Studies on Organophosphorus Compounds: Synthesis and Reactions of Some New 5′-Cyano-2′-(4-methoxyphenyl)spiro[cycloalkane-1,6′-[1,3,2]thiazaphosphixane]-2′,4′-disulfide Derivatives

2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson's Reagent, LR, 1 ) reacts with cycloalkylidenecyanothioacetamides ( 2 and 3 ) to give 5'-cyano-2'-(4-methoxyphenyl)spiro [cyclopentane(cyclohexane)-1,6'-perhydro-[1,3,2]thiazaphosphixane]-2',4'-disulfide ( 4 and 5 ). The reaction of compounds 4 and 5 with f -halo compounds led to the formation of the substituted thio-compounds 6a-e and 7a-e , respectively, these compounds, upon treatment with sodium ethoxide, produce the corresponding thienothiazaphosphixine derivatives 8a-e and 9a-e respectively. Compounds 8a-e and 9a-e react with LR under different reaction conditions to give polyfused heterocyclic compounds 10a-d and 11a-d respectively. Treatment of compounds 8b and 9b with CS 2 and (CH 3 ) 2 SO 4 gave the corresponding dithiocarbamate methyl ester derivatives 12 and 13 , respectively, which on treating with hydrazine hydrate yielded compounds 14 and 15 respectively. Compounds 14 and 15 reacted with LR to yield compounds 16a , b and 17a , b respectively.     

First isolation of 1,3,2-dithiaphosphetane 2-sulfide

The treatment of tert-alkyl phenyl thioketones with Lawesson’s reagent (LR) gave two diastereomeric 1,3,2-dithiaphosphetane 2-sulfides in high yields. The structure of one of the major diastereomers was determined by X-ray crystallography. The reaction of 2-adamantanethione with LR yielded the corresponding spiro-1,3,2-dithiaphosphetane 2-sulfide derivative in 87% yield.     

Synthesis,Crystal Structure,and Flame Retardance of 2-(3-Silatranyl-Propylamino)-4-(2,4-Dichlorophenyl)-5,5-Dimethyl-1,3,2-Dioxaphosphinane-2-Sulfide

Abstract

2-(3-Silatranylpropylamino)-4-(2,4-dichlorophenyl)-5,5-dimethyl-1,3,2-dioxa phosphinane-2-sulfide 4 was synthesized by a nucleophilic substitution reaction of 2-chloro-1,3,2-dioxaphosphinane-2-sulfide 2 with γ-aminopropylsilatrane 3, which was prepared by the cyclization reaction of triethanolamine and γ-aminopropyltriethoxysilane. The structure of the title compound was confirmed by IR, ¹H NMR, ³¹P NMR, EI-MS, and elemental analysis as well as by single crystal X-ray diffraction and its thermal properties were studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). Thermal analysis and preliminary fire retardance testing suggest that compound 4 should function as a good flame retardant.     

Studies on organophosphorus compounds—XLI : Formation of 3-pyrazoline-5-thione disulfides from 3,5-pyrazolidinediones. C-alkylation of 3,5-pyrazolidinediones

4-Substituted-1,2-diphenyl-3,5-pyrazolidinediones (Phenylbutazone analogous) 1a–d react with 2,4-bi-(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-difulside (Lawesson Reagent (LR) with formation of the corresponding 3,3′-dithiobis (1,2-dihydro-3H-pyrazole-5-thione)'s 2a–d. When the 4-substituent contains a sulfoxide group this is deoxygenated to the sulfide by LR at room tmeperature. 1-Phthalazinone-4-thione, 1,4-phthalazine-dithione and ethyl aminothioxoacetate have also been prepared from the corresponding carbonyl compounds. Alkylation or acylation of 2a–d yielded 3H-pyrazole-3-thione derivatives 8 and 9. Alkylation of 1 with MeI in the presence of Et₃N at room temp. yielded the C-alkylated products 10 exclusively. X-RAy crystallographic investigations of 2b and 9a are presented.     

