Methyl Cyanoacetate Research Articles

ChemInform Abstract: THE REACTION OF 2,4,6‐TRIPHENYL‐1,3‐THIAZINYLIUM PERCHLORATE WITH ACTIVE METHYLENES

AbstractTitelverbindung (I) reagiert mit CH‐aciden Verbindungen wie Cyanessigester und Benzoylacetonitril unter Bildung von Cyantriphenylpyridin (II).

Synthesen mit Nitrilen, LVIII. Ein neuer Weg zu Isoxazolo[5,4‐ b ]pyridinen

Syntheses with Nitriles, LVIII. A New Route to Isoxazolo[5,4-b]pyridines Reaction of dimeric malononitrile (2-amino-1-propene-1,1,3-tricarbonitrile) (1) with benzo-hydroximoyl chlorides in alkaline medium leads to substituted isoxazolo[5,4-b]pyridines 6a – e. The isoxazole derivative 4a is an isolable intermediate. Condensation of the mixed dimer from malononitrile and methyl cyanoacetate (methyl 3-amino-2,4-dicyanocrotonate) (3) with benzo-hydroximoyl chlorides yields methyl 3-amino-3-(5-amino-3-aryl-4-isoxalyl)-2-cyanoacrylates (5a – c). 6,7-Dihydro-6-oxoisoxazolo[5,4-b]pyridines 7a,c are obtained from 5a,c by elimination of alcohol.

The reaction of 2-cyano-3-(5-phenylsulphonyl-2-thienyl) acronitrile with nucleophiles

5-Phenylsulphonyl- and 5-phenylthio-2-thiophenaldehydes react with malononitrile and methyl cyanoacetate under the conditions of Knoevenagel reaction to give the corresponding condensation products. It has been found that when 2-cyano-3-(5-phenylsulphonyl-2-thienyl)-acrylonitrile is treated with nucleophiles the phenylsulphonyl group is substituted.

The Reaction of 2,4,6-Triphenyl-1,3-thiazinylium Perchlorate with Active Methylenes

Abstract The reaction of 2,4,6-triphenyl-1,3-thiazinylium perchlorate (4) with several active methylenes was studied. Methyl cyanoacetate or benzoylacetonitrile reacted with 4 to give 3-cyano-2,4,6-triphenylpyridine, while malononitrile led to 1-mercapto-1,3-diphenyl-4,4-dicyanobutadiene and cyanoacetamide led to 2-hydroxy-3-cyano-4,6-diphenyl-pyridine. The reaction of diethyl malonate, nitromethane, or nitroethane with 4 gave 2-[bis(ethoxycarbonyl)methyl]-, 2-nitromethyl- or 2-(1-nitroethyl)-2,4,6-triphenyl-2H-1,3-thiazine respectively. These results showed that the reaction manner of 4 to these active methylenes is significantly different from that of 2,4,6-triphenyl-1,3-oxazinylium salt.

ChemInform Abstract: REACTION OF ETHYL 4‐HALO‐3‐OXOBUTANOATE WITH DIETHYL MALONATE, METHYL CYANOACETATE, AND MALONONITRILE

AbstractDie Reaktion des 4‐Halogenacetessigesters (I) mit Malonester (II) in Gegenwart von NaH ergibt den Triester (III) und den Diester (IV), mit Cyanessigester (V) gelangt man zu den Cyanoxoestern (VI) und (VII), mit Malonsäuredinitril (VIII) werden das Furan (IX) und das Methylencyclopenten (X) gebildet.(IR‐, NMR‐Spektren).

ChemInform Abstract: STUDIES ON TERTIARY AMINE OXIDES. LXII. A NOVEL FORMATION OF QUINOLINIUM METHYLIDES BY THE REACTION OF QUINOLINE 1‐OXIDES WITH ACTIVE METHYLENE COMPOUNDS IN THE PRESENCE OF AN ACYLATING AGENT

AbstractChinolin‐N‐oxid (I) ergibt bei der Umsetzung mit Cyanessigsäurethylester in DMF oder DMSO und in Gegenwart von Essigsäureanhydrid ein Gemisch aus den normalen Substitutionsprodukten (III) und (IV) sowie als Hauptprodukt das N‐Ylid (V).

Reaction of nucleophilic reagents with D-glycosyl- and D-gluconyl isothiocyanates.

