bluuebunny/crossref_metadata_2025_split huggingface dataset:
1,3‐Phosphorotropic rearrangement of pyridyl phosphates to hydroxypyridyl phosphonates
Authors: Onys'ko Peter P. , Suvalova Elena A. , Chudakova Tatiana I. , Sinitsa Anatolii D. 
Published: January 2005

AbstractThe lithium diisopropylamide (LDA) induced regioselective 1,3‐rearrangement of 3‐ and 2‐ pyridyl phosphates into the corresponding 3‐hydroxy‐4‐pyridyl‐and 2‐hydroxy‐3‐pyridylphosphonates has been observed and investigated. The rearrangement is proposed as a useful method for a directed introduction of a phosphoryl group into a hydroxypyridine nucleus.
Facile methods of the synthesis of S‐trialkylstannyl esters of dithio‐ and tetrathiophosphoric acids
Authors: Nizamov Il'yas S. , Kuznetzov Vladislav A. , Batyeva Elvira S. , Al'fonsov Vladimir A. , Pudovik Arkady N. 
Published: January 2005

AbstractS‐Trialkylstannyl dialkyldithiophosphates 3 and tetrathiophosphates 6 were easily obtained in the reaction of tetraphosphorus decasulfide 1 with trialkylalkoxystannanes 2 or alkylthiostannanes 5 under mild conditions. Tetraphosphorus decasulfide 1 and hexaalkyl distannylsulfides 4 produce tris(trialkylstannyl) tetrathiophosphates 9.
Benzodiselenagermoles and spirobisbenzodiselenagermoles
Authors: Tavarès Pascale , Meunier Philippe , Kubicki Marek M. , Gautheron Bernard , Dousse Gabriel , Lavayssière Hélène , Satgé Jacques 
Published: January 2005

AbstractSynthesis of benzodiselenagermoles and bisbenzodiselenagermoles was carried out by transmetallation group 4 → group 14 between diselenophenylenezirconocenes and dialkyl‐, diaryl‐ or alkylaryldichlorogermanes, aryltrichlorogermane or germanium tetrachloride. The new compounds were studied by1H,77Se NMR and mass spectrometry. In the case of compounds with substituted phenyl groups, double irradiation and 2D NMR experiments were performed to determine the chemical shifts of the two selenium atoms. The crystal structure of a spirobisbenzodiselenagermole has been established by X‐ray diffraction analysis.
Phosphoryl transfer reaction of phospho‐histidine
Authors: Li Yuan‐Chao , Tan Bo , Zhao Yu‐Fen 
Published: January 2005

AbstractN‐phosphorylhistidine was converted into its ester and phosphoric ester exchanged products in alcoholic media. It was demonstrated that the co‐participation of the three functional groups of phosphoryl, imidazolyl, and carboxyl in the molecule is essential for these reactions to occur. Also, the neat phosphoryl transfer reaction occurs with Nα, NIm‐Bis‐phosphohistidine.
Oxidation of congested thiophene 1,1‐dioxides with m‐chloroperbenzoic acid. Formation of epoxides and thiete 1,1‐dioxides and steric acceleration
Authors: Kamiyama Hiroaki , Hasemi Ryuji , Nakayama Juzo 
Published: January 2005

AbstractA series of thiophene dioxides (3), including highly congested ones, were synthesized. Their oxidation with m‐chloroperbenzoic acid (m‐CPBA) was investigated either in the presence or in the absence of Na2CO3. The following conclusions were reached. (1) Oxidation in the presence of Na2CO3 affords the corresponding epoxides (4) in moderate to excellent yields. (2) Oxidation in the absence of Na2CO3 produces the ring‐contracted thiete 1,1‐dioxides (5) as the principal product, thus providing a novel synthesis of the sulfur‐containing unsaturated four‐membered ring system. If necessary, 5 can also be derived by treatment of 4 with BF3·Et2O. In an extreme case, the oxidation of 3,4‐di(1‐adamantyl)thiophene afforded the corresponding thiete dioxide 5b directly in 78% yield. (3) Oxidation takes place faster with a more congested 3, probably because of destabilization of the HOMO by steric repulsion between bulky substituents and also owing to relief of steric crowding on going from the ground to the transition state. (4) The formation of 5 from 3 in the absence of Na2CO3 can be explained by the occurrence of an acid‐catalyzed rearrangement of 4 initially formed. However, a competitive pathway leading directly to 5 may also be operative.
New functionalization at the 5‐position of uracils by selenenylation
Authors: Kim Yong Hae , Lee Chun Ho , Lee Dong Hoon 
Published: January 2005

