Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: VII. Synthesis and Properties of Phenylthio-substituted Phthalocyanine Metal Complexes

New phenylthio-substituted phthalodinitriles have been synthesized: 5-amino-4-phenylthio-, 5-acetylamino-4-phenylthio-, 5-octanoylamino-4-phenylthio-, 5-phenoxy-4-phenylthio-, 5-(4-carboxyphenoxy)-4-phenylthio-, 5-(4-tert-butylphenoxy)-4-phenylthio-, and 4,5-bis(phenylthio)phthalodinitriles. Their complexes with metals have been prepared and examined by spectral methods.     

Synthesis and Applications of 3-Phenylthio-2-Sulfolenes

Treatment of 3-phenylthio-2-sulfolene ( 1 ) with an equimolar proportion of butyllithium at ?78 °C in THF followed by addition of an electrophile gave the 2-substituted 3-phenylthio-2-sulfolenes (2). The deprotonation was found to proceed only at the vinylic C-2 position. Some of the 2-sulfolenes 2 underwent desulfonylation upon heating with base. Of particular interest was the conversion of 3-phenylthio-2-trimethylsilyl-2-sulfolene ( 2h ) to its 3-sulfolene isomer 6 by sequential addition of butyllithium and salicylic acid at low temperatures. The 3-sulfolene 6 was desulfonylated by Kugelrohr distillation at 150° C under vacuum to give (Z)-2-phenylthio-l-trimethylsilyl-1,3-butadiene ( 8 ). The regiochemistry of the Diels Alder reaction of this highly reactive diene 8 was found to be controlled by the phenylthio group, and the stereochemistry is endo addition. Diene 8 was oxidized to its sulfone derivative 12 which also underwent a stereospecific Diels-Alder reaction.     

Synthesis of 6-phenylthiobenzo[b]thiophenes

A method of synthesizing 2-acetylamino-7-hydroxy-6-phenylthio-3-carbethoxybenzo[b]thiophenes from 6-phenylthio-7-oxo-4,5,6,7-tetrahydrobenzo[b]thiophenes has been developed. A method is also proposed for synthesis of 7-phenylthiobenzothieno[2,3-d]pyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 534–536, April, 1991.     

β-Substituted ketene thioacetals as β-lithioacrylate equivalents. The synthesis of (±)-eldanolide

Lithiation of 1,1-bis(phenylthio)-3-phenylthio-1-propene 3 and reaction with a range of electrophiles gave exclusively the γ-substituted product 4. This reagent has been used in a short synthesis of the pheromone, (±)-eldanolide.     

Regioselective synthesis of functionalized 2-(phenylthio)benzoates by ‘[3+3] cyclization/homo-Michael’ reactions of 1-methoxy-1-trimethylsilyloxy-3-phenylthio-1,3-butadienes with 1,1-diacylcyclopropanes

2-(Phenylthio)benzoates containing a remote halide function are regioselectively prepared by ‘[3+3] cyclization/homo-Michael’ reactions of 1-methoxy-1-trimethylsilyloxy-3-phenylthio-1,3-butadienes with 1,1-diacylcyclopropanes.     

2-Phenylthio-3-bromopropene, a valuable synthon, easily prepared by a simple rearrangement

[reaction: see text] Treatment of allyl phenyl sulfide with bromine, followed by aqueous sodium hydroxide, provides a good yield of 2-phenylthio-3-bromopropene 2 via a mechanism that is elucidated by isolation of the 1,3-dibromo-2-(phenylthio)propene intermediate 7. Three uses of 2 as an annulating agent for cycloheptanone are illustrated, demonstrating that this reagent is a synthetic equivalent of acetonyl halide and an alpha-halo vinyllithium. It is also readily converted to the useful synthons 2,3-bis(phenylthio)propene 16 and 2-phenylthio-3-(phenylsulfonyl)propene 17.     

Furopyridines. XII . Reaction of 3-bromo, 2-phenylthio and 2-phenylthio-3-bromo derivatives of furo[2,3-b]-, furo[3,2-b]-, furo[2,3-c]- and furo[3,2-c]pyridine with several alkyllithiums

This paper describes reactions of 3-bromo- 1a-d , 2-phenylthio- 5a-d and 2-phenylthio-3-bromofuropyridines 6a-d with n-butyl-, t-butyl- and methyllithium and lithioacetonitrile. Lithiation of compounds 1a-d with n-butyl- or methyllithium gave the parent furopyridines 2a-d and o-ethynylpyridinols 3a-d. Reaction of compounds 5a-d with methyllithium afforded o-(phenylthioethynyl)pyridinols 7a-d , which were also yielded by reaction of compounds 6a-d with t-butyl- or methyllithium. The phenylthio group in compounds 7a-d were substituted with t-butyl group by the reaction with excess t-butyllithium. In contrast, 2-phenylthio group in compounds 5a-d and 6a-d was substituted with cyanomethyl group by reaction with lithioacetonitrile to give compounds 11a-d and 10b, c respectively.     