Reactions of various amino compounds with D-glycosyl-and D-gluconylisothiocyanates gave the corresponding thioureides in good yields. Attempts to cause the ring closure of N-glucopyranosyl-N'-phenyl thioureide with methyl cyanoacetate or methyl propiolate under acidic conditions were unsuccessful.

A new method of preparation of α-amino derivatives of furan

The reaction of 5-nitro-2-furfuryl nitrate with sodium azide and malononitrile or methyl cyanoacetate was studied. Products of this treatment are 5-amino-2-furfurylidenemalonodinitrile and methyl 3-(5-amino-2-furyl)-2-cyanoacrylate.

Cyclisierung von Oligomeren des Malodinitrils mit Amidinen Synthesen mit Nitrilen, 55. Mitt

Condensation of formamidine-acetate with dimeric malononitrile (1 a) leads to 2,4-diamino-3,5-pyridine-dicarbonitrile (3 a), with acetamidine-HCl the methyl derivative3 b is obtained. Reaction of the codimer of malononitrile and methyl cyanoacetate (1 b) with formamidine yields the aminopyridine3 c, while acetamidine and benzamidine, resp. with1 b react to the 1,4-dihydro-4-pyrimidinylidene-methyl-cyanoacetates4 a-b.

Polyketo-enols and chelates. Synthesis of 2-pyrones, 2-pyridones, 2-methoxypyridines, and m-hydroxyanilines by control of the cyclisation of nitrile-substituted glutaconic types

Sodium methoxide-initiated condensation between methyl cyanoacetate and methyl methoxymethyleneacetoacetate leads, via a nitrite-substituted propene (glutaconic ester), to a 2-pyridone at low base molarities and to a 2-pyrone at high ones. Employment of high molarities of magnesium methoxide gives, in addition, a m-hydroxyaniline. When malononitrile replaces methyl cyanoacetate a 2-methoxypyridine is also formed at high methoxide molarities.

Study of reaction of substituted nitrophenyl acetates and benzoates with nucleophiles

Reaction of 2-substituted 4,6-dinitrophenyl acetates and benzoates with methoxide, 4-bromophenoxide and acetate anions and with anion of methyl cyanoacetate has been studied in methanol at 25 °C, and the respective rate constants have been determined along with the rate constant ratios of nucleophilic attacks at carbonyl carbon (CCO) and C1 carbon of the aromatic ring (CAr). Content of the 2-substituted 4,6-dinitrophenols formed by nucleophilic attack at CCO increases in the product with increasing hardness of the nucleophiles in the series methyl cyanoacetate anion < 4-bromophenoxide anion < methoxide anion. The substituents polar effects are decisive for the attack at CAr, whereas both polar and steric effect operate in the attack at CCO. Methoxide anion attacks the CCO of 2,4-dinitrophenyl ester even faster than the CCO of 2,4,6-trinitrophenyl ester.

Preparation and Reactivities of Phenylethynyl[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I) Complex

Abstract Phenylethynyl[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I), [Cu(C≡CPh)(tdpme)]tdpme=1,1,1-tris(diphenylphosphinomethyl)ethane, has been prepared in good yield by a reaction between phenylethynyl-copper(I), [{Cu(C≡CPh)}n], and tdpme. From physicochemical and spectroscopic studies the complex is considered to have a monomeric tetrahedral structure. It reacts with p-cresol to give [Cu(O–C6H4–CH3-P)(tdpme)] and also with highly active hydrogen compounds, methyl cyanoacetate and methyl nitroacetate, to give [Cu{CH(CN)CO2CH3}(tdpme)] and [Cu{CH(NO2)CO2CH3}(tdpme)], respectively. However, moderately active hydrogen compounds, such as acetonitrile, dimethyl malonate, and nitromethane, do not react with [Cu(C≡CPh)(tdpme)]. The reactivities of the complex with active hydrogen compounds are discussed in correlation with the pKa values of the latter compounds.

Reaction of ethyl 4-halo-3-oxobutanoate with diethyl malonate, methyl cyanoacetate, and malononitrile.

Ethyl 4-bromo (and chloro)-3-oxobutanoate (1 and 2) reacts with diethyl malonate in the presence of sodium hydride to give diethyl 5-ethoxycarbonyl-3-oxohexanedioate (3) and diethyl 5-carboxy-3-oxohexanedioate (4). Similarly, reaction of the haloester (1, 2) with methyl cyanoacetate gives 1-ethyl methyl 5-cyano-3-oxohexanedioate (6) and 1-ethyl hydrogen 5-cyano-3-oxohexanedioate (7). On the other hand