AbstractElectrophilic substitution of phenylselenenyl chloride at the 5‐position of uracils in the presence of silver reagents, such as Ag2O, AgBF4, or CF3CO2Ag, afforded the corresponding 5‐phenylselenenyluracils in excellent yields. 1,3‐Dimethyl‐5‐phenylselenenyluracil(2a), 5‐phenylselenenyl‐(2′,3′,5′‐tri‐O‐acetyl)uridine(2b), 5‐phenylselenoxyl‐1,3‐dimethyluracil(3a) and 5‐phenylselenoxyl‐(2′,3′,5′‐tri‐O‐acetyl)uridine(3b) were used for various transformations at C‐5 or C‐6 of pyrimidine bases via nucleophilic substitution, a free radical process, and a Michael‐type addition utilizing the unique properties of organo‐seleno groups located on C‐5 of pyrimidine bases.
Synthesis and reactions of optically pure cyclohexyl(o‐methoxyphenyl)phosphine‐borane and t‐butyl‐(o‐methoxyphenyl)phosphine‐borane
Authors: Imamoto Tsuneo , Matsuo Masatoshi , Nonomura Taro , Kishikawa Kuniyuki , Yanagawa Masao 
Published: January 2005

AbstractCyclohexyl(o‐methoxyphenyl)menthyloxyphosphineborane and t‐butyl(o‐methoxyphenyl)menthyloxyphosphine‐borane were prepared from dichlorocyclohexylphosphine and t‐butyldichlorophosphine by successive treatments with (−)‐menthol, o‐methoxyphenylmagnesium bromide, and borane‐THF complex. The separated pure diastereomers of each of the compounds underwent reaction with lithium naphthalenide to afford optically pure cyclohexyl(o‐methoxyphenyl)phosphine‐borane and t‐butyl(o‐methoxyphenyl)phosphine‐borane, respectively. These secondary phosphine‐boranes reacted readily with various electrophiles in the presence of bases with virtually net retention of configuration. A new chiral phosphine ligand, (S,S)‐1,2‐bis[cyclohexyl(o‐methoxyphenyl)phosphino]ethane was synthesized via the optically pure phosphine‐boranes.
Dense energetic compounds of C, H, N, and O atoms. III. 5‐[4‐nitro‐(1,2,5)oxadiazolyl]‐5H‐[1,2,3]triazolo[4,5‐c][1,2,5]oxadiazole
Authors: Gunasekaran Ananthakrishnan , Boyer Joseph H. 
Published: January 2005

AbstractDiazidoazofurazan 8 was obtained from the bis‐diazonium salt of diaminoazofurazan 7 by treatment with sodium azide and underwent thermolysis to 5‐[4‐azido‐(1,2,5)oxadiazolyl]‐5H‐[1,2,3]triazolo[4,5‐c][1,2,5] oxadiazole 5. The corresponding amine 13 was obtained from the azide 5 by reduction with stannous chloride and was oxidized by ammonium persulfate to 5‐[4‐nitro‐(1,2,5)oxadiazolyl]‐5H‐[1,2,3]triazolo[4,5‐c][1,2,5]oxadiazole 1. The azide 5 was converted to a phosphinimine 9 in a reaction with triphenylphosphine.
Homopolyatomic and heteropolyatomic halogen cations
Authors: Tornieporth‐Oetting Inis C. , Klapötke Thomas M. 
Published: January 2005

