Efficient synthesis of functionalized spiro-2,5-dihydro-1,2-λ-oxaphospholes

The reaction of ethyl propiolate with triphenylphosphine (Ph₃P) in the presence of N-alkylisatins led to ethyl 2,2,2-triphenyl-2,5-dihydro-1,2-λ⁵-oxaphosphole-4-carboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones in good yield. The reaction of dialkyl acetylenedicarboxylates with Ph₃P in the presence of N-alkylisatins led to dialkyl 2,2,2-triphenyl-2,5-dihydro-1,2-λ⁵-oxaphosphole-3,4-dicarboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones and alkyl 4-(alkoxy)-5-oxo-2,5-dihydro-3-furancarboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones.     

Synthesis of 4-Hydroxy-3-(1-aryl-2-acetylethyl)-7,8-diaryl-2H-thieno(3,2-h)chromen-2-ones Using Cerium(III) Chloride

A new series of 4-hydroxy-3-(1-aryl-2-acetylethyl)-7,8-diaryl-2H-thieno(3,2-h)chromen-2-ones were synthesized in good yields by reacting 4-hydroxy-7,8-diaryl-2H-thieno(3,2-h)chromen-2-ones with various α,β-unsaturated ketones in presence of cerium(III) chloride in acetonitrile.     

Reaction of 1,3-diaryl-2,3-dibromo-1-propanones with urea in basic and acidic medium. Synthesis of pyrimidine,imidazoline and imidazolidine derivatives

Reaction of 1,3-diaryl-2,3-dibromo-1-propanones 1 with urea in basic medium afforded 4,6-diaryl-5-bromo-5,6-dihydropyrimidine-2(1H)-ones 4 . Oxidation of these bromopyrimidines 4 in dimethylsulphoxide gave 4,6-diaryl-1,6-dihydropyrimidine-2,5-diones 6 , which were further converted to their thione analogues 7 . Reaction of 1,3-diaryl-2,3-dibromo-1-propanones 1 with urea, phenylurea and sym-diphenylurea in glacial acetic acid medium gave in appreciable yields 4-phenyl-5-α-(bromoarylmethyl)imidazolin-2-one 8 and 1,3-diphenyl-4-aroyl-5-arylimidazolidin-2-one 11 respectively.     

Reaction of N1, N2-diarylamidines with chloranil and 2,3-dichloro-1,4-naphthoquinone

Nucleophilic attack by N² of N¹ N²-diarylformamides 1a-c on C-2 of chloranil (2) and subsequently by N¹ on C-1 of 2 initiates the formation of benzimidazolinones 8a-c. In contrast, when 1b-e is reacted with 2,3-dichloro-1,4-naphthoquinone (9) , both chlorine atoms are successively substituted by the two nitrogen atoms and 2-(arylamino)-3-(N-formylarylamino)-1,4-naphthoquinones 13b-e result, which (probably via their cyclic tautomers 12b-e ) may be cyclodehydrogenated to form N¹,N³-diarylnaphtho[2,3-d] imidazoline-2,4,9-triones (as 14b,c ). On the other hand, N¹,N²diarylacetamidines 15a-d attack 2 and 9 at C-2 with N² but subsequently exert nucleophilic character at the acetamidine α-carbon attacking C-1 of 2 and 9 , respectively, thus forming 1-aryl-2-(arylimino)-3a-hydroxy-2,3,3a,6-tetrahydro-1N-indol-6-ones 18a-d and 3-aryl-2-(arylimino)-9b-hydroxy-2,3,5,9b-tetrahydro-1-H-benz[e]indol-5-ones 19b,c , respectively. The latter may be thermally dehydrated to the fully conjugated 2,5-dihydro-3H-benz[e]indol-5-ones 20b,c. Unambiguous structural assignments for 18b and 20c are made on the basis of X-ray crystal structure analyses.     

Reactions of 4-acyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones with nucleophilic reagents

4-Acetyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones reacted with amines to give 1-alkoxyaryl-5-aryl-4-(1-R-aminoethylidene)pyrrolidine-2,3-diones. Reactions of amines with 4-benzoyl-substituted analogs involve nucleophilic attack on the C³ atom in the heteroring to produce the corresponding 3-R-amino-1-alkoxyaryl-5-aryl-4-benzoyl-2,5-dihydro-1H-pyrrol-2-ones. Reactions of the title compounds with hydrazine hydrate, regardless on the substituent on C₄, afforded 4-aryl-3-methyl(phenyl)-5-[2(4)-methoxyphenyl]-4,6-dihydropyrrolo[3,4-c]pyrazol-6-ones.     