Self-assembly, structures, and photophysical properties of 4,4'-bipyrazolate-linked metallo-macrocycles with dimetal clips

By employing functional diimine ligands coordinated dipalladium(II,II) or diplatinum(II,II) clips as corners and the coplanar 4,4'-bipyrazolate dianion (L(2-)) ligand as linker, a series of bipyrazolate-bridged metallo-macrocycles, namely, [M8L4](NO3)8 (M = Pd(dmbpy), 1; Pd(bpy), 2; Pt(bpy), 3a; Pd(phen), 4; Pt(phen), 5; Pd(15-crown-5-phen), 6; Pd(18-crown-6-phen), 8; Pd(benzo-24-crown-8-phen), 10a; Pt(15-crown-5-phen), 7a, Pt(18-crown-6-phen), 9a; Pt(benzo-24-crown-8-phen), 11a) and [M6L3](NO3)6 (M = Pt(bpy), 3b; Pt(15-crown-5-phen), 7b; Pt(18-crown-6-phen), 9b; Pd(benzo-24-crown-8-phen), 10b; Pt(benzo-24-crown-8-phen), 11b), have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligands in aqueous solution. All these compounds have a crown-shaped cavity that can serve as host to solvent molecules and anions. The structures are characterized by elemental analysis, (1)H and (13)C NMR, ESI-MS, and in the cases of 1a (the BF4(-) salt of 1), 2a (the BF4(-) salt of 2), and 3b by single-crystal X-ray diffraction analysis. Photophysical properties for complexes 1 and 2 are discussed.     

AN UNUSUAL ADDITION AND RING-CLOSURE REACTION OF 1-(2-BROMOETHYL)-2,3-DIHYDRO- 3-PROPYL-1,3,2-BENZO-DIAZAPHOSPHORIN-4(1H)-ONE 2-OXIDE WITH CARBON DISULFIDE FOR A NEW AND CONVENIENT SYNTHESIS OF THE FUSED PHOSPHORUS HETEROCYCLIC COMPOUND

ABSTRACT

The reaction of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide takes an alternative pathway in the use of different bases. The sodium hydride mediated reaction leads to the formation of the tricyclic fused 1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-4-thia-3,4b,4a-thiazphosphaphenanthridine 4a-oxide via addition of H-P bond across the double bond of carbon disulfide followed by intramolecular cyclization. In the presence of triethylamine, refluxing a mixture of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide in benzene takes an unusual course with formation in excellent yield of the first example of fused phosphorus heterocyclic 4-[1′-(β-bromoethyl)-4′-oxo- 3′-propyl-1′,2′,3′,4′-tetrahydro-1,3,2-benzodiazaphosphorin-2′- sulfide]-1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-3,4b, 4a-thiazphosphaphenanthridine 4a,2′-dioxide, which was confirmed by spectroscopic methods, microanalyses and single crystal X-ray structure determination.     

Benzazole-N(SINGLE BOND)BH3 adducts. Reductive transposition of 2-benzimidazole, 2-benzothiazole,and 2-benzoxazole N(SINGLE BOND)BH3 adducts to 1,3,2-benzimidazaborole, 1,3,2-benzoxaborole,and 1,3,2-benzothiazaborole

1,3,2-Benzimidazaborole, 1,3,2-benzoxaborole, and 1,3,2-benzothiazaborole were synthesized from the corresponding 2-benzazole N(SINGLE BOND)BH₃ and 2-benzazole S(SINGLE BOND)BH₃ adducts through a reductive transposition from the isolobal fragment X(SINGLE BOND)C(sp²) (DOUBLE BOND) N(sp²) (SINGLE BOND) B(sp³) (X (DOUBLE BOND) N, O, S) to the fragment X(SINGLE BOND)B(sp²) (DOUBLE BOND) N(sp²) (SINGLE BOND) C(sp³). N(SINGLE BOND)BH₃ substitution shifts to lower frequencies 4-H, C-3a, and C-7a resonances. The X-ray diffraction analysis of 2-(o-methoxyphenyl)benzothiazole N(SINGLE BOND)BH₃ adduct is reported. Two new tetracyclic boron-bridged compounds were observed as by-products (6,9-(ethyl)-diaza-2-oxa-1-bora[3,4,7,8]-dibenzobycyclo[4.3.0]-nona-3,7-diene, 6d, and 8-aza-9-oxa-2-thia-1-bora-[3,4,7,8]dibenzobycyclo[3.4.0]nona-3,7-diene, 15d, when 2-(o-methoxyphenyl)-1-ethylbenzimidazole-BH₃ 6b and 2-(o-methoxyphenyl)-benzothiazole-BH₃ 15b adducts were heated. © 1996 John Wiley & Sons, Inc.     

