Reaction of 2-Ethyl-1,3,2-bezoxaphospholine with Calix[4]resorcinarenes

By reaction of calix[4]resorcinarene with 2-ethyl-1,3,2-benzoxazaphospholine in 1:1 ratio we prepared a cavitand possessing one dioxaphosphocinic fragment on the upper circle of the molecule. Reaction of the same compounds in ether solution in 1:4 and 1:8 ratio according to the data of spectral methods leads initially to formation of addition product, the P-H phosphorane with composition 1:4. This compound is not stable and on keeping forms 2-oxo-2-ethyl-1,3,2-benzoxazaphospholine, spirophosphorane, o-aminophenol and phosphorylated calixarene. In the reaction of the aminoalkylated calixarene with 2-ethyl-1,3,2-benzoxazaphospholine we isolated a compound possessing four hydrophoshonyl fragments on the upper circle of the calixarene matrix.     

Synthesis and Transformations of 2-Hydroxy-2-(benzotriazol-1-yl)-1,4-naphthoquinone

2-Hydroxy-3-(benzotriazol-1-yl)-1,4-naphthoquinone reacts with o-phenylenediamine and 4-chloro-2-aminophenol to give cyclization products: 5-oxo-6-(benzotriazol-1-yl)-5,6H-benzo[a]phenazine and 5-oxo-6-(benzotriazol-1-yl)-10-chlorobenzo[a]phenoxazine; the reaction with aniline yields the quaternary anilinium salt, and benzoyl chloride and benzenesulfonyl chloride acylate the nitrogen atom of the benzotriazolyl moiety.     

Heterocyclic compounds from 3,3-dimercapto-1 -aryl-2-propen-1-ones. Note 2. Condensation with o-aminothophenol and o-aminophenol

The condensation of 3,3-dimercapto-1-phenyl-2-propen-1-one with o-aminothiophenol and o-aminophenol in hot xylene gave 2-phenacylbenzothiazole ( 3 ) and 2-phenacylbenzoxazole ( 5 ). When the reaction with o-aminophenol was carried out in hot benzene, 2-beuzoylthioacctamidophenol ( 4 ) was obtained, which, heated in hot xylene gave 5. Ethyl benzoylacetale by reaction with o-aminothiophenol gave 3 , whereas by reaction with o-aminophenol gave no heterocyclic compound. However, we were able to isolate 2-benzoylacetamidophenol ( 6 ), ethyl β-phenyl-β-(o-hydroxy)phenyliminopropionate ( 7 ), and 2-[β-(o-hydroxy)anilino] cinnamoylamidophenol ( 8 ). Ir and nmr spectra of synthesized compounds point out the existence of tautomers.     

Synthesis of dimeric 1,3,2λ5-benzoxazaphospholes from phosphinic acid derivatives by silylation/desiloxylation

The reaction of N,N,O-tris(trimethylsilyl)-o-aminophenol with two equivalents of phosphinic chloride yielded dimeric 2,2-disubstituted 1,3,2λ⁵-benzoxazaphospholes and trimethylsilyl phosphinate. The chlorides having the bulk substituents (o-chlorophenyl or tert-butyl) at phosphorus or containing P N and P O bonds (instead of a P C bond) either didn't react at all or reacted to retain the phosphoryl group. Being stable in solution at 20°C, the individual diastereoisomers of dimeric 1,3,2-benzoxazaphospholes were converted upon warming to an equilibrium mixture of isomers. When reacted with another dimer each gave a mixed dimeric compound having two different phosphorus atoms in the molecule.     

Chemistry of 2-methylene-2,3-dihydro-3-furanones

2-p-Chlorobenzoylmethylene-5-phenyl-2,3-dihydro-3-furanone reacts with arylamines orN-arylideneamines to form the products of ring opening, 1,6-diaryl-1-arylamino-4-hydroxy-1,4-hexadiene-3,6-diones. The reaction of 5-aryl-2-p-chlorobenzoylmethylene-2,3-dihydro-3-furanones witho-aminophenol afforded 3-p-chlorobenzoylmethylene-3,4-dihydro-2H-benzo[b]-1,4-oxazin-2-one. Nucleophilic attack of amines is directed either to electrophilic centers at the C(5) and C(2) atoms or to the carbonyl group of the 2-phenacylidene substituent of the 3-oxofuran ring. For communication 15, see Ref. 1. Translated fromIzestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1340–1345, July, 1997.     