AbstractThis review is not exhaustive in scope but rather focuses on the most recent years of work in the field of cationic halogens, covering the literature up to mid 1992. This area is still currently developing. The review summarizes structure, preparation, and reactivity of cationic halogens. Modern theoretical aspects (ab initio MO calculations) as well as the energetics (thermodynamics) of these species are also included. In particular, the symmetric and unsymmetric structures of heteropolyatomic cations, the charge delocalization and bond lengths alternation in npπ–npπ species (n < 2), and the dimerization by π*‐π* interactions are discussed.
Generation of methylenephosphine oxides by thermal fragmentation of derivatives of the 2‐phosphabicyclo [2.2.2] octa‐5,7‐diene oxide ring system
Authors: Keglevich György , Újszászy Kálmán , Quin Louis D. , Quin Gyöngyi S. 
Published: January 2005

AbstractDifferential thermal analysis and differential scanning calorimetry showed that the title compounds decomposed at 240–260°C with release of the fragment RP(O) = CH2. Mass spectral studies also showed this to be a fragmentation pathway. The extruded methylenephosphine oxide could be trapped with ethanol, hydroquinone, or by reaction with the surface OH groups of silica gel.
Biimidazol‐2‐yl–BF2 complexes
Authors: Ross Timothy W. , Sathyamoorthi Govindarao , Boyer Joseph H. 
Published: January 2005

AbstractNonfluorescent 4,4′,5,5′‐tetramethyl‐ and 4,5,4′,5′‐bistetramethylene biimidazol‐2‐yls 5 and 6 combined with boron trifluoride to give the tetramethyl and bistetramethylenebiimidazol‐2‐yl–BF2 complexes 9 and 10 isolated as strongly fluorescent BF3 salts, λf (dichloromethane): 377 nm Φ 0.93 and 386 nm Φ 0.90. Similarly, fluorescent bibenzimidazol‐2‐yl 7, λf (ethanol), 370 nm Φ 0.14, gave a BF2 complex 11 isolated as a BF3 salt λf (ethanol), 417 nm Φ 0.68.
Reactions of p‐quinone monoimines with lawesson reagent and phosphorus pentasulfide
Authors: Boulos Leila S. , Hennawy Ibtisam T. , Arsanious Mona H. N. 
Published: January 2005

Abstract2, 4‐Bis‐(4‐methoxyphenyl)‐1, 3, 2, 4‐dithiadiphosphetane‐2, 4‐disulfide [Lawesson reagent (LR)] 1 reacts with p‐quinone monoimine‐2a to give the novel benzo‐1,3,2‐oxathiaphosphol‐5‐(methanesulfonamido)‐2‐(4‐methoxyphenyl)‐2‐sulfide 4. On the other hand, the reaction of 2b and 3 with LR 1 leads to the formation of the benzo‐ and the naphtho‐1,3,2‐dithiaphosphol‐5 ‐(benzenesulfonamido)‐ 2‐ (4‐methoxyphenyl) ‐2‐sulfide 5, 6. Thiation of 2a, 2b, and 3 with P4S10 yields phenoxathiin derivatives 8a, 8b, and 9, respectively. The identity of the new products is established from analytical and spectroscopic evidence.
Reactivity of fused 1,3‐benzothiaphospholes: Formation of pentacoordinated derivatives
Authors: Baccolini Graziano , Orsolan Giorgio , Mezzina Elisabetta , Sgarabotto Paolo , Rizzoli Corrado 
Published: January 2005

AbstractFused 1,3‐benzothiaphospholes 2 (cis‐2,6,10‐trimethyl‐[1, 3]benzothiaphospholo[2,3‐b][1, 3]benzothiaphosphole) reacts with H2O2 and S8, giving the corresponding oxide and sulfide, respectively. The reactions of 2 with diethyl azodicarboxylate (DEAD)/catechol or DEAD/o‐aminophenol, o‐azidophenol, and tetrachloro‐o‐benzoquinone (TOB) give the first examples of spiro pentacoordinated phosphorus derivatives of this heterocyclic system. The X‐ray structural analysis of spiro compound 3 showed a trigonal bipyramidal configuration at phosphorus in which the three rings assume axial‐equatorial positions.
Intramolecular ring opening of a 2,3‐epoxy alcohol by a xanthate anionic center; stereospecific preparation of 2‐mercapto‐1,3‐diol units
Authors: Uenishi Jun'ichi , Motoyama Mitsuhiro , Nishiyama Yoshitaka , Hirota Yuichi , Kubo Yuki , Akashi Haruo 
Published: January 2005

