Stevens rearrangement of heterocyclic ammonium salts containing prop-2-yn-1-yl group

Stevens rearrangement was studied of ammonium salts where piperidinium or morpholinium groups are linked to prop-2-yn-1-yl moiety and labile hydrogen atom functions (methoxycarbonylmethyl, phenacyl, cyanomethyl). In the case of phenacyl analog furan derivatives were formed, in other cases dienamines were the reaction products.     

Stevens rearrangement of ammonium salts containing 2-propynyloxy or tert-butoxycarbonylmethyl groups

The Stevens rearrangement of ammonium salts containing 2-alkenyl, 2-alkynyl, or benzyl groups along with 2-propynyloxy or tert-butoxycarbonylmethyl was studied. Under the action of a suspension of sodium phenolate in benzene the salts containing a 2-propynyloxycarbonylmethyl group form 2-propynyl esters of 2-dialkylamino-4-pentenoic acids, whereas with sodium methylate as the basic reagent, rearrangement is preceded by an almost complete transesterification. The salts containing a tert-butoxycarbonylmethyl group undergo almost no transesterification under the action of sodium methylate. The tert-butyl fragment in the ester group of the salt with a benzyl group exerts a fairly strong effect on the regiochemistry of the rearrangement and on the prototropic isomerization of the 3,2-Stevens rearrangement of the salts with 2-butynyl or 3-phenyl-2-propynyl groups.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1321–1326.Original Russian Text Copyright © 2004 by Babakhanyan, Ovakimyan, Grigoryan, Kocharyan.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis of the unsaturated diamines by the Stevens rearrangement of 4-diethylaminobutyn-2-yl-containing ammonium salts

Ammonium salts containing 4-diethylaminobutyn-2-yl and 2-alkenyl groups undergo the Stevens 3,2-rearrangement under the action of potassium hydroxide in anhydrous benzene to form the unsaturated diamines.     

Cyclization of dialkyl(4-hydroxy-2-butynyl)-(3 isopropenylpropargyl)ammonium salts and intramolecular recyclization of the resultant products

2,2-Dialkyl(4-hydroxy-2-butynyl)(3-isopropenylpropargyl)ammonium chlorides in the presence of 0.2 molar equivalents of KOH in water undergo facile cyclization to give 2,2-dialkyl-4-hydroxymethyl-6-methylisoindolinium chlorides, which recyclize to dialkyl(6-methyl-1,3-dihydro-4-isobenzofuranylmethyl)amines by the action of a two-fold molar excess of KOH in water. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 528–532, April, 2007.     

Reaction of 2-allyloxy(thio)-4-methylquinolines with halogens

It was established that the halogenation of 2-allyloxy(thio)-4-methylquinolines leads to the formation of 3halogenomethyl-2, 3-dihydrooxazolo(thiazolo)[3, 2-a]quinolinium halides.Chelyabinsk State University, Chelyabinsk 454136. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1252–1254, September, 1996. Original article submitted July 7, 1996.     

4-(5-aryl-2-oxazolyl)benzenesulfonic acid derivatives containing a dimethylamino group

Condensation of 4-chlorosulfonyl- and 4-fluorosulfonyl-benzoyl chlorides with p-dimethylamino--aminoacetophenone followed by cyclodehydration of the resulting amides leads to the formation of 4-(5-dimethylaminophenyl-2-oxazolyl)benzenesulfonyl halides, and the corresponding sulfonic ester, sulfomorpholide, sulfonamide, and sodium salt are synthesized from them. The spectral and luminescence properties of the compounds synthesized have been studied in toluene, ethanol, and DMF. The ability of the sulfonyl group to transmit the electronic effects of the substituents on it to the overall molecular -electron system of 2,5-diaryloxazole has been demonstrated. Salvation fluorochromia has been detected in polar solvents. In some of the compounds studied the Stokes shift exceeds 200 nm.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 234–237, February, 1993.     

Cyclodimerization of the Stevens Rearrangement Products from 4-Alkoxy-2-butynyl(alkoxycarbonylmethyl)dimethyl-ammonium Salts into Cyclohexene Derivatives

4-Alkoxy-2-butynyl(alkoxycarbonyl)dimethylammonium salts undergo 3,2-Stevens rearrangement by the action of the corresponding sodium alkoxides. Hydrolysis of the rearrangement products with dilute hydrochloric acid gives 3-alkoxy-2-oxo-3-pentenoic acid esters which are converted into 3-methylene-2-oxo-4-pentenoates via 1,4-elimination of alcohol. [2 + 4]-Cyclodimerization of 3-methylene-2-oxo-4-pentenoates leads to 1,4-bis(alkoxalyl)-4-vinylcyclohexenes.     