Ein Netzwerk aus Iodid-Ionen und Iod-Molekülen in der Kristallstruktur von [Pr(Benzo-15-Krone-5)2]I21

A Three Dimensional Network of Iodide Ions and Iodine Molecules in the Crystal Structure of [Pr(Benzo-15-Crown-5)₂]I₂₁ Black polyhedra of [Pr(benzo-15-crown-5)₂]I₂₁ were grown from an ethanol / dichlormethane solution of PrI₃, benzo-15-crown-5 and I₂. The crystal structure (orthorhombic, P2₁cn, a = 1201.1(1), b = 2168.3(1), c = 2571.1(1) pm, Z = 4) is built up from sandwich like cations [Pr(benzo-15-crown-5)₂]³⁺ and polyiodide anions I₂₁^3-. This unique polyiodide anion exhibits a complex connection pattern of iodide ions and iodine molecules with variable bond lengths forming a complicated network.     

The Reaction of Phosphorus Decasulfide with some Hydrazides and their Hydrazones: New Route for Construction of Four‐membered,Five‐membered,and Six‐membered Phosphorus Heterocycles

Reaction of some selected benzoic acid hydrazides 1a – c with phosphorus decasulfide P₄S₁₀ in dry pyridine afforded some novel pyridine solvate of 1,3,4,2‐thiadiazaphospholes 2a – c . Similarly, treatment of their corresponding hydrazones 3a – c toward phosphorus decasulfide under the same reaction conditions gave the corresponding thio‐analog 4 and 1,3,2‐benzoxazaphosphinine and benzodiazaphosphinine pyridine solvates 5a,b , respectively. Treatment of (thio)semicarbazides and their corresponding (thio)semicarbazones with phosphorus decasulfide in dry pyridine yielded the novel 1,2,4,3‐triazaphospholidines 6a,b , and 1,3,2‐diazaphosphetidines 8a,b , respectively. Moreover, cyclization of (thio)carbohydrazides and their mono‐ (thio)carbohydrazones with phosphorus decasulfide produced 1,2,4,3‐triazaphospholidines 9a,b and 11a,b , respectively. The structures of these products were confirmed from analytical and spectral data.     

Synthesis of 5-substituted 2-(4- or 3-methoxyphenyl)-4(1H)-quinolones

5-Substituted 7-methoxy-2-(4- or 3-methoxyphenyl)-4(1H)-quinolones 8-17 have been synthesised in good yields from the corresponding 7-methoxy-2-(4- or 3-methoxyphenyl)-5-trifluoromethanesulfonate-4(1H)-quinolones 7 via palladium-mediated cross-coupling reactions or aromatic nucleophilic substitution (SN_Ar) reactions.     

Dual roles of substituted thiourea as reductant and ligand in CuAAC reaction

A highly efficient catalytic system, CuSO₄·5H₂O/1-(4-methoxyphenyl)-3-phenylthiourea, for the copper(I)-catalyzed azide–alkyne cycloaddition reaction (CuAAC) was discovered. In the above catalytic system, substituted thiourea acts both as a reductant and a ligand. CuSO₄·5H₂O/1-(4-methoxyphenyl)-3-phenylthiourea is both an economical and efficient catalyst for the CuAAC reaction. In addition, the new catalytic system has advantageous features including mild and green reaction conditions, and broad substrate compatibility. A variety of 1,4-disubstituted 1,2,3-triazoles have been prepared with good to excellent yields with the CuSO₄·5H₂O/1-(4-methoxyphenyl)-3-phenylthiourea catalytic system in aqueous solution.     