Formation and characterization of 1-substituted 1,2-dithiolanyl radicals by laser flash photolysis

Photolyses of 1-alkylthio-3-propanethiols, 1,3-propanedtthiol and 1-phenylthio-3-propanethiol in acetonitrtle, 2-propanol or aqueous mixtures of these solvents lead to five membered cyclic sulfuranyl radicals of the type \(\left[ {R - \overline {S - S - CH_2 - CH_2 - C} H_2 } \right]\) which exhibit characteristic uv/vis absorption spectra. These 1-substituted 1,2-dithiolanyl radicals are formed by intramolecular cyclization of the primarily formed thiyl radicals generaeed by S-H- bond cleavage in the excited starting material. The wavelength of the absorption maximum observed for these transients depends on the natuee of the substituntt R on the sulfur atom (R=H, alkyl, aryl).     

贫电子环丙烷衍生物与苯硫酚的反应研究

顺-1乙酰基-2-对位取代苯基-6,6-二甲基-5,7-二氧-螺-[2,5]4,8-辛二酮(1a～ld)与苯硫酚(2)在封管中100℃反应得β-乙酰基-r-苯硫基-r-对位取代苯基丁酸苯硫酯(3a～3d),当反应物为1a时,还同时得到α-苯硫羰基-β-乙酰基-r-对甲苯基-r-丁酸内酯(4)。     

Stereoselective Synthesis and Diels-Alder Reactions of (Z)- and (E)-1,2-bis(Phenylthio)-1,3-Butadiene

Bromination of 3-phenylthio-2-sulfolene (2) with N-bromosuccinimide gave 2-bromo-3-phenylthio-2-sulfolene (3) which was converted mainly to 2,3-bis(phenylthio)-2-sulfolene (4) by treatment with sodium phenylthiolate. Thermal desulfonylation of 4 at different temperatures in the presence of a base (DBU) yielded stereoselectively the (Z)- and (E)-1,2-bis(phenylthio)-1,3-butadiene (6). These two geometric isomers could be thermally interconverted. The Diels-Alder reactions of 6 were also investigated. Only the (Z)-diene 6a could undergo the Diels-Alder reaction; the (E)-diene 6b was in situ converted to the Z isomer before undergoing (he Diels-Alder reaction. The reaction of 6a with N-phenylmaleimide gave the cycloaddition product 7 with complete endo selectivity, but under daylight or during chromatography it readily underwent a thioallylic rearrangement to yield 8 with inversion of configuration. The cycloaddition of 6a with methyl acrylate proceeded regiospecifically, but generating a mixture of endo and exo isomers. The endo/exo ratio could be increased by using ZnCl₂ as the catalyst.     

A stereoselective route to alkenyl sulfides through the palladium-catalyzed cross-coupling reaction of 9-alkyl-BBN with 1-bromo-1-phenylthioethene or (E)- and (Z)-2-bromo-1-phenylthio-1-alkenes

The reaction of 9-alkyl-9-BBNs with 1-bromo-1-phenylthioethene or (E)- and (Z)-2-bromo-1-phenylthio-1-alkenes takes place readily in the presence of Pd(PPh₃)₄ and sodium hydroxide to afford stereodefined vinylic sulfides in excellent yields.     

Rearrangement of allylic azide and phenylthio groups of 3′-azido- or 3′-phenylthio-4′,5′-didehydro-5′-deoxyarabinofuranosyluridines

The reversible intramolecular [3,3]-sigmatropic rearrangement between 1-(3-azido-3,5-dideoxy-β-d-threo-pent-4-enofuranosyl)uracil (3) and 1-(5-azido-3,5-dideoxy-β-d-glycero-pent-4-enofuranosyl)uracil (4) and irreversible radical rearrangement of 1-(3,5-dideoxy-3-phenylthio-β-d-threo-pent-4-enofuranosyl)uracil (5) and 1-[3,5-dideoxy-3-(4-tolyl)thio-β-d-threo-pent-4-enofuranosyl]uracil (7) into 1-(3,5-dideoxy-5-phenylthio-β-l-glycero-pent-4-enofuranosyl)uracil (6) and 1-[3,5-dideoxy-5-(4-tolyl)thio-β-l-glycero-pent-3-enofuranosyl]uracil (8) were attained at room temperature.     

