Formic Acetic Anhydride Research Articles

The Reaction between Acetic Formic Anhydride and Salicylamide.

The Reaction between Acetic Formic Anhydride and Salicylamide.

A highly efficient and general [formula omitted]-monomethylation of functionalized primary amines via formylation--borane:methyl sulfide reduction

Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding N -methylamines in excellent isolated yields, uncontaminated bybis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.

Synthesis, spectroscopy and polymerization of methyl α‐([13C,15N]isocyano)propionate; acetic formic anhydride as N‐formylating reagent

AbstractMethyl α‐([13C,15N]isocyano)propionate was prepared starting from (±)‐[15N]alanine. The amino acid was converted into the methyl ester, which was formylated with acetic [13C]‐formic anhydride, to afford the methyl ester of N‐[13C]formyl[15N]alanine. Dehydration of the latter compound gave the isocyanide, which was polymerized with nickel chloride. 1H, 13C, 15N NMR and IR data of the labelled compounds are presented.

Triazines and related products. Part 24. Synthesis of pyrazol-4-ylidenehydrazinoimidazoles by hydrazinolysis of imidazo[5,1-c][1,2,4]-triazines and 2-arylazoimidazoles by diazonium coupling reactions

4-(Substituted)imidazo[5,1-c][1,2,4)triazine-8-carboxamides with ester, ketone, or cyano-groups in the 3-position undergo ring-opening with hydrazine and phenylhydrazine to yield substituted (pyrazol-4-ylidenehydrazino)imidazole-4-carboxamides. In some cases ring cleavage is initiated by attack of the hydrazine at C-4 of the imidazotriazine, and in others by nucleophilic attack at the 3-substituent. Examples of the same series of hydrazones can be prepared by coupling 5-diazoimidazole-4-carboxamide with activated pyrazoles. Diazotised arylamines couple with 5-aminoimidazole-4-carboxamide at C-2 to yield a series of intensely coloured 5-amino-2-arylazoimidazole-4-carboxamides, which can be cyclised to 8-arylazo-9H-purin-6(1H)-ones with ethyl formats in sodium ethoxide, and form mono- or di-acylamino-derivatives in formic acid or acetic anhydride. In no case was it found possible to prepare 2,5-diaminoimidazole-4-carboxamide by reductive cleavage of 5-amino-2-arylazoimidazole-4-carboxamides; only arylamines or unstable hydrazo-intermediates were identified. Reduction of 5-amino-2-(2-cyanophenylazo)imidazole-4-carboxamide with sodium dithionite or with hydrogen over a 10% palladium–charcoal catalyst afforded 5-amino-2-(3-aminoindazol-2-yl)imidazole-4-carboxamide.

The reaction of formyl fluoride with transition metal complexes

Formyl fluoride reacts with metal carbonyl anions in a manner similar to acetic formic anhydride. Although formyl complexes may have been formed as unstable intermediates, no neutral formyl complexes could be isolated but rather the expected decomposition products, the metal carbonyl hydrides or ?imers, were produced. The attempted oxidative addition of formyl fluoride to various coordinately unsaturated metal complexes also did not result in the formation of formyl derivatives. HF adducts were obtained from the reaction ?fIr(CO)Cl(PR 3) 2 or M(PPh 3) 4 (M Pt or Pd) with formyl fluoride whereas Ru(NO)Cl(PPh 3) 2 and Rh(PPh 3) 3 Cl give the CO complexes Ru(NO)(CO)Cl(PPh 3) 2 and Rh(CO)Cl(PPh 3) 2, respectively.

3'-O-Formyl-(N-acyl)-2'-deoxyribonucleosides as building units in the synthesis of oligodeoxyribonucleotides

5'-O-Dimethoxytrityl-(N-acyl)-2'-deoxyribonucleosides afford 3'-O-formyl-(N-acyl)-2'-deoxyribonucleosides Ia-Id by the action of formic acetic anhydride followed by the action of 80% aqueous acetic acid. The formyl group is removed from Ia-Id by treatment with 1 mol l-1 triethylamine 3'-O-Formyl-2'-deoxythymidine (Ia) gives 3'-O-dimethoxytrityl-2'-deoxythymidine (V) by subsequent treatment with acetic anhydride, triethylamine, dimethoxytrityl chloride and methanolic ammonia. The use of compounds I for the synthesis of d-GGAGG (XIX) and d-T16 (XXXII) is described. Systems for thin-layer chromatography of 5'-O-dimethyltrityl-oligodeoxyribonucleotides on silica gel are described.

Heats of solution and neutralization ofLewis acids and bases in acetic anhydride

Heats solution of someLewis acids and bases in acetic anhydride have been determined and the following order of their relative strengths is proposed: SbCl5>SO3>SnCl4>TiCl4>AsCl3 and piperidine> n-butylamine>potassium acetate>sodium acetate≈ α-picoline>quinoline. Heats neutralization of theseLewis acids and bases in acetic anhydride suggest that the major enthalpy change in these neutralization reactions is due to the combination of a proton and the (CH2COOCOCH3)-ion, resulting in the formation of acetic anhydride.