A facile synthesis and spectral (ir, 1H, 13C, 31P nmr) studies of 2,10-dichloro-6-aryloxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfides

The synthesis of new 2,10-dichloro-6-aryloxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfides 4 was achieved in two steps with high yields from the simple materials 5,5′-dichloro-2,2′-dihydroxydiphenyl-methane (1) and thiophosphoryl chloride (2) which produced the key intermediate 2,6,10-trichloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfide (3) . Treatment of 3 with substituted phenols under phase transfer catalytic (PTC) conditions led to members of 4 . Long range coupling [⁵J_(P,H) = 3.6 Hz] was observed between phosphorus and one of the bridged methylene protons in 4 . A ¹³C nmr analysis revealed ²J_(P,O,C), ³J_(P,O,C) ⁴J(P,O,C) and ⁵J(P,O,C) couplings. All ³¹P nmr chemical shifts for thirteen members of these new heterocycles are reported for the first time. The nmr data are not totally definitive to confirm a boat-chair as the major conformer for the central eight-membered dioxaphosphocin ring, but such a conformer is tentatively suggested as favored.     

The Synthesis and Biological Activities of N-(3-pyridylmethyl) N ′-(trans-2-thio-4-substitutedphenyl- 5,5-dimethyl-1,3,2-dioxaphosphinane-2-yl)thioureas

A series of novel title compounds were synthesized by the addition reaction of trans 2-isothiocyano-4-substitutedphenyl-5, 5-dimethyl-1,3,2-dioxaphosphinane 2-sulfide to 3-aminomethylpyridine or 2-chloro-5-amino methylpyridine. Their structures were confirmed by ¹H NMR, ³¹P NMR, IR, MS, and elemental analyses. Results of preliminary bioassay showed that all new compounds possess good fungicidal activity and insecticidal activity to some extent.     

Axial and Equatorial Substitution of Dimethylamine on Phosphorus in the 1,3,2-Oxazaphosphorinane Ring System: Structures of 2-Dimethylamino-Phenyl-2H-1,3,2-oxazaphosphorinane-2-Oxides

X-ray structures of trans-2-dimethylamino-5-phenyl-2H-1,3,2-oxazaphosphorinane-2-oxide, 5b , and trans-2-dimethylamino-6-phenyl-2H-1,3,2-oxazaphosphorinane-2-oxide, 6c , have been determined. These two compounds have been prepared in a straightforward manner by a reaction of cyclization of Mc₂NP(O)Cl₂ with the corresponding 3-amino-2-phenylpropanol and 3-amino-1-phenylpropanol, respectively, to produce (5b, 6b) and (5c, 6c) , and were separated into pure forms by chromatography. Crystal data of 5b : space group P_ccn, a = 10.675(5), b = 31.685(9), c = 7.217(3) Å, R = 0.065 for 1040 reflections. Crystal data of 6c: space group P-1, a = 9.803(6), b = 12.455(5), c = 12.690(2) Å, α = 114.11(2), β = 80.88(2), γ = 111.64(4)°, R = 0.035 for 3534 reflections. For the pair 5b and 6b , the slowly-migrating 5b is trans (Ph and P = O group trans) with the configuration of 2RS, 5RS, hence 6b is the cis isomer. For the pair 5c and 6c , the slowly migrating 6c is trans with the configuration of 2RS, 6SR; hence 5c is the cis isomer. In both X-ray structures the 1,3,2-oxazaphosphorinane rings are chair-like with the P-end essentially flattened. With a conformationally demanding 5-phenyl substituent, 5b has an axial Me₂N whereas with also a conformationally demanding 6-phenyl substituent, 6c has an equatorial Me₂N. For 6c , the exocyclic P-N bond has partial double bond character: the geometry about exocyclic N is planar. On the other hand, for 5b , the geometry about exocyclic N deviates considerably from planarity, the sum of the angles around N being 343.3°. In the crystalline state, the two crystallographically independent molecules of 6c are linked together in a hydrogen-bonded system involving the water molecule.     

