Chlormethyl-2,3-dihydro-1,4-benzoxathiine durch intramolekulare Sulfenylierung

Molecule Linkage by Sulfur Chlorides. V. The Addition Reaction of Dichlorosulfane with Allyl-phenyl-ethers. A Synthesis for 3-Chloromethyl-2,3-dihydro-benz-1,4-oxathiines via Intramolecular Sulfenylation Intermediates in the reaction of dichlorosulfane (sulfur dichloride) with allylphenyl-ethers are sulfenyl chlorides (1:1 adducts). The sulfenyl chlorides with anti-Markovnikov-structure cyclize at the activated aromatic nucleus via intramolecular sulfenylation to 3-chloromethyl-2,3-dihydro-benz-1,4-oxathiines.     

Stereospecific synthesis of chiral 2,3-dihydro-1,4-benzodithiine and methyl-2,3-dihydro-1,4-benzodithiine derivatives and their toxic effects on Trypanosoma brucei

Preparation of chiral 2,3-dihydro-1,4-benzodithiine and methyl-2,3-dihydro-1,4-benzodithiine derivatives with known absolute configurations from the easily accessible chiral synthons benzyl 4-O-trifloxy-2,3-anhydro-beta-L-ribopyranoside and benzyl 4-O-trifloxy-2,3-anhydro-alpha-D-ribopyranoside is described. These compounds showed significant in vitro toxicity of the bloodstream form of Trypanosoma brucei with an IC50 of 11 microM. The parasites' energy metabolism and consumption of oxygen were found to be affected during incubation.     

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     

用于舰船防污涂料的环氧甲萘醌微胶囊的性能调控

该文以聚丙烯酸酯为囊壁,环氧甲萘醌为囊芯制备了环氧甲萘醌微胶囊,并将其应用于舰船防污涂料中。采用透射电镜(TEM)和纳米粒度仪对微胶囊形貌进行表征。考察了微胶囊核壳质量比对涂料中环氧甲萘醌渗出量及涂料防污效果的影响。结果表明,制备的环氧甲萘醌微胶囊平均粒径约为323.5 nm。环氧甲萘醌微胶囊的核壳质量比为1∶7时,制备的涂膜中环氧甲萘醌的释放速率最平稳,涂层防污效果最好。该类微胶囊的研究,为获得使用寿命长、毒性小、价格低廉的舰船防污涂料提供了新途径和新思路。     

2,3-dihydroanthra(1,2-b)(1,4)oxazine-7,12-diones. Dyes for synthetic polymer fibres

Condensation of 2-bromo-1,4-dihydroxyanthraquinone with 2-amino-2-methyl- 1,3-propanediol affords, initially, 2-(1,1-bis-hydroxymethyl)ethylamino-1,4-dihydroxyanthraquinone, which is then converted under more stringent reaction conditions into the ring closed 2,3-dihydro(1,2-b)(1,4)oxazine-7,12-dione analogue. This compound has two resolved long wavelength maxima at 20 and 60 nm longer wavelength than the uncyclised precursor and gives deep violet-red colorations of excellent fastness to light on polyester. Similar reactions with analogous aminoalcohols are also reported.     

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species

New monocyclic 1,4-diaza-2,3-diborine derivatives 3ad, 3ae and 3bc and bicyclic 1,4-diaza-2,3-diborine 8a were prepared by reacting 1,4-diaza-2,3-diene dianion (5) with 1,2-dichlorodiborane (6) and 1,2-dichloro-1,2-diborolane (7). The structures of these new derivatives, which are likely ligands for metal complexes, have been characterized by nuclear magnetic resonance (NMR). The crystal structures of 3ad and 3bc have been determined by single crystal X-ray diffraction technique. In the crystal structure of 3ad, the asymmetric unit contains one-half of the molecule, with the other half generated by (x,y,3/2-z) symmetry operation. Considering the X-ray crystallographic results of these compounds, the B–B bonds are typical for single bonds, with the bond lengths of 1.700 and 1.697 Å. Optimized geometric results and Natural Bond Orbital analysis also endorsed that these bond types are single bonds. In 3ad, diazadiborine ring is almost planar, while this ring is in half-chair conformation in 3bc. These compounds, although many aminoboranes are stable in air, were observed not to be stable in air. They have also shown non-aromatic characteristics.     

(E)-2,3-二溴-2-丁烯-1,4-二醇的合成

在2-丁炔-1,4-二醇与溴的加成反应体系中,添加适量的溴化钠,不但可以有效地提高(E)-2,3-二溴-2-丁烯-1,4-二醇的收率,而且反应可以在室温下进行,避免了低温冷却,更有利于工业化的生产。