Dithiophosphorylation of racemic and enantiomerically pure trimethyl-N-(1-phenylethyl)silanamine

Trimethylsilyl P-aryl-N-[(RS)-, (S)-(?)-, and (R)-(+)-(1-phenylethyl)]phosphonamidodithioates were synthesized by reactions of 2,4-diaryl-1,3,2λ⁵,4λ⁵-dithiadiphosphetane 2,4-disulfides with racemic and and enantiomerically pure trimethyl-N-(1-phenylethyl)silanamine.     

13C NMR spectra of some 1,2-disubstitutedN-vinyl-1H-1,2,4-triazoles

¹³C NMR spectra (20 and 75 MHz, in DMSO-d₆) of a series of 1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)- and 1,3-diaryl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ones were registered. It was shown that the chemical shifts of both the carbon atom of the alkene group and C(3) reflect regio- and stereoisomerism of these compounds. Taking this into account the isomeric structures of several 1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ones were identified and the configurations relative to the double bond of a number of 1,3-diaryl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ones were determined.     

Reactions of 1,1-diaryl-2-isopropylidene-3-methylenecyclopropanes with C,N-diarylnitrones and nitrile oxides

The reactions of unactivated bis(methylene)cyclopropanes with nitrones and nitrile oxides have been investigated. The 1,1-diaryl-2-isopropylidene-3-methylenecyclopropanes react with the C,N-diarylnitrones to give a mixture of 2,2-dimethyl-1,6-diaryl-3-(diarylmethylene)piperidin-4-ones and 5-methyl-1-aryl-1-(arylamino)-4-(diarylmethylene)hex-5-en-3-ones. 2,3-Dihydro-3-methylenepyridin-4(1H)-ones are obtained by reaction of 1,1-diaryl-2-isopropylidene-3-methylenecyclopropanes with nitrile oxides.     

P,P′-(2,5-Dimethoxy-3,6-dimethyl-2,5-dioxo-2λ5,5λ5-[1,4,2,5]dioxadiphosphinan-2,5-diyl)-bis-phosphonsäuretetramethylester

P,P′-(2,5-Dimethoxy-3,6-dimethyl-2,5-dioxo-2λ⁵,5λ⁵-[1,4,2,5]dioxadiphosphinane-2,5-diyl)-bis-phosphonic acid tetramethylester The title compound 1 is formed by reaction of the corresponding phosphonic acid 2 and orthoformicacidmethylester as a mixture of four stereoisomeres. The RRSS isomer was separated. It crystallizes in the triclinic space group P ?1 with a = 649.2 pm, b = 976.1 pm, c = 1 571.7 pm, α = 80.9°, β = 88.1°, γ = 78.6° and Z = 2. The ³¹P and ¹³C NMR spectra (4 and 5 spin systems) are discussed.     

4-alkyl(aryl)-1-germacyclohexa-2,5-diene

enThe 1(Z),4(Z)-1,5-dilithium-3R-3-methoxypenta-1,4-dienes react with diaryldichlorogermanes and dialkyldichlorogermanes to give the 1,1-diaryl- and 1,1-dialkyl-4R-4-methoxy-1-germacyclohexa-2,5-dienes, respectively.With phenyltrichlorogermane, methyl- and ethyl-trichlorogermanes the E/Z-isomeric 1-phenyl(methyl,ethyl)-1-chloro-4R-4-methoxy-1-germacyclohexa-1,3-dienes are obtained, reduction of these with LiAlH₄ makes the corresponding 1-aryl-(alkyl)-1H-4R-4-methoxy-1-germacyclohexa-2,5-dienes available.Reduction of 1-ethyl-1-chloro-4-phenyl-4-methoxy-1-germacyclohexa-2,5-diene with LiAlH₄ yields by additional ether cleavage 1-ethyl-1H-4-phenyl-1-germacyclohexa-2,4-diene.The ¹H NMR (60 MHz, 90 MHz), ¹³C NMR, IR and mass spectra are discussed, several ¹H NMR spectra are calculated according to the LAOCOONLAME program.     