Purines, pyrimidines, and imidazoles. Part 56. Some aminoimidazole-carboxamidines and derived adenines

5-Amino-4-cyano-1-cyclohexylimidazole, prepared from aminomalononitrile, triethyl orthoformate, and cyclohexylamine with methanolic hydrogen chloride, produced methyl 5-amino-1-cyclohexylimidazole-4-carboximidate, which with ammonia gave 5-amino-1-cyclohexylimidazole-4-carboxamidine, formylation of which gave 9-cyclohexyl-N6-formyladenine, which was also prepared by formylation of 9-cyclohexyladenine. 9-(2,3-Dihydroxypropyl)-N6-formyladenine was produced in a similar series of reactions and the reaction of 5-aminoimidazole-4-carboxamidine with formic acetic anhydride has also been shown to produce not, as previously thought, the formylamidine, but N6-formyladenine which could also be obtained by formylation of adenine, whereas adenosine was not N-formylated under the same conditions.

1,3-Dialkyluracils as a source of formyl acetate for synthesis

1,3-Dialkyluracils as a source of formyl acetate for synthesis

Addition of acetic formic anhydride to [formula omitted]-[ IrCl(CO)(PMe 2Ph) 2]; anion-, including hydrido-, transfer reactions

Addition of acetic formic anhydride to trans -[ IrCl(CO)(PMe 2Ph) 2] leads, via a series of intermolecular anion (hydrido, formato and chloro) ligand exchange reactions, to the formation of the cis -dihydrido, trans -tertiary-phosphino complex [ IrClH 2(CO)(PMe 2Ph) 2].

The synthesis of 3-spirooxindole derivatives. VII. Total synthesis of alkaloids (.+-.)-rhynchophylline and (.+-.)-isorhynchophylline.

The total synthesis of (±)-rhynchophylline (Ia) and (±)-isorhynchophylline (Ib) which are oxindole alkaloids of Uncaria rhynchophylla MIQ (Ourouparia rhynchophylla MATSUM), has been completed through eight stages starting from the condensation of 2-hydroxytryptamine hydrochloride (III) with ethyl sodium formyl acetate (IV). The success in the first-stage condensation is significant since ethyl sodium formyl acetate (IV) is rather unstable and has not been existent as the liberated ester. The sterostructures of the intermediates are discussed and mostly assigned.

Nucleic Acid Related Compounds. 14. 3′-O-Aminoacyl-2′-O-methyladenosines and 2′-O-Aminoacyl-3′-O-methyladenosines Related to Charged tRNA Termini

Aminoacyl nucleosides derived from 2′-O-methyladenosine and 3′-O-methyladenosine have been isolated as pure solids and completely characterized for the first time. Coupling of 5′-O-(mono-p-methoxytrityl)-2′-O-methyl- (and 3′-O-methyl-) adenosines (1 and 6, respectively) with N-tert-butyloxycarbonyl(N-tBOC)-amino acid anhydrides (2a–c) (generated insitu from the corresponding N-tBOC-amino acids and N,N′-dicyclohexylcarbodiimide) in the presence of 4-N,N-dimethylaminopyridine gave the 3′-O-(N-tBOC-aminoacyl)-5′-O-(mono-p-methoxytrityl-2′-O-methyladenosines (3a–c) and 2′-O-(N-tBOC-aminoacyl)-5′-O-(mono-p-methoxytrityl-3′-O-methyladenosines (7a–c), respectively, in good yields. The L-leucine (a), L-phenylalanine (b), and L-methionine (c) compounds were prepared in each series. Complete deblocking was effected using 98% formic acid since usual procedures had disadvantages with these molecules. The 3′-O-(L-aminoacyl)-2′-O-methyladenosines (4a–c) and 2′-O-(L-aminoacyl)-3′-O-methyladenosines (8a–c) were obtained in high yields with no detectable hydrolysis of the aminoacyl or glycosidic bonds under these conditions.N-Formylmethionyl and N-acetylphenylalanyl derivatives were prepared in each series by acylation of the deblocked products with acetic formic anhydride and p-nitrophenyl acetate, respectively. Biochemical rationale for the use of these compounds in the study of protein biosynthesis and initiation processes are discussed. The puromycin-like activity of 3′-O-phenylalanyl-2′-O-methyl-adenosine (4b) was confirmed.

An electron diffraction investigation of the molecular structure of formic anhydride

The molecular structure of formic anhydride, (HCO) 2O, in the gas phase has been determined by electron diffraction, using the sector-microphotometer method. The structure is asymmetric with a nonbonded O ⋯ H interaction; the formyl fragments are twisted out of the C-O-C plane. The twist angles are 17° and 26°. The bondlengths r g(1) are: r(C0) = 1.384 and r(C-H) = 1.10 Å. The valency angles are: α(O-C-H) = 119°,α(0-C0) = 123.4° and α(C-O-C) = 115°. The nonbonded O ⋯ H distance is 2.5 Å. The structures of formic, acetic and formic acetic anhydride are compared.