Heteroadamantanes and their derivatives. 3. The synthesis of 6-hydroxy-5-methoxycarbonyl-1,3-diazaadamantane

The interaction of methyl 3-oxo-4-(phenylthio)butyrate with formaldehyde and ammonium acetate yielded 5-methoxycarbonyl-6-oxo-7-phenylthio-1,3-diazaadamantane, which, on being heated with skeletal nickel in isopropanol was converted into 6-hydroxy-5-methoxycarbonyl-1,3-diazaadamantane. The structures of the compounds have been confirmed by IR and PMR spectroscopy.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 661–663, May, 1985.     

Preparative methods for (Z)-2-methoxy-1-phenylthio-1,3-butadienes. Rearrangement during copper(I)-induced elimination of thiophenol from some γ,δ-unsaturated thioacetals

(Z)-2-Methoxy-1-phenylthio-1,3-butadienes which are substituted with an alkyl group at the 4-position are not preparable by copper(I)-induced elimination of thiophenol from 4-alkyl-2-methoxy-1,1-bis(phenylthio)-3-alkenes; a 2-step stereospecific synthesis of one such diene ($\text{18}$) is described.     

Palladium Acetate Mediated Synthesis of 3,4-Benzo and Naphtho-β-Carbolines

An efficient synthesis of 2-(N-arylaminomethyl)indole derivatives 5 in good yields in four steps from 2-bromomethyl-3-phenylthio-1-benzenesulfonyl indole¹ is reported. Palladium acetate mediated cyclisation of 5 gives benzo and naphtho-ß-carbolines (6 & 7).     

Transformation of alkyl esters of 4-oxo-3-phenylthioalkanoic acids into substituted 4-phenylthio-2(5H)-furanones and 3-phenylthiofurans

When the solutions of methyl and ethyl esters of 4-oxo-3-phenylthioalkanoic acids are boiled in toluene in the presence of p-toluene sulfonic acid, substituted 4-phenylthio-2(5H)-furanones are formed in good yields. In the reaction with diisobutylaluminum hydride or organomagnesium compounds, the latter convert into the corresponding 3-phenylthiofurans.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 24, No. 3, pp. 313–316, March, 1988.     

A new synthesis of allylic alcohols or their derivatives via reductive elimination from γ-phenylthio-β-nitroalcohols with tributyltinhydride

Allylic alcohols are readily prepared by the Bu₃SnH-promoted elimination reaction from γ-phenylthio-β-nitroalcohls which are obtained by the joint reaction of nitroolefins, thiophenol, and aldehydes.     

Effect of γ-substitution on the thermoluminescence properties of terbium (III) acetylacetonate complexes with 1,10-phenanthroline

The coordination compounds [Tb(NO₃)₂ acac(phen)₂]H₂O (where acac is acetylacetone or its derivatives substituted in the γ-position) were synthesized and studied by luminescence, IR, and UV spectroscopy. Thermoluminescence of the complexes containing acetylacetonate, 3-phenylthio-2,4-pentadioñate, and 3-(p-methoxyphenylthio)-2,4-pentadionate was found. The structural and electronic aspects of the crystal thermoluminescence were discussed.     

A New Synthesis of 2-(6-Methoxycarbonylhexyl)-Cyclopent-2-EN-1-One Using α-Silylallyl Sulphide

Acylation of the α-trimethylsilylallyl phenyl sulphide (2). by reaction with the acid chloride (3), catalyzed by aluminium chloride in CH₂Cl₂ at ?78°C, gave methyl 9-oxo-12-phenylthio-11-dodecene (4). Hydrolysis of (4) followed by aldol condensation gave 2-(6-methoxycarbonylhexyl)-cyclopent-2-en-1-one (6).     

A new synthetic method for β-trimethylsilyl-α,β-unsaturated carbonyl compounds employing 1-methoxy-3-phenylthio-3-trimethylsilyl-1-propene

A new synthetic method for functionally substituted β-trimethylsilyl-α,β-unsaturated carbonyl compounds from 1-methoxy-3-phenylthio-3-trimethylsilyl-1-propene is described.