A facile synthesis of 2-substituted-4-(substituted)phenyl-Δ2-1,3,4-oxadiazolin-5-ones

The title compounds, 3, are formed at ambient temperature from 4,4-dimethyl-2-(substituted)-phenylsemicarbazides (1) and carboxylic acid chlorides in the presence of triethylamine. 2-Dimethylamino-4-(substiluted)phenyl-Δ²-1,3,4-oxadiazolin-5-ones are formed from 1 and dialkyl-carbamoyl chlorides at elevated temperature (about 15° ). Acylation of 1 with carboxylic acid anhydrides, also at elevated temperature, is accompanied by loss of dimethylamine from the intermediate l-acyl-4,4-dimethyl-2-(substituted)phenylsemicarbazides, 2, to give 3.     

Acylation of 2-methoxypropene with anhydrides and halides of perfluorocarboxylic acids in the presence of tertiary amines

3-Methoxy-1-(perfluoroalkyl)but-2-en-1-ones were synthesized byC-acylation of 2-methoxypropene with perfluorocarboxylic acid anhydrides, acid chlorides, and acid fluorides in the presence of tertiary amines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1813–1815, September, 1999.     

Electrogenerated base-induced N-acylation of chiral oxazolidin-2-ones. Part 2

An improved and efficient electrochemical N-acylation of chiral oxazolidin-2-ones has been achieved. The generation of the nitrogen anion is obtained under mild conditions and without addition of base or probase, by direct electrolysis of a solution of MeCN-TEAP containing the oxazolidinone. Acylation agents (acid chlorides or anhydrides) were added at the end of the electrolysis. N-Acylated products were isolated in high to excellent yields.     

Synthesis of 5-and 7-fluoroquinazolin-4(1<Emphasis Type="Italic">H</Emphasis>)-ones

5-Fluoroquinazoline-2,4-diones and their 2-thio analogs were obtained from 6-fluoroanthranilic acid. Two convenient routes to 5-fluoroquinazolin-4-ones involved cyclocondensation of 6-fluoroanthranilamide with acid chlorides (anhydrides) or with aromatic (heterocyclic) aldehydes. A method for the synthesis of 7-fluoroquinazolin-4-one from 2,4-difluorobenzoic acid was proposed. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1758–1764, September, 2007.     

Synthesis,antiviral and antimicrobial screening of some new 2-oxoindoline derivatives

New 3-(2-(5-(aryldiazenyl)-4-methylthiazol-2-yl)hydrazono)indolin-2-ones were prepared by the reaction of isatin β-thiosemicarbazone with different hydrazonoyl chlorides. Imide derivatives were prepared by the reaction of isatin hydrazone with various anhydrides, and a series of new sulfonimides was also synthesized. All new compounds were tested for their biological activities.     

Acyl and Sulfonyl Derivatives of 3,5-Diamino-1-R-1,2,4-triazoles

3-Acylamino-5-amino-1-R-1,2,4-triazoles are formed regioselectively on acylating 3,5-diamino-1-R-1,2,4-triazoles with an equimolar amount of anhydrides, carboxylic acid chlorides, and sulfonyl chlorides. With an excess of anhydride and carboxylic acid chloride 3,5-diacylamino-1-R-1,2,4-triazoles are formed. 3-Acylamino-5-amino-1-R-1,2,4-triazoles do not interact with sulfonyl chlorides. The higher reactivity of the 3-amino group towards acylating agents is determined by electronic and not steric factors. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1342–1350, September, 2005.     

Acylation of 5-amino-3H-1,3,4-thiadiazolin-2-one

Acylation of 5-amino-3H-1,3,4-thiadiazolin-2-one (2) was undertaken selectively at either the 3-NH position or at 5-amino group depending on reaction conditions. The 3-NH is highly acidic and acylation takes place with acid anhydrides at this position in high yields in the presence of pyridine or triethylamine. The diacylation of both the 3-position and the 5-amino group was only possible via the 5-amino-3-acyl-1,3,4-thiadiazolin-2-one intermediates 4 . Under neutral conditions, acylation only occurs at the 5-amino group with acyl chlorides forming 5-acylamino-3H-1,3,4-thiadiazolin-2-ones 5 . 5-Acetylamino-3H-1,3,4-thiadiazolin-2-one can also be synthesized by the thermal transformation of 5-amino-3-acetyl-1,3,4-thiadi-azolin-2-one in acetic acid.     