AbstractStereospecific ring openings of optically active 2,3‐epoxy alcohols were performed by the reaction of 1, 3, 5, and 7 with carbon disulfide and sodium hydride to give the five‐membered xanthates 2, 4, 6, and 8. Both enantiomers of 2‐mercapto‐1,3‐diol triacetates, 11 and 14, were derived from 4 and 6, respectively. The ring opening reaction proceeded at −78°C to −30°C, and the yields were around 80%. However, at a higher temperature between 0°C to room temperature, a complicated reaction took place and led to the formation of two isomers of the cyclic thiol carbonates 15 and 16 from 1 or 5. These processes were also stereospecific, and mechanisms have been proposed. In the case of the 3,4‐epoxy alcohol 20, the epoxide ring opening gave the six‐membered xanthate 21 stereospecifically.
Reactions of dithioxo‐1,3,2λ5,4λ5‐dithiadiphosphetanes with trialkylsilyl and stannyl derivatives
Authors: Nizamov Il'yas S. , Kuznetzov Vladislav A. , Batyeva Elvira S. , Al'fonsov Vladimir A. , Pudovik Arkady N. 
Published: January 2005

AbstractThe reactions of homologues of Davy's reagent 1 and Lawesson's reagent 9 with trimethylalkylthiosilanes 2, trimethylsilyl enol ether 4, trimethyl(diethylamino)silane 7, trialkylalkoxystannanes 14, and trialkylalkylthiostannane 15 were studied. On the basis of these studies, novel advantageous methods of synthesizing S‐trialkylsilyl and stannyl esters of tetrathio‐, trithio‐, and amidotrithiophosphoric acids 3, 5, 6, and 4‐methoxyphenyldithio‐ and trithiophosphonic acids 10–13 were developed
The reaction of sulfur with dilithio compounds. The syntheses and structures of phenanthro [1, 10‐cd]‐1,2‐dithiole and phenanthro[4,5‐cde] [1,2]dithiin
Authors: Ashe Arthur J. , Kampf Jeff W. , Savla Paresh M. 
Published: January 2005

AbstractThe sequential reaction of selected polycyclic aromatic hydrocarbons with butyllithium/TMEDA/hexane and sulfur allows preparation of ring‐fused dithiins, dithioles, and thiophenes. In this manner, phenanthrene has been converted to phenanthro[4,5‐cde][1,2]dithiin and phenanthro[1,10cd]‐1,2‐dithiole. Yellow crystals of the dithiin form in C2/c (#15) space group with Z = 4, a = 13.537(3) Å, b = 8.933(2) Å, c = 9.601(4) Å, and β = 116.19 (2)°; while orange crystals of the dithiole form in P212121 (#19) space group with Z = 4, a = 4.1507(5) Å, b = 14.436(3) Å, and c = 16.972(3) Å. Full structures have been determined for both compounds.
New phenylboronic esters derived from inositol [1]
Authors: Salazar‐Pereda Verónica , Martínez‐Martínez Laura , Flores‐Parra Angelina , de Jesús Rosales‐Hoz María , Ariza‐Castolo Armando , Contreras Rosalinda 
Published: January 2005