Properties of 4-Chloromethyl-2,2-dimethyl-1,2-dihydrobenzo[f]isoquinoline

We have shown that 2,2-dimethyl-4-chloromethyl-1,2-dihydrobenzo[f]isoquinoline, which displays the properties of an enamine, reacts with oxalyl chloride with annelation of the dioxopyrroline ring. At the same time, this compound reacts with S-, O-, and CN-nucleophiles.     

Reactions of 6-Amino-5-Cyano-3-Methyl-1,4-Diphenyl-1H 4H-Pyrano[2,3-C]Pyrazole and its Methanimidate

Reaction of 6-amino-5-cyano-3-methyl-1,4-diphenyl- 1H,4H-pyrano[2,3-c]pyrazole 1 with triethyl orthoformate in acetic anhydride gave its methanimidate 2, which reacts with primary aliphatic and aromatic amines to give 4,6-dihydro-3-methyl-1,4-diphenyl-6- (alkyl)pyrazolo[4′,3′:5,6]pyrano[2,3-d]pyrimidine-5(lH)- imine 3 and the starting compound 1 , respectively. Treatment of 1 with o-aminophenol gave 5-(2-benzoxalyl)- 1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazol- 6-amine 9.     

Condensation of o-aminophenol and α-dicarbonyl compounds. Part 2. Dibenzoxazolines

The study of 2′-aryl-2,2′-dibenzoxazolines (II), obtained together with 2-hydroxy-(2H)-1,4-benzoxazines (1) by condensation of o-aminophenol with a series of phenylglyoxal derivatives, emphasized that these compounds are an equilibrium mixture of dibenzoxazolines and related tautomeric ketimine forms. This behaviour was widely investigated by ir, uv and pmr spectroscopy. J. Heterocyclic Chem., 14, 957 (1977)     

Über die sterische Anordnung von Chrom(III)- und Kobalt(III)-1:2-Azofarbstoff-Komplexen mit annellierten 5/5- und 5/6-Chelatringen,gebildet mit Azofarbstoffen aus 4,5-Diphenylimidazol als Kupplungskomponente

On cuppling 4,5-diphenylimidazole with a diazotised o-aminophenol or with a diazotised anthranilic acid, tridentate ligands are produced which, on co-ordination with the metal atom, form ortho-condensed 5/5- or 5/6-membered rings. Both ligand systems can form 1:2 chromium (III) and 1:2 cobalt (III) complexes having the DREW -PFITZNER arrangement. The dimensions of the o-carboxyazo dyestuff fit well, those of the o-hydroxyazo dyestuff fit badly into the octahedral crystal lattice. In the same way, on co-ordination one dyestuff is not deformed but the other is very greatly deformed, as can be concluded from a comparison of the electron spectra of the metal-free dyestuff with those of the complexes.     

Synthesis and Some Properties of 2-(5-Methyl-2-Phenyl-2H-1,2,3-Diazaphosphol-4-yl)-4H-Benzo[d]-1,3,2-Dioxaphosphorin-4-One

Abstract

2-(5-Methyl-2-phenyl-2Н-1,2,3-diazaphosphol-4-yl)-4H-benzo[d]-1,3,2-dioxaphosphorin-4-one 1 readily reacts with hexafluoroacetone, mesoxalic acid diethyl ester, trifluoropyruvic acid ethyl ester and chloral to give 2-(5-methyl-2-phenyl-2H-1,2,3-dizaphosphole-4-yl)-derivatives of 1,3,2- and 1,4,2-dioxaphosphepines.     