Preparation of 3-(4-chlorophenyl)-2-(2-aminothiazol-4-yl)-5-methoxybenzo[b]furan derivatives and their leukotriene B(4) inhibitory activity

A series of 3-(4-chlorophenyl)-2-(2-aminothiazol-4-yl)benzo[b]furan derivatives 6-10 were prepared and their leukotriene B(4) inhibitory activity was evaluated. We found that several compounds showed strong inhibition of calcium mobilization in CHO cells overexpressing human BLT(1) and BLT(2) receptors. Among them, 3-(4-chlorophenyl)-2-[5-formyl-2-[(dimethylamino)methyleneamino]thiazol-4-yl]-5-methoxybenzo[b]furan 9b showed the most potent and selective inhibition for the human BLT(2) receptor, and its IC(50) value was smaller than that of the selected positive control compound, ZK-158252.     

Chelating ion-exchangers containing 4-(2-pyridylazo)-resorcinol as the functional group

The synthesis of a cross-linked polystyrene-azo-PAR resin, and its chelating ion-exchange properties with nine ionic species, are described. A resin structure, containing both PAR and azophenol chelating groups is proposed. The effects on capacity of varying ionic concentration and the nature of the co-ion were studied.     

Transformations of dialkyl(4-hydroxy-2-butynyl)-(3-phenylallyl)ammonium bromides in an KOH aqueous solution or in the presence of powdered KOH

Under the action of a twofold excess of KOH and heating in aqueous solution, and also under the conditions of the Stevens rearrangement (with KOH powder and a small amount of methanol) dialkyl-(4-hydroxy-2-butynyl)(3-phenylallyl)ammonium bromides form dialkyl[4-(1-phenylallyl)-2,5-dihydro-2-furyl]amines. Rearrangement–cleavage reaction also occurs under the same conditions.     

Quaternary salts containing the pentafluorosulfanyl (SF5) group

The first quaternary salts of pyridine (2), N-methyl imidazole (3), N-propyl triazole (4), and pyridazine (5) that contain the pentafluorosulfanyl (SF(5)) group were prepared and characterized. Neat reactions of the aromatic nitrogen compounds with SF(5)(CF(2))(n)(CH(2))(m)I (n = 2 or 4, m = 2 or 4) gave quaternary iodides 6a-c, 7a-c, 8a, and 9a,b, which were metathesized with LiN(SO(2)CF(3))(2) to form the bis(trifluoromethylsulfonyl)amides 10a-c, 11a-c, 12a, and 13a,b, in high yields. With the exception of the pyridine bis(trifluoromethylsulfonyl)amide salts, the compounds melted or exhibited a T(g) at <0 degrees C. The methylimidazolium, pyridinium, and pyridazinium salts exhibited densities of approximately 2 g/cm(3). Particularly striking was the density of CF(3)(CF(2))(5)(CH(2))(2)-pyridazinium N(CF(3)SO(2))(2) measured at 2.13 g/cm(3); however, an atypically high density for the 1-CF(3)(CF(2))(5)(CH(2))(2)-3-methyl imidazolium amide (14) was also observed at 1.77 g/cm(3). All quaternary salts were characterized via IR, (19)F, (1)H, and (13)C NMR spectra and elemental analyses.     

Halogenation of quaternary phosphonium salts containing prop-1(2)-enyl group

Bromination of prop-2-enyltributyl- and -triphenylphosphonium bromides affords the products of addition to the double bond. The structure of the triphenylphosphonium adduct was established by X-ray diffraction analysis. The latter is formed also by radical bromination of prop-1-enyltriphenylphosphonium bromide. The chlorination of prop-1- and 2-enyltriphenylphosphonium bromides leads to the formation of 3-chloroprop-1-enyltriphenylphosphonium bromide.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

三氯化铁催化选择性合成普罗布考单丁二酸酯

研究了以三氯化铁为催化剂选择性合成普罗布考单丁二酸酯的反应.考察了催化剂、反应溶剂、碱、酰化剂及配料比对反应的影响.实验结果表明金属盐对反应的收率和单酰化反应的选择性有显著的影响,当以三氯化铁为催化剂,丁二酸酐为酰化剂,叔丁醇钠为碱,四氢呋喃为溶剂,普罗布考、叔丁醇钠、丁二酸酐及三氯化铁的摩尔比为1:4:5:0.17,...     

Ergebnisse der Verfahrensforschung,I. Synthese von o-{(+)-D-2-[4-(4-(Trifluormethyl)phenoxy)phenoxy]propionyl}-aceton-oxim

Results of process Research I. Synthesis of O-{(+)-D-2-[4-(4-(triluoromethyl)phenoxy)phenoxy]propionyl}-acetone oxime Efficient and simple procedures for the preparation of O-{L-[(sulfonyl)oxy]-propionyl}-oxime derivatives 7b-e have been developed. The alleviation of 4-[4-(trifluoromethyl)phenoxy]phenol ( 11 ) with 7d , the final step of a technical synthesis of 1 , has been studied in detail.