AbstractWe have prepared two new tetracyclic phenylboronic esters 4 and 5 derived from myo‐inositol and from 1,2‐O‐isopropylidene‐myo‐inositol, respectively. The structures of these compounds were established from NMR and IR spectra, elemental analyses, and an X‐ray diffraction study in the case of 4. Compound 4 is a tetracyclic derivative of the less stable conformer of inositol (five axial hydroxy groups and one equatorial) with two dioxaboroline rings at opposite faces of the six‐membered ring, one formed between the boron atom and the axial hydroxyl groups at C‐3 and C‐5 and the other between the boron atom and the hydroxyl groups at C‐4 and C‐6, and a dioxaborolidine ring bridging C‐1 and C‐2 at axial and equatorial positions. A similar structure was found for 5 with the difference that bridging C‐1 and C‐2 there is a dioxolane ring. The boron atoms are planar with their attached atoms, stabilized by retrocoordination between the boron and oxygen and carbon atoms, respectively. The two phenyl rings that are in the same face of the molecule are essentially parallel, with a dihedral angle between planes of 28.26 ± 0.79°.
Molecular and electronic structure of bromamines
Authors: Novak Igor 
Published: January 2005

AbstractMolecular and electronic structures and properties of NH2Br, NHBr2, and NBr3 have been studied using ab initio calculations at the Hartree–Fock (HF) and MP2 levels with the aim of complementing very scarce experimental information available for the title molecules. The properties and molecular structures of bromamines are discussed in relationship to other haloamines (fluor‐ and chloramines).
Generation of germyl, stannyl, and plumbyl anions through nucleophilic cleavage of digermanes, distannanes, and diplumbanes
Authors: Buncel E. , Venkatachalam T. K. 
Published: January 2005

AbstractNucleophilic cleavage by potassium t‐butoxide on hexaphenyl digermanes, distannanes, and diplumbanes, in N,N′‐dimethylpropyleneurea (DMPU) solvent, provides a facile method for preparation of triphenyl germyl, stannyl, and plumbyl anions.
Heteroarylthiomethylsilanes. Synthesis and application to heteroarylthiomethylation of carbonyl compounds [1]
Authors: Hojo Makoto , Ishibashi Naruyasu , Hosomi Akira 
Published: January 2005

AbstractHeteroarylthiomethyltrimethylsilanes bearing a 2‐pyridyl, 2‐imidazolyl, 5‐tetrazolyl, or 2‐pyrimidinyl group, readily prepared by the reaction of heteroarylmercaptans with halomethyltrimethylsilane in the presence of a base, are synthetic equivalents of heteroarylthiomethyl anions, otherwise inaccessible, and are effective reagents for the introduction of a heteroarythiomethyl group at a carbonyl carbon atom in the presence of a catalytic amount of tetrabutylammonium fluoride.
Silyl stabilization of unsymmetrical bisketenes: 3‐(Trimethylsilyl) and 3‐(triisopropylsilyl)‐2‐substituted‐1,3‐butadiene‐1,4‐diones
Authors: Allen Annette D. , Ji Ruizhi , Lai Wing‐Yan , Ma Jihai , Tidwell Thomas T. 
Published: January 2005

AbstractThe bisketenes 2‐phenyl and 2‐methyl‐3‐(trimethylsilyl)‐1,3‐butadiene‐1,4‐dione (8 and 10 ) are calculated on the basis of additivity of substituent effects to be less stable than the 3‐phenyl and 3‐methyl‐4‐(trimethylsilyl)cyclobut‐3‐ene‐1,2‐diones ( 7 and 9 ) by 1.9 and 2.6 kcal/mol, respectively. In agreement with this prediction, 8 and 10 are formed by photolysis of 7 and 9, respectively, and undergo thermal reversion to their precursors at similar rates. The concentration of 8 in thermal equilibrium with 7 in CDCl3, as measured by 1H NMR spectroscopy, varied from 2.8% (161°C) to 0.5% (100.5°C), whereas the amount of 10 present at equilibrium with 9 was distinctly less. These measurements allowed the calculation of values ofΔG° (25°C) = 4.4 kcal/mol, ΔH° = 6.9±(1.3) kcal/mol, and ΔS° = 8.5 (±3.2) cal/deg mol for the conversion of 7 to 8, and the equilibrium concentration of 8 at 25°C was estimated to be 0.06%. The triisopropylsilyl analog 12 of 8 was prepared and at 66°C was 2.6 times more reactive in ring closure to the corresponding cyclobutenone compared to 8. Reactions of 8 and 10 with MeOH in CDCl3 give the isolable monoketenes 3‐phenyl and 3‐methyl‐2‐(trimethylsilyl)‐3‐carbomethoxy‐1‐ene‐1‐one (20,21). Reaction of 20 with excess MeOH or H2O gave the diastereomeric dimethyl 2‐(trimethylsilyl)‐3‐phenylsuccinates (22) or ester‐acids 24, respectively. Reaction of 8 with excess N‐methylaniline gave the diamide 25.
Reactions of the phosphinimine, (Me3Si)2NP  NSiMe3 with some unsaturated bifunctional alcohols, ketones, and amines
Authors: Angelov Christo M. , Cavell Ronald G. , Schmutzler Reinhard 
Published: January 2005