Vibrational spectra and normal coordinate analysis of formic acetic anhydride

The infrared and Raman spectra of formic acetic anhydride, (HCO)O(CH 3CO), and its mono-, tri- and tetra-deuterated forms were recorded from 180 to 3200 cm −1 and normal coordinate calculations were carried out, including all four species in the least squares refinement of force constants. The small carbonyl splitting (~ 20 cm −1 against ~ 60 cm −1 in symmetrical anhydrides) is discussed. From a comparison of the force fields of methyl formate and formic acetic anhydride it is concluded that there is no evidence of an intramolecular hydrogen bond in the latter compound.

An electron diffraction investigation of the molecular structure of formic acetic anhydride

The molecular structure of formic acetic anhydride, (HCO)O(CH 3CO), in the gas phase has been determined by the sector-microphotometer method of electron diffraction. The formyl and acetyl fragments are twisted out of the C-O-C plane by 21° and 46°, respectively, giving a dihedral angle between the two moieties of 126°. The bonded interatomic distances, r g(1), are: r(CO) = 1.195, r(C-O) = 1.397 and r(C-C) = 1.495 Å. The valency angles in the acetyl group are: α(O-C-C) = 112° and α(O-CO) = 122°, the formyl valency angles are α(O-CO) = 118° and α(O-C-H) = 120°, and the central C-O-C angle is 113°. The formyl C-H and acetyl CO bonds are nearly parallel, resulting in an H ⋯ O distance of 2.7 Å. The structures of acetic-, formic acetic-, and formic anhydride are compared.

The reaction of some indoles with acetic‐formic anhydride

The reaction of some indoles with acetic‐formic anhydride

Preparation of 5-Aminothiazole-4-carboxylic Acid Derivatives

Cyclization of 2-acylamino-2-thiocarbamoylacetamides (Va, b) with acetic formic anhydride gave good yields of 5-formamidothiazole-4-carboxamides (VIa, b) which were converted to 5-aminothiazole-4-carboxamides (VIIa, b) by hydrolysis. For the purpose of the preparation of the free base (VIIa), however, cyclization of Va with polyphosphoric acid was proved to give better result, that is, heating of Va-c and ethyl 2-acylamino-2-thiocarbamoylacetates (Vd-f) in polyphosphoric acid gave VIIa-c and ethyl 5-aminothiazole-4-carboxylates (VIId-f) in excellent yields. 5-Aminothiazole-4-carbonitriles (VIIg, h) were prepared by treatment of Va, b with phosphorus oxychloride.

Peculiarities of the chemical properties of vicinally disubstituted veratrole and synthesis of 1-methyl-4,5-dimethoxybenzimidazole derivatives

Various paths for the synthesis of 4-methylamino-3-aminoveratrole (I) from 4-amino-3-nitroveratrole (II) were investigated, and it was found that I can be obtained in a high overall yield of 65% through the tosyl derivative of II. 1-Methyl-4,5-dimethoxybenzimidazolone, 1-methyl-4,5-dimethoxybenzimidazole and its 2-phenyl-, 2-chloro-, and 2-dimethylamino derivatives were synthesized on the basis of I in order to investigate their biological activity. It was established that the chemical properties of vicinally disubstituted veratrole, particularly the increased basicity of II, are determined to a significant degree by steric strains caused by bulky substituents. It is shown that 85% formic acid can be successfully used in place of 98–100% formic acid for the N-formylation of aromatic amines with a mixture of formic acid and acetic anhydride.

Mixed carboxylic anhydrides. Part VIII. Synthesis of aryl thiolformates

AbstractAn attractive synthesis of pure aryl thiolformates has been found in the base‐catalysed esterification of thiophenols with acetic formic anhydride or with a formic acid/acetic anhydride reaction mixture.

Azole Series. III. Reactions of 2-Acylamino-2-cyanoacetamides leading to 5-Aminooxazole-4-carboxamides and to Oxazolo [5, 4-d] pyrimidines

Reaction for preparation of a new series of 5-acylaminooxazole-4-carboxamides has been found. 5-Acetamidooxazole-4-carboxamides were obtained by heating 2-acylamino-2-cyanoacetamides with acetic anhydride in the presence of perchloric acid. Analogous 5-form-amido derivatives were also obtained by heating the same substrates with a mixture of formic acid and acetic anhydride in the presence of hydrochloric acid. Trials for synthesis of oxazolo [5, 4-d] pyrimidine-7-ol from the 5-acylaminooxazole-4-carboxamide obtained were also successful in some cases by means of heating with potassium bicarbonate solution.