Exceptional Products of the Desulfurization of N,2-Diaryl-5-(arylimino)- 2,5-dihydro-4-nitroisothiazol-3-amines

The desulfurization of several N,2-diaryl-5-(arylimino)-2,5-dihydro-4-nitroisothiazol-3-amines 5 with Ph₃P led to complex mixtures of products in low yields. For instance, quinoxaline-2-carboxamide 1-oxides of type 6 (Scheme 2) and, in some cases, also 3-nitroquinolines of type 7 (Scheme 5) were isolated. By the desulfurization of the substituted derivatives 5b – e , a rearrangement of the intermediates yielded 6 and 7 with a different substitution pattern from that expected from the starting materials (Scheme 3). The additional formation of two isomeric 1,2,5-oxadiazole-3-carboxamides 8 was observed only in the case of 5d (R¹=R²=F) (Scheme 6). Under the same reaction conditions, the major product of the desulfurization of 5c was the quinoxaline-2-carboxamide 1-oxide 9 (Scheme 7). Reaction mechanisms involving intermediate ketene imines and O transfer from the NO₂ group to the neighboring ketene imine are proposed. The structures of 6a , 6e , 6k , 7b , and 8d were established by X-ray crystallography, while the structure of 9 was elucidated by 2D-NMR spectroscopy and corroborated by X-ray crystallography.     

Cyclische Verbindungen aus Phosphor,Kohlenstoff und Schwefel

Cyclic Compounds Made of Phosphorus, Carbon, and Sulfur By reaction of P₄S₁₀ with excess tri-n-dodecylamine and tribenzylamine bis(didodecylammonium)-3,6-diundecyl-2,5-dithioxo-1,4,2λ⁵,5λ⁵-dithiaphosphorinan-2,5-disulfide ( IId ) and bis(tribenzylammonium)-3,6-diphenyl-2,5-dithioxo-1,4,2λ⁵,5λ⁵-dithiaphosphorinan-2,5-disulfide ( IIe ), respectively, are formed. Reactions of the ammonium-3,6-dialkyl-2,5-dithioxo-1,4,2λ⁵,5λ⁵-dithiaphosphorinan-2,5-disulfides with aqueous alkali solutions and CH₃I as well as their therolysis are described.     

Novel preparation of N′-arylthiocarbamoyl-N,N-dialkylamidines and their synthetic utilities

Treatment of 5-(arylimino)-4-(dialkylamino)-5H-1,2,3-dithiazoles (2) with NaOH in aqueous EtOH at room temperature gave N′-arylthiocarbamoyl-N,N-dialkylamidines (3) in good to excellent yields. The reaction of 3 with sulfur monochloride, thiophosgene, thionyl chloride, sulfuryl chloride, N-phenylimidoyl dichloride, and phthaloyl chloride in CH₂Cl₂ gave 2, 5-(arylimino)-4-(dialkylamino)-Δ³-thiazoline-2-thiones (5), 5-(arylimino)-4-(dialkylamino)-5H-2-oxo-1,2,3-dithiazoles (6), 5-(arylimino)-4-(dialkylamino)-5H-2,2-dioxo-1,2,3-dithiazoles (7), 5-(arylimino)-4-(dialkylamino)-2-(phenylimino)-Δ³-thiazolines (8), and 3-(arylimino)-4-(dialkylamino)-2,5-benzothiazocine-1,6-diones (10) as major products, respectively.     

TRITHIA-DIPHOSPHABIYCLO[2.2.1]HEPTANE

Abstract

3,6-Dialkyl-2,5-Dithioxo-1,4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfides (1) react with PSCI₃, to give 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵ diphosphabicyclo[2.2.1]heptanes (2). The reaction mechanism of their formation. and the stereochemistry are discussed. By reduction of 2 with (n-C₄H₉)₃P or (C₆H₅),P 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1]heptanes (3) are formed. 2c reacts with one mole of (C₆H₅)₃P to give 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo(2.2.1]heptane, 4c.

3,6-Dialkyl-2,5-dithioxo-1.4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfide (I) reagieren mit PSCI₃ zu 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵-diphosphabicyclo[2.2.l]heptanen (2). Der Reaktionsmechanismus ihrer Bildung und ihre Stereochemie werden diskutiert. Die Reduktion von 2 mit (n-C₄H₉)₃,P oder (C₆H₅)₃P führt zu 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1] heptanen(3). 2c reagiert mit einer äquimolaren Menge (C₆H₅)₃,P zu 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo[2.2.1]heptan, 4c.     