ortho effect on the nitrosation of the 2,3-diphenyl-5(2-methoxyphenyl)pyrrole

A comparison of the behaviour on the nitrosation of the isomers 5-(2-methoxyphenyl)- ( 1a ) 5-(3-methoxyphenyl)- ( 1b ) and 5-(4-methoxyphenyl)2,3-diphenylpyrroles ( 1c ) carried out in the usual way with iso-amyl nitrite in a solution of sodium ethoxide in ethanol evidences that 1a is dramatically less reactive with respect to 1b and 1c . The different reactivity was ascribed to the occurrence of a strong hydrogen bond involving pyrrole N? H and the ortho-methoxy group.     

Synthesis of Halogenated 1,5-Diarylimidazoles and Their Inhibitory Effects on LPS-Induced PGE2 Production in RAW 264.7 Cells

A series of halogenated 1,5-diarylimidazole compounds were synthesized and their inhibitory effects on LPS-induced PGE₂ production in RAW 264.7 cells were evaluated. A wide variety of 2,4-, 4-, and 2-halogenated 5-aryl-1-(4-methylsulfonylphenyl)imidazoles were synthesized for SAR study via two different pathways. Overall, 4-halogenated 5-aryl-1-(4-methylsulfonylphenyl)imidazoles, regardless of the species of halogen, exhibited very strong inhibitory activities of PGE₂ production. Among them, 4-chloro-5-(4-methoxyphenyl)-1-(4-methylsulfonylphenyl)imidazole (3, IC₅₀ 3.3 nM ± 2.93), and 4-chloro-5-(4-chlorophenyl)-1-(4-methylsulfonylphenyl)imidazole (13, IC₅₀ 5.3 nM ± 0.23) showed the best results.     

Stereochemistry of organophosphorus cylic compounds—XV: Synthesis of tetramethylammonium salt of 2-oxo-2-thio-1,3,2,-oxazaphosphorinan and its crystal and molecular structures

2-Hydroxy-1,3,-2-oxazaphosphorinan-2-thione (5) was prepared by alkaline hydrolysis of 2-chloro-1,3,2-oxazaphosphorinan-2- thione (6). Treatment of the latter with sodium methoxide afforded the 2-methoxy-derivative 7 from which the tetramethylammonium salt of the thioacid 5 was obtained by the action of trimethylamine. The structure of this salt has been determined by the direct method and refined by least-squares to R = 0.0734, a = 12.303(4), b = 9.041(3), c = 10.419(2) Å, space group P2₁2₁2₁. The 2-oxo-2-thio-1,3,2-oxazaphosphorinanyl anion is in the chair form with the exocylic S and O atoms in an axial and equatorial position, respectively. An intermolecular H-bond between S and the endo-cyclic N atom is present in the solid-state structure.     

Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali Cations

A series of double-armed benzo-15-crown-5 lariats (3–8) have been synthesized by the reaction of 4′, 5′-bis(bromomethyl)-benzo-15-crown-5 (2) with 4-hydroxybenzaldehyde, phenol, 4-chlorophenol, 4-methoxyphenol, 2-hydroxybenzaldehyde, and 4-acetamidophenol in 43 ~ 82% yields, respectively. The complex stability constants (K _S) and thermodynamic parameters for the stoichiometric 1:1 and/or 1:2 complexes of benzo-15-crown-5 1 and double-armed crown ethers 3–8 with alkali cations (Na⁺, K⁺, Rb⁺) have been determined in methanol–water (V/V=8:2) at 25 °C by means of microcalorimetric titrations. As compared with the parent benzo-15-crown-5 1, double-armed crown ethers 3–8 show unremarkable changes in the complex stability constants upon complexation with Na⁺, but present significantly enhanced binding ability toward cations larger than the crown cavity by the secondly sandwich complexation. Thermodynamically, the sandwich complexations of crown ethers 3-8 with cations are mostly enthalpy-driven processes accompanied with a moderate entropy loss. The binding ability and selectivity of cations by the double-armed crown ethers are discussed from the viewpoints of the electron density, additional binding site, softness, spatial arrangement, and especially the cooperative binding of two crown ether molecules toward one metal ion.     