Condensed isoquinolines 24. Reaction of 6,11-dihydro-13H-isoquino[3,2-<Emphasis Type="Italic">b</Emphasis>]quinazolin-13-one with carbonyl compounds

The reaction of 6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-one with carbonyl compounds occurs at the C₍₆₎ and/or N₍₅₎ atoms depending on the nature of the reagent and the conditions. Condensation with aldehydes gives 6-arylidene-6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-ones. Acylation using acid anhydrides or acid chlorides gave 5-acyl-, 6-acyl-, and 5,6-diacyl-5,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-ones depending again on the reaction conditions. Acylation using chloroacetyl chloride is accompanied by an intramolecular alkylation to give 7H,8H-2a, 7a-diaza-cyclopenta[f,g]naphthacene-1,7(2H)-dione. Phenyl isocyanate gave the derivative containing a CONHPh group at position 6. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1509–1520, October, 2007.     

β-Diketone Synthesis by Reaction of α-Haloketones with Acid Chlorides or Acid Anhydrides Promoted by Samarium Triiodide

Promoted by SmI₃, α-haloketones were reacted with acid chlorides or acid anhydrides and β-diketones were synthesized via intermediate samarium enolates.     

Research on arylhydrazones of substituted glyoxylic acids

Reaction of the hydrazides and acetylhydrazides of cyanoacetic acid with aryldiazonium chlorides gives arylhydrazones of the hydrazide and acetylhydrazide of cyanoglyoxylic acid. 2-Acetyl-3-imino-4-arylpyrazol-5-ones and 3-imino-4-arylazopyrazol-5-ones are obtained by cyclizing the arylhydrazones.For Part IX see [1].     

A study of the acylation of 4-hydroxy-6-methyl-2-pyrone and 4 hy(lroxy-6-phenyl-2-pyrone

The acylation of 4-hydroxy-6-melhyl-2-pyrone (1) and 4-hydroxy-6-phenyl-2-pyrone (XXII) with aliphatic acid anhydrides, or with aliphatic acid chlorides in trifluoroacetic acid, has been found to product; first the corresponding ester, which then rearranges, partially or wholly, depending on the conditions and on the nature of the acyl moiety, to form the corresponding 3-acylpyrone. With aromatic acid chlorides in pyridine or in trichloroacetic acid only the corresponding ester was obtained. These esters, however, could be rearranged to the corresponding 3-acylpyrones with aluminum chloride. Acetoaeetylation of 1 and 4-hydroxycoumarin (XXIX) with diketene gave, in both cases, the C-acetoacetylated product.     

N-Acyl andN-sulfonyl derivatives of thiazolidines

The major reaction center in the reaction of 4,4-dialkyl-5-methylene-2-phenyliminothiazolidines with acid chlorides or anhydrides and with arenesulfonyl chlorides is the nitrogen atom at position 3 of the ring.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2968–2970, December, 1996.     

Reaction of anthranilic acid amides with cyclic anhydrides

Anthranilic acid amide reacts with cyclic anhydrides to give the corresponding N-acyl derivatives at the amino group, while analogous reactions of o-aminobenzohydroxamic acid lead lead to formation of 3-hydroxy-quinazolin-4-ones under mild conditions. N-Acyl derivatives of anthranilic acid amide undergo intramolecular cyclization to imides on microwave irradiation or on melting, and their treatment with acetic anhydride in the presence of sodium acetate on heating yields quinazolin-4-ones.     

Chemistry of hetero analogs of isoflavones 25. Synthesis of 2-alkyl-3-(2-benzimidazolyl)-chromones

2-Alkyl-3-(1-methyl-2-benzimidazolyl)-7-acyloxychromones were synthesized by the reaction of substituted or unsubstituted 2-(2,4-dihydroxyphenacyl)-1-methylbenzimidazoles with the acid chlorides and anhydrides of carboxylic acids. The products were converted into 2-alkyl-7-hydroxychromones as a result of acid hydrolysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 26–30, January, 2008.     