Specific Features of Reaction of 2-R-Benzo[e][1,3,2]dioxaphosphinin-4-ones with Perfluorodiacetyl. Synthesis and Steric Structure of 4′,5′-Bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ 5-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2]dioxaphosphole]

2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones react with perfluorodiacetyl under mild conditions to form relatively labile spirophosphoranes containing a 1,3,2-dioxaphosphole ring. These compounds gradually convert to more stable 2-R-4,5-bis(trifluoromethyl)-1,3,2λ⁵-dioxaphosphole 2-oxides and diastereometic 2-R-4-(trifluoroacetyl)-4-(trifluoromethyl)benzo[f][1,3,2λ⁵]dioxaphosphepine 2-oxides, whose structure was confirmed by means of NMR and IR spectroscopy. The structure of 4′,5′ -bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ ⁵-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2]dioxaphosphole] was confirmed by X-ray diffraction analysis.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 587–599.Original Russian Text Copyright © 2005 by Konovalova, Mironov, Ivkova, Zagidullina, Gubaidullin, Litvinov, Kurykin.     

On the condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-dioxaborines with cyano acetic acid derivatives. Formation and transformation of 3-cyano-4-methyl-benzo[b]pyran-2-ones and their 2-imine precursors

Summary By condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-2H-dioxaborines (12) with cyano acetic acid derivatives in presence of weak bases, 3-cyano-4-methyl-benzo[b]pyran-2-ones (13) or their 3-cyano-4-methyl-benzo[b]pyran-2-imine precursors (14) are available in satisfactory yields.

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Zur Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen mit Cyanessigsäure- Derivaten. Bildung und Umwandlung von 3-Cyano-4-methyl-benzo[b]pyran-2-onen und ihrer 2-Imino-Vorstufen

Zusammenfassung Durch Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen (12) mit Cyanessigsäure-Derivaten in Gegenwart von Hilfsbasen entstehen in befriedigenden Ausbeuten 3-Cyan-4-methyl-benzo[b]pyran-2-one (13) oder ihre 3-Cyan-4-methyl-benzo[b]pyran-2-imino-Vorstufen (14).

     

Complexes of 2,2′,2″-Nirtilotriphenol. Part IV. Cage Compounds with Phosphorus(III) and Phosphorus(V)

The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite ( II ), 2,2′,2″-nitrilotriphenyl phosphate ( III ) and of a hydrolysis product of II , 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate ( IV ), are reported, as well as crystal structures of II and IV . Phosphite II shows a bicycloundecane framework; no N?Pinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.     

Reactions of Phenylenedioxytrihalophosphoranes with Arylacetylenes: III. Features of Reactions of 5,6-Dihalo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-Dichloride with Arylacetylenes

According to the NMR, IR, and high-resolution mass spectra, the major products of the reactions of 5,6-dibromo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-dichloride with arylacetylenes are 4-aryl-6,7-dibromo-2-chloro-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxides. The steric structure of one of the hydrolysis products, 2-hydroxy-6,7-dibromo-4-phenyl-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxide, was studied by single crystal X-ray diffraction.     

Electro-oxidation of o-aminophenol studied by cyclic voltammetry and surface enhanced Raman scattering (SERS)

Cyclic voltammetry and surface enhanced Raman scattering (SERS) spectra were used over a wide pH range to examine the products of o-aminophenol oxidation on a roughened silver electrode. The results of the study indicated that at least two oxidation products are formed at the stationary potential of the electrode. The major product in alkaline and neutral media was identified as 2,2′-dihydroxyazobenzene, a linear dimer formed by N---N coupling of o-aminophenol cation radicals. In acidic solutions the cyclic dimer 3-aminophenoxazone formed by C---N coupling of o-aminophenol cation radicals dominates on the silver electrode.     

