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.     

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.     

Cyclisierungsreaktionen β,γ-ungesättigter Kohlensäurederivate. V . Reaktionen β,γ-ungesättigter Carbamidsäureester mit Sulfenylchloriden - Synthese von 3,5,5-trisubstituierten Oxazolidin-2-onen

Cyclization Reactions of β,γ-Unsaturated Derivatives of Carbonic Acid. V. Reactions of β,γ-Unsaturated Carbamic Acid Esters with Sulfenyl Chlorides — Synthesis of 3,5,5-Trisubstituted Oxazolidine-2-ones N,N-Disubstituted β,γ-Unsaturated urethanes 1 have been cyclized to 3,5,5-trisubstituted oxazolidine-2-ones 3 by aromatic sulfenyl chlorides in methylene chloride. The same oxazolidine-2-ones 3 were obtained by reaction of 5-bromomethyloxazolidine-2-ones 8 with thiophenols.     

Cyclisierungsreaktionen β,γ-ungesättigter Kohlensäurederivate. XI [1] Untersuchungen zur Stereochemie der Cyclofunktionalisierung β,γ-ungesättigter Carbamidsäureester

Cyclization Reactions of β,γ-Unsaturated Derivatives of Carbonic Acid. XI. Investigation of Stereochemistry of the Cyclofunctionalization of β,γ-Unsaturated Carbamic Acid Esters N, N-Disubstituted β,γ-unsaturated urethanes 1 have been cyclized to 3,5-disubstituted oxazolidine-2-ones 3 by aromatic sulfenyl chlorides 2 . The stereochemistry of the products and the cyclofunctionalization reaction were investigated.     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden. 2-Arylthiomethyl-2,3-dihydrobenzofurane aus 2-Allyl- und 2-Methallyl-phenolen und Arylsulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides: Synthesis of 2-Arylthiomethyl-2,3-dihydrobenzofurans by Reaction of 2-Allyl- and 2-Methallyl-phenols, Respectively, and Arylsulfenyl Chlorides Reactions of acetylamino substituted 2-allyl-phenols ( 1 and 2 ), and 2-methallyl-phenol ( 6 ), respectively, with different arylsulfenyl chlorides ( 3a—d ) yield the products of a cyclofunctionalization 5- or 7-acetylamino-2-arylthiomethyl-2,3-dihydrobenzofurans ( 4a–d ) or ( 5a–d ) and 7-acetylamino-2-arylthiomethyl-2-methyl-2,3-dihydrobenzofurans ( 7a–d ). The compounds 7 are the first examples of cyclofunctionalization of 2-methallylphenols by means of sulfur chlorides. The identification of the products was carried out by mass spectrometry, ¹H-n.m.r. spectroscopy and elemental analysis.     

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.     

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 .     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden. III. 2-Arylthiomethyl-2,3-dihydrofuro[3,2-h]chinoline aus 7-Allyl- bzw. 7-Methallyl-8-hydroxychinolin und Aryl-sulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides. III. 2-Arylthiomethyl-2,3-dihydrofuro[3,2-h] quinolins from 7-Allyl- and 7-Methallyl-8-hydroxyquinoline, respectively, and Arylsulfenyl Chlorides Reactions of 7-allyl- ( 3 ) and 7-methallyl-8-hydroxyquinoline ( 4 ) with selected arylsulfenyl chlorides ( 5a – d ) yield the products of cyclofunctionalization corresponding 2-arylthiomethyl-2,3-dihydrofuro[3,2-h]quinolins ( 6 and 7 ). The products are identified by ¹H-n.m.r.-spectroscopy, mass spectrometry and microanalyses.     

Versuche zur Synthese sterisch gehinderter Thiazylarene und deren Beziehung zu Arylsulfenylnitrenen

Attempts to Synthesize Sterically Hindered Thiazyl Arenes and Their Relationship to Arylsulfenyl Nitrenes Up till now all attempts to synthesize organic thiazyl compounds in substance failed. Stabilization leads to the corresponding disulfide 2 , the thioaminyl radical 7 and the sulphur diimide 8 . Formally thiazyl compounds 1 and sulfenyl nitrenes 1 were resonance structures. Via sulfenyl nitrenes 1 the formation of 2 , 7 , 8 can be discussed. An in situ preparation of sulfenyl nitrene 1a via the sulfenyl chloride 5a , synthesized by chlorination of the disulfide 2a , and the sulfenyl azide 6a is described in detail. 1a can also be prepared from the sulfenyl amide 4a by oxidation. The structures of the radicals 7a – f and 12f are discussed.     