Axial and Equatorial Dimethylamine Substitution on Phosphorus in the 1,3,2-Oxazaphosphorinane Ring System: Structures of 2-Dimethylamino-4-Phenyl-2H-1,3,2-Oxazaphosphorinane-2-Oxides

Single crystal x-ray structures of the diastereomeric 2-dimethylamino-4-phenyl-2H-1,3,2-oxazaphosphorinane-2-oxides, 5c and 6c, have been determined. The pair has been prepared in a straightforward manner by reaction of 3-amino-3-phenylpropanol with Mo₂P(O)Cl₂, and separated into pure forms by column chromatography. Crystal data of 5c: space group P2₁/n, a = 11.087(3), b = 6.087(6), c = 18.465(6)Å, β = 98.40(3)°, R = 0.035 for 1845 reflections. Crystal data of 6c: space group P2₁/n, a = 11.176(2), b = 6.893(2), c = 16.673(3)Å, β = 95.29(1)°, R = 0.037 for 1253 reflections. The fast-migrating 5c is cis (Ph and P = O group cis) with the configuration of 2RS, 4SR. The slow migrating 6c is trans with the configuration of 2RS, 4RS. In both structures the 1,3,2-oxazaphosphorinane rings are chair like with the P-end essentially flattened, The skeleton made up with 4-phenyl-1,3,2-oxazaphosphorinane is essentially the same. With a conformationally demanding 4-phenyl substituent, 5c has an axial Mc₂N whereas 6c has an equatorial Me₂N. For 6c, the exocyclic P-N bond has a partial double bond character the geometry about exocyclic N is planar. On the other hand, for 5c, the geometry about exocyclic N deviates considerably from planarity, the sum of the angles around N being 348.1°. In the crystalline state, the screw-related 5c molecules are hydrogen bonded whereas in the crystalline state, the centro-symmetrically related 6c molecules are paired-up by hydrogen bonds, both through the N-H and P = O system.     

New Reactions of Olefins with Tetraphosphorus Decasulfide,Thiophosphoryl Trichloride,and Phosphorus Trichloride

Abstract

In contrast to difficultly characterizable products of olefins with P₄S₁₀ alone, the reactions of olefins with P₄S₁₀ in the presence of PSCI₃ (and in some cases, PCl₃) afforded distillable products amenable to characterization. Ethylene with P₄S₁₀, PSCl₃, and PCl₃ gave 1,2-ethanediylbis (phosphonothioic dichloride) in good yield. Propylene with P₄S₁₀ and PSCl₃ afforded several open-chain phosphonothioic chlorides and at higher temperatures 2-chloro-1,2-thiaphospholane 2-sulfide. 1- or 2-Butene yielded the 5-methyl homolog. Cyclohexene yielded 7-chloro-6-thia-7-phosphabicyclo [3.2.1] octane 7-sulfide and 4-methylcyclohexene yielded the 5-methyl homolog. Norbornene gave stereoisomeric 3-chloro-2-thia-3-phosphatricyclo [4.3.0.0^4,8] nonane 3-sulfides. Norbornadiene gave 3-chloro-2-thia-3-phosphatricyclo [4.3.0.0^4,8] non-6-ene 3-sulfide. Camphene reacted with P₄S₁₀ and PSCl₃ in good yield at ambient pressure and moderate heating to produce a characteristic Wagner-Meerwein rearrangement product, 3-chloro-3-phospha-4-thia-10, 10-dimethyltricyclo-[5.2.1.0^1,5] decane 3-sulfide. Butadienes with P₄S₁₀ and PSCl₃ afforded Diels-Alder-like 2-chloro-3,6-dihydro-2H-1, 2-thiaphosphorins. These products were characterized by nmr and, in some instances, by hydrolysis to characterizable products. The products are generally consistent with electrophilic mechanisms.