AbstractReactions of (Me3Si)2NPNsiMe3 with chloroalkanols, N‐methylpropargylamine, 3‐butyne‐2‐one, sucinimide, and chloroacetic acid were investigated. The first step in the reaction is always an addition of the nucleophilic part of the reagent (OH or NH) to the P‐atom. The second step in the reaction, migration of the proton to phosphorus, depends on the substituents on the phosphorus. Highly electronegative substituents increase the stabilization of the P(III) final product.
Phosphonic systems. Part 15. Addition of diethyl prop‐2‐enylphosphonate to aldehydes: Fragmentation vs. isomerization of kinetic products
Authors: Muller Elmar L. , Modro Tomasz A. 
Published: January 2005

AbstractLithiated diethyl prop‐2‐enylphosphonate adds to an aliphatic or an aromatic aldehyde, yielding a diastereomeric mixture of the kinetically controlled α‐adduct. Upon warming, these adducts decompose back to starting materials to give finally the thermodynamically controlled γ‐adducts, or undergo fragmentation to diethyl phosphate and (E) dienes. The distribution of the first product between these two pathways is a function of the aldehyde (aromatic vs. aliphatic) and of steric interactions operating within the two diastereomers of the adduct.
Matrix‐isolation and electronic structure of vinyl‐substituted silylenes and their complexes with bases [1]
Authors: Kira Mitsuo , Maruyama Toyotaro , Sakurai Hideki 
Published: January 2005

AbstractVinyl‐substituted silylenes, 2,5‐bis(methylene)‐1‐silacyclopentane‐1,1‐diyl (1) and 2‐methylene‐1‐silacyclopentane‐1,1‐diyl (2), generated photochemically from the corresponding trisilanes in 3‐methylpentane (3‐MP) at 77 K, showed broad bands at 505 and 475 nm, respectively, which were assigned to the n(Si)‐3p(Si) transition. The origin of the red shift in the n(Si)‐3p(Si) transition is ascribed to the significant lowering of the 3p(Si) orbital level caused by the vinyl substitution on the silylene; the relatively high‐lying 3p(Si) orbital can interact more effectively with the antibonding π* orbital than with the bonding π orbital of the vinyl group. The absorption spectra for 1 and 2 in the presence of several bases in 3‐MP glass matrix shifted significantly to blue due to the formation of the corresponding base complexes. Analysis of the spectral change of the silylenes upon complexation with bases was very constructive for the understanding of the structural characteristics of substituted silylenes.
Stereospecific synthesis of 6,7‐dihydro‐5H‐1,2,4‐triazolo[3,4‐b][1,3,4]thiadiazines
Authors: Ibrahim Yehia A. , Elwahy Ahmed H. M. , El‐Fiky Ayman E. M. 
Published: January 2005