Action of 1,2-diamines and o-aminophenols on 1-alkyl-3-carboxyindole-2-acetic acid anhydrides. Preparation of new ring systems

1-Alkyl-3-carboxyindole-2-acetic acid anhydrides (I) react with ethylenediamine and with o-phenylenediamine to give directly 10-alkylimidazo[3,2:1′,2′]pyrido[4,5-b]indol-5(1H)-ones (II) and 5,6-dihydro-5-alkyl-13H-indolo[2′,3′:4,5]pyrido[1,2-a]benzimidazol-13-one (V), respectively. However, anhydrides I react with o-aminophenol and with o-aminothiophenol to give carboxyindole-acetanilide derivatives IX, which can be cyclised to indolo[2′,3′:4,5]pyrido[2,1-b]benzoxazolone and indolo[2′,3′:4,5]pyrido[2,1-b]benzthiazolone (XI). Some derivatives of II and V were prepared to help in elucidating the structures.     

An Efficient and Facile Synthesis of Novel Benzimid-(Thi) Azole Dicarboxaldehydes as a Versatile Precursors for new Ox-, Thi-and Diazepine Derivatives

Abstract

Novel 2-cyanomethylbenzimid-(thi)-azole-2,2-dicarboxaldehydes were prepared in quantitative yields and reacted easily with o-aminophenol derivatives to yield new multi-functionallized ox-, thi- and diazepine derivatives in one-pot reaction.     

Die Struktur des Adduktes aus 3-Dimethylamino-2,2-dimethyl-2H-azirin und 3-Methyl-2,4-diphenyl-1,3-oxazolium-5-olat. Vorläufige Mitteilung

Structure of the adduct from 3-dimethylamino-2,2-dimethyl-2H-azirine and 3-methyl-2,4-diphenyl-1,3-oxazolium-5-olate 3-Dimethylamino-2,2-dimethyl-2H-azirine ( 1 ) reacts with 3-methyl-2,4-diphenyl-1,3-oxazolium-5-olate ( 5a ) to give a 1:1 adduct ( 7 ) in a 88% yield. Its crystal structure has been determined by X-ray analysis (direct methods) and refined with 1056 structure amplitudes to R = 0,032. The crystal system is monoclinic, space group P2₁/c, with unit cell dimensions a = 10.663, b = 9,828, c = 18,592 Å, and β = 90,63°. It is obvious that 4-dimethylamino-5,5-dimethyl-2-[α-(N-methyl-benzamido)benzyliden]-Δ³-1,3-oxazoline ( 7 ) arises from an addition of 1 to the valence-polaromeric ketene form 5b of the mesoionic oxazolone 5a (Scheme 3).     

New 3,3′[2,2′‐oxy‐bis‐(oxazaborolidine)]‐ethylenes. Structural studies by NMR,X‐ray,and quantum chemistry methods

3,3′‐[2,2′‐Oxy‐bis‐(4S‐methyl, 5R‐phenyl‐1,3,2‐oxazaborolidine)]ethylene ( 4a ) and 3,3′‐[2, 2′‐oxy‐(4S‐methyl‐5R‐phenyl‐1,3,2‐oxazaborolidine)‐ (1,3,2‐benzoxazaborolidine)]ethylene ( 4b ) were synthesized by the reaction of N,N′‐bis‐[(1R,2S)‐norephedrine]oxalyl ( 3a ) or N,N′‐[((1R,2S)‐norephedrine, o‐hydroxyphenylamine]oxalyl ( 3b ) with BH₃‐THF. The molecular structure of these compounds was established by NMR and infrared spectroscopy. The molecular geometry for 4 was studied by means of theoretical methods, resulting in structures that were in total agreement with those obtained by spectroscopy data and X‐ray diffraction. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:513–519, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20151     

Synthesis and Biological Activity of 4-Chloromethyl-substituted 1,3,2-Dioxaphosphorinanes Phosphates and Amidophosphates

A series of 2-N and 2-O-substituted 2-oxo-4-chloromethyl-1,3,2-dioxaphosphorinanes were prepared by reaction of amines and alcohols with 2-oxo-2-chloro-4-chloromethyl-1,3,2-dioxaphosphorinane. The structure of compounds obtained was proved by means of ¹H and ^{1 3}C NMR spectroscopy. Some cyclic amidocyclophosphates possessed biological activity as inhibitors of mitotic fission and of Na⁺/H⁺ exchange.