Synthesis and derivatization of angular 3-chloro-3-chlorosulfenyl naphtho[1,2-b]pyran(4H)-4-ones with evaluation of antiviral activity

Angular 2,3-dihydronaphtho[1,2-b]pyran(4H)-4-ones 1a,b react with an excess of thionyl chloride to give the α-chlorosulfenyl chlorides 2a,b, which are reduced by iodide ion to give the corresponding 1,3,4-oxadithiino derivatives 3a,b. However, the aducts 4a,b and 5a,b were obtained by reduced 2a,b with iodide ion in the presence of 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene, respectively. Direct oxidation of 2a,b afford 3,3-dichloronaphthopyran-4-ones 6a,b, whilst conversion to the sulfenamides 7a,b prior to oxidation provides 3-chloronaphthopyranones 8a,b. While α-chloro β-oxo sulfenyl chlorides 2a,b undergo straight forward substitution with 1-methylpiperazine and with potassium cyanide to give 9a,b and 10a,b, respectively. Some of the prepared products were selected and tested for their antiviral activity against herpes simplex virus type-1 (HSV-1). Plaque reduction infectivity assay was used to determine virus count reduction as a result of treatment with test compounds. Compound 5a showed moderate effect against HSV-1.     

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.     

Cycloadditionen. 26. Einfluß von Substituenten in der allenischen ω-Position auf das Thermische Verhalten von Allencarbonsäurearylester

Cycloadditions. 26. Influence of Substituents in the Allenic ω-Position on the Thermal Behaviour of Aryl Allenecarboxylates The [(aryloxycarbonyl)methyl]triphenylphosphonium salts ( 1a and i ), obtained by reaction of aryl bromoacetates with triphenylphophine, react with the acid chlorides 3 in the presence of two equivalents of triethylamine to give the phenyl-or the (1-naphthyl)-2,3-alkadienoates ( 4a–d and 4e–h ), respectively, in the most cases accompanied by the arylalkynoates 6 and 7 and/or with the naphthyl esters 8 of the used acids. Treatment of the [(aryloxycarbonyl) methyl] triphenylphosphonium salts (1a–i) with triethylamine furnishes the phosphoranes 2a–i , which are transformed by reaction with diphenylketene into the aryl 3,3-diphenyl-2,3-butadienoates (5) . Heating of the derivatives 4a–d and 5a , bearing the unsubstituted phenyl nucleus in the ester moiety, leads to destruction, while heating of the naphthyl esters 4e–h and 5i – room temperature is sufficient in some cases-induces the IMDA-reaction to give the benzo-tricycles 9a–e . Heating of the 4,4-diphenyl-2,3-butadienoates (5b–h) , bearing the alkylsubstituted phenyl ring within the ester component, induces radical dimerization to give the cylobutanes 10b–h , which represent the head to tail dimers.     

Über die Reaktion von Chloranil mit Cyanidionen – eine ESR-Studie

On the Reaction of Chloranil with Cyanide Ions – an ESR Study The reaction of chloranil 1 with cyanide ions in acetonitrile and methanol solutions has been studied. The ESR Spectra revealed the formation of semiquinone anion radicals 7,8 , and 9 . The latter has been found as its protonated form in methanol only. In addition, both 1 and 2,3-dicyano-5,6-dichloro-1,4-benzoquinone 4 gave tetracyanoethylene anion radicals 6 upon reaction with cyanide ions in acetonitrile. Using ¹³C-labelled cyanide 6 was shown to originate from the fragmentation of the cyanide addition product to 4 . Using the spin trapping technique it was found that no cyanyl free radicals are formed during the thermal reaction of either 1 or 4 with cyanide ions.     

Dienoligomerisierung. XVI. Nickelkomplexkatalysierte Codimerisierung von isomeren Octatrienen mit Ethen

Dienoligomerization. XVI. Catalytic Codimerization of Isomeric Octatrienes with Ethene by Nickel Complexes The isomeric octatrienes (n-octa-1,3c,t,7-triene 1 , n-octa-1,3c,6t-triene 2 and 3-methylhepta-1,4t,6-triene 3 ), which are easily obtained in high yields by transition metal catalysed dimerization of butadiene, react with ethene 4 in the presence of the cationic tetrakis-(triethylphosphite)-nickelhydride complex 5 to the dodimers 3-methylnona-1,4c,t,8-triene 6 , 4-vinylocta-2c, 7-diene 7 , 3-methyl nona-1,4c,t,7t-triene 8 , 4-vinylocta-2c,6t-diene 9 , 3,6-dimethylocta-1,4c,t,7-triene 10 and 3-methyl-4-vinylhepta-1,5c-diene 11 . The concentration-time dependence and a possible reaction mechanism of the codimerization are discussed and the structure data of the reaction products are reported.     

Cyclisierungen mit Cyanthioacetamid in Gegenwart von Schwefel

Cyclizations of Cyanothioacetamide in the Presence of Sulphur Cyanothioacetoamide 1 reacts with sulphur in the presence of triethylamine to form the 2,5-diamino-thiophene derivative 3 and in the presence of sodium ethoxide the 1,4-dihydropyridine derivative 2 , respectively. 3 easily undergoes ring opening to yield the butadiene derivative 6 . Catalyzed by amine from 1 , cyclic ketones, and sulphur the 2-spiro[thieno[2,3-d]pyrimidine-4-thiones] 8 arise. Analogously to other cyanoacetic acid derivatives 1 react with sulphur and isothiocyanates to form the 4-amino-Δ⁴-thiazoline-2-thiones 9 and with sulphur and carbon disulfide to yield the 5-amino-1,2-dithiol-3-thione derivative 12 . Among the o-amino-thiocarboxamides 3 , 9 , 12 the compounds 3 and 9 can be converted into the 5,6-heterocondensed pyrimidine-4-thiones 4 and 10 .     