Cycloaddition-elimination reactions of 4-methyl-5-(substituted)-imino-Δ2-1,2,3,4-thiatriazolines with isocyanates

4-Methyl-5-(substituted)imino-1,2,3,4-thiatriazolines 1 (R² ≠ Me) undergo cycloaddition-elimination reactions with isocyanates to yield 4-methyl-5-(substituted)imino-1,2,4-thiadiazolidine-3-ones 5 via the thermodynamically less stable isomers 4 . The latter have not been isolated, except for 4q which was shown to iso-merize rapidly into 5q with phenylsulfonyl isocyanate. The reactions of 1 are accelerated by using less bulky R² substituents and more electrophilic isocyanates, in accordance with the viewpoint that 1 reacts as a masked 1,3-dipole. The products 4i-n (= 5i-n ), derived from 1b , add isocyanates reversibly to give 2,3,4,5-tetrahydro-6aλ⁴-thia-1,3,4,6-tetraazapentalene-2,5-diones 9i-n , which have been isolated and characterized spectroscopically. Such compounds with a hypervalent sulfur atom thus occur as intermediates during the isomerization of 4 to 5 under the influence of isocyanates.     

Cycloacylation of 3-oxo-3-R1-N-R2-propanethioamides by 3-aryl-2-propenoyl chlorides

The products of cyclocondensation of 3-oxo-3-R¹-N-R²-propanethioamides with 3-aryl-2-propenoyl chlorides in acetone in the presence of potassium carbonate are 5-acyl-1-aryl(alkyl)-4-aryl-6-thioxopiperidin-2-ones, 5-acyl-2-aryl-6-aryl(alkyl)amino-2,3-dihydro-4H-thiopyran-4-ones, and 2-acetonylidene-3,6-diaryl-5,6-dihydro-4H-1,3-thiazin-4-ones, the structure of which is proven by both spectral methods and chemical conversions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 623–628, April, 2006     

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ5,5λ5-[1,4,2,5]-dioxadiphosphinan-2,5-diyl)-bis-phosphonsäure

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ⁵,5λ⁵-[1,4,2,5]dioxadiphosphinane-2,5-diyl)-bis-phosphonic Acid The tetrahydrate 1 of the title compound crystallizes in the monoclinic space group P2₁/c with a = 845.8, b = 1 098, c = 981.7 pm, β = 113.02° and Z = 2. The anions of the oxonium compound (H₃O⁺ · H₂O)₂(C₄H₁₀O₁₂P₄^2?) are layered by hydrogen bridges. The ¹H, ¹³C and ³¹P NMR spectra (4 and 5 spin systems) are discussed.     

Chemistry of 1,5-diketones: II. Specificity of transformations of polycyclic 1,5-diketones in acid media

2-(1,3-Diaryl-3-oxopropyl)cyclohexan-1-ones underwent carbo-and heterocyclization in a mixture of acetic acid with acetic anhydride in the presence of perchloric acid. The transformation of 2-(1,3-diaryl-3-oxopropyl)cyclohexan-1-ones into 2,4-diaryl-5,6,7,8-tetrahydrochromenylium salts was shown to involve intermediate 2,4-diarylbicyclo[3.3.1]non-2-en-9-ones. The structure of 2,4-diaryl-substituted bicyclo[3.3.1]non-2-en-9-ones and products of their reactions with halogens and hydroxylamine hydrochloride was confirmed by ¹H and ¹³C NMR spectroscopy.     

Synthesis and study of new 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxaline derivatives

New derivatives of photochromic 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxalines were synthesized by condensation of 4-methyl-and 4,5-dimethyl-1,2-phenylenediamine with 1,3-diaryl-2,3-dibromopropan-1-ones. The reactions of 4-methyl-1,2-phenylenediamine produce mixtures of regioisomers. The chemical properties of the reaction products were studied. The structure of one of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–356, February, 2006.     

Reaction of aryl-substituted glycineamidines with oxalic acid derivatives

The reaction of N¹,N²-diaryl-N-arylglycineamidines with oxalyl chloride and diethyl oxalate leads to 1,4-diaryl-5-aryliminopiperazine-2,3-diones and 1,3-diaryl-4-aryliminoimidazolidin-2-ones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 230–232, January, 1991.