Condensed isoquinolines 30. Acylation and alkylation of 5,13-dihydro-11H-isoquino-[3,2-<Emphasis Type="Italic">b</Emphasis>]quinazolin-11-one

It was shown that 6-acyl-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-ones are formed when 5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-one is heated with the chlorides and anhydrides of carboxylic acids in the presence of bases (pyridine, NaOAc) while 5-acyl-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-ones are formed in the presence of NaH. In the presence of NaH 6-acyl-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-ones form the products from acylation and alkylation at position 5. The action of heat on 5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-one in oxalyl chloride leads to 7H,8H-2a,7a-diazacyclopenta[fg]naphthacene-1,2,8-trione. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 741–750, May, 2008.     

A one-step synthesis of γ-pyrones

The potassium enolate of 4-methoxy-3-buten-2-one reacts with acid chlorides anhydrides and acylimidazoles by C-acylation and $\text{in situ}$ cyclization to afford 2-substituted γ-pyrones directly.     

Reactions of β-aminopropionic acid N"-acylhydrazides with carbonyl compounds

The reactions of -aminopropionic acid N"-acylhydrazides with aromatic and heterocyclic aldehydes and acetone afford compounds that exist in solutions predominantly as mixtures of 2-substituted 3-acylaminotetrahydropyrimidin-4-ones (ATHP) and tautomeric Schiff"s bases. These compounds in the crystalline state probably have structures of ATHP. The ratio of tautomers depends on the type of substituent in the aromatic ring and solvent. The reactions of 2-aryl-3-benzamidotetrahydropyrimidin-4-ones with carboxylic or sulfonic acid chlorides afford derivatives of 1-acyl- and 1-tosyl-3-benzamidotetrahydropyrimidin-4-ones.     

Potassium Fluoride Promoted Reaction of 3-Acylsubsti-Tuted 2H-1-Benzopyran-2-Ones with Acid Anhydrides. An Improved Method for the Synthesis of 4-(2-Oxoalkyl)-2H-Chroman-2-Ones. Part III1

The reaction of 3-acylsubstituted 2H-1-benzo-pyran-2-ones 1, 5 and 11a-c with acid anhydrides in the presence of potassium fluoride (KF)/molecular sieves 4A gives the 4-(2-oxoalkyl)-2-oxochromans 2, 6 and 12a-c as the main products. Also the 3-carboxylic acid derivatives, such as esters and N,N-dialkylamides, of 2H-1-benzopyran-2-one (11d-g) react with isobutyric acid anhydride in the presence of KF/molecular sieves 4A to give the corresponding 2-oxochroman-4-acetic acid derivatives.     

Synthese von 3-Dimethylamino-3a,4,5,7a-tetrahydro-1H-iso-indol-1-onen durch intramolekulare Diels-Alder-Reaktion

Synthesis of 3-Dimethylamino-3a,4,5, 7a-tetrahydro-1H-isoindol-1-ones by Intramolecular Diels-Alder Reaction Thermolysis of N²-acylamidines, the acyl group of which derives from an α,β,γ,δ-unsaturated carboxylic acid ( 2, 5 – 7 ), yields 3-dimethylamino-3a,4,5,7a-tetrahydro-1H-isoindol-1-ones ( 3,8 – 10 , Schemes 1 and 3) in 63–78%. Only the thermodynamically controlled cis-fused ring system is formed. The starting materials are readily available by the reaction of 3-dimethylamino2H-azirines ( 1 and 4 ) and carboxylic acid chlorides.     

New facile synthesis of furan-2(3H)-ones and 2,3,5-trisubstituted furans via intramolecular Wittig reaction of acid anhydride

A new facile preparation of furan-2(3H)-ones and 2,3,5-trisubstituted furans by a sequential O-acylation/Wittig(/O-acylation) reaction has been developed. The easily accessible 2-(triphenylphosphoranylidene)-succinic acid 1-ester 3 reacted with acid chloride produced furan-2(3H)-ones 4 in good yields in the presence of DMAP via sequential O-acylation and intramolecular Wittig reaction of acid anhydride. Subsequently, the 2,3,5-trisubstituted furans 5 were prepared from furan-2(3H)-ones 4 and diverse aryl chlorides in presence of triethylamine through further O-acylation.