Direct coloration of textiles with photochromic dyes. Part 2: The effect of solvents on the colour change of photochromic textiles†

Polyester, acrylic and nylon textile substrates dyed with two spirooxazine dyes, 1,3,3‐trimethyl‐spiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1a ) and 6′‐piperidino‐1,3,3‐trimethyl spiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1b ), exhibit significantly higher photochromic colour build‐up when wet compared with after drying. A study of this phenomenon, extended beyond water to the influence of a series of selected organic solvents on photochromic behaviour, using colour measurement of the photochromic textiles under controlled ultraviolet irradiation conditions, is reported. The results of molecular modelling calculations (AM1 in water and PM5 in water) have been used as a means of interpreting the observed effects, in conjunction with qualitative arguments based on solvation and fibre swelling.     

还原型辅酶Q_(10)的合成研究

2,3-二甲氧基-5-甲基-1,4-苯酚与异癸异戊二烯醇在改性BF3.OEt2的催化下发生傅克烷基化反应合成还原型辅酶Q10。经过优化,在n(氢化辅酶Q0)∶n(异癸异戊二烯醇)∶n(催化剂)=5∶1∶0.2,反应温度30℃,反应时间10 m in的条件下收率达75%。     

Syntheses of deep coloured aminonaphthoquinonoid dyes. Reaction of dichloronaphthazarins with 2-aminobenzenethiol and related compounds

The reaction of 2,3-dichloronaphthazarin 1a with potassium 2-amino-benzenethiolate gives the ring-closure product 10,11-dithia-5H,16H-5, 16-diazadinaphtho[2,3a],[2,3c]-1,4-naphthoquinone 9 in 86.2% yield together with small amounts of 5-hydroxy-6-chloro-7-thia-12H-12-azanaphtho[2,3a]-1,4-naphthoquinone 8. Dye 9 is green in colour and absorbs infrared light at 727 nm. Oxidation of 9 by hydrogen peroxide gives 10,11-dithia-5H,16H-5,16-diazadinaphtho[2,3a],[2,3c]-1,4-naphtho-quinone-10,11-dioxide 14 which absorbs infrared light at 827nm. The reaction of 1a with 2-aminoethanethiol gives 5-hydroxy-6-chloro-7-thia-10-aza-8, 9,10-trihydrobenzo[2,3a]-1,4-naphthoquinone 4 and 2,3-di-chloro-5-hydroxy-7-thia-10-aza-8, 9,10-trihydrobenzo[2,3a]-1,4-naphtho-quinone 5 in yields of 14.2 % and 3.2 %, respectively.     

Oxime‐Derived Palladium Complexes as Very Efficient Catalysts for the Heck–Mizoroki Reaction

Oxime‐derived, chloro‐bridged palladacycles 16 are efficient complexes for the Heck vinylation of aryl halides. The isolated catalysts are thermally stable, not sensitive to air or moisture and easily accessible from inexpensive starting materials. The reaction can be performed under aerobic conditions, with aryl iodides, bromides and chlorides with acrylic esters and olefins displaying turnover numbers (TON) of up to 10¹⁰ for phenyl iodide and turnover frequencies (TOF) of 1.4×10⁸ h⁻¹. Deactivated aryl bromides undergo the Heck reaction with styrene with TON and TOF values up to 97,000 and 6063 h⁻¹, respectively. Even aryl chlorides undergo the coupling reaction with olefins with TON up to 920. Complexes 16 catalyze the synthesis of 2,3‐disubstituted indenones and indoles in good yields via annulation reaction of internal alkynes with o‐bromo‐ or o‐chlorobenzaldehyde and o‐iodoaniline, respectively.     

Comparative study on polyimides from 3,3′-and 4,4′-linked diphthalic anhydride

1,4-Bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, bis(2,3-dicarboxyphenoxy)sulfide dianhydride, bis(3,4-dicarboxyphenoxy)sulfide dianhydride, and 2,3,3′,4′-tetracarboxy diphenyl sulfide dianhydride were synthesized from 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. Bis(2,3-dicarboxyphenyl)sulfone and bis(3,4-dicarboxyphenyl)sulfone were obtained by the oxidation of the corresponding bis(dicarboxyphenyl)sulfide by hydrogen peroxide. The polyimides from the dianhydrides mentioned above and 4,4′-oxydianiline were prepared. The properties, such as dynamic mechanical behavior, thermooxidative stability, stress-strain behavior, chemical resistance, and permeability to some gases have been in investigated for the isomeric polyimides. © 1996 John Wiley & Sons, Inc.