AbstractThe reaction of 3‐mercapto‐4‐arylideneamino‐1,2,4‐triazoles 2b‐d, 3a‐d with ethyl bromoacetate and/or phenacyl bromide in hot DMF and triethylamine affords the stereochemically pure 7‐acyl‐6‐aryl‐6,7‐dihydro‐5H‐1,2,4‐triazolo[3,4‐b][1,3,4]thiadiazines 4b‐d, 5a‐d, 6b,d in which the consecutive hydrogen atoms N(5)H‐C(6)H‐C(7)H are cis to each other. This stereochemistry was determined by 1H NMR spectroscopy and confirmed by comparison with the spectrum of 3,6‐diphenyl‐6,7‐dihydro‐5H‐1,2,4‐triazolo[3,4‐b][1,3,4]thiadiazine 10. The latter was prepared by NaBH4 reduction of 3,6‐diphenyl‐5H‐1,2,4‐triazolo[3,4‐b][1,3,4]thiadiazine 9. The reported reactions offer two interesting stereospecific syntheses of the condensed heterocyclic compounds.
Mechanism of the controlled hydrolysis of (NPCl2)2NSOCl: Crystal and molecular structure of [KC12H24O6]+[NHPO2NPCl2NSOCl]−
Authors: Winter Herman , Meetsma Auke , van de Grampel Johan C. , Spek Anthony L. 
Published: January 2005

AbstractThe reaction mechanism of controlled hydrolysis of the inorganic ring system (NPCl2)2NSOCl in the presence of KCl and 18‐crown‐6 has been revised and is explained from steric constraints rather than from electronic considerations. The X‐ray structure of one of the hydrolysis products, [KC12H24O6]+‐[NHPO2NPCl2NSOCl]−, shows a dimeric structure of two centrosymmetrically related formula units kept together by hydrogen bridges and K … O coordination. Crystals are monoclinic, space group C2/c with a = 25.698(5), b = 8.223(2), c = 23.665(4) Å, β = 106.03(1)°, V = 4806(2) Å3, and Z = 8. The final R and Rw values are 0.048 and 0.044, respectively.
Sulfur derivatives of 3‐methyl‐5‐phenyl‐1,2,4,3‐triazaphosphole
Authors: Schmidpeter Alfred , Steinmüller Franz , Karaghiosoff Konstantin 
Published: January 2005

AbstractThe triazaphosphole 1 adds sulfur along with HCl or H2S to yield, respectively, the dihydrotriazaphosphole thiochloride 4 and sesquisulfide 5 (two diastereomers). In pyridine solution, 1 adds sulfur alone to yield the trimer of a triazaphosphole monosulfide 7. Its central cyclotriphosphazane trisulfide ring has a trans structure and a boat conformation.
Laser active cyanopyrromethene–BF2 complexes
Authors: Sathyamoorthi Govindaro , Boyer Joseph H. , Allik Toomas H. , Chandra Suresh 
Published: January 2005

AbstractTreatment with a mixture of formic and hydrobromic acids converted ethyl 3,4‐diethyl‐5‐methyl‐pyrrole‐2‐carboxylate 7a to 3,3′,4,4′‐tetraethyl‐5,5′‐dimethylpyrromethene hydrobromide 8a presumably via the condensation of α‐unsubstituted and α‐formylpyrrole intermediates 7c and 7e formed in situ. The corresponding 6‐cyanohexaalkylpyrromethane 9a was obtained by the addition of hydrogen cyanide to the pyrromethene 8a and was oxidized with bromine to an unstable pyrromethene 10a, an intermediate converted to 1,2,6,7‐tetraethyl‐3,5‐dimethyl‐8‐cyanopyrromethene–BF2 complex 3, (PMTEDC), λlas (plastic) 613–639 nm, in a reaction with boron trifluoride etherate. Ethyl 3,4,5‐trimethylpyrrole‐2‐carboxylate 7b was similarly converted to 1,2,3,5,6,7‐hexamethyl‐8‐cyanopyrromethene–BF2 complex 4, (PMHMC), λlas (plastic) 615–639 nm. Immediately after formation by a condensation between propionyl chloride and 2,4‐dimethyl‐3‐cyanopyrrole 16, unstable 3,3′,5,5′‐tetramethyl‐6‐ethyl‐4,4′‐dicyanopyrromethene hydrochloride 17 was treated with boron trifluoride etherate to give 1,3,5,7‐tetramethyl ‐2,6‐dicyano‐8‐ethylpyrromethene–BF2 complex 18, λlas (ethanol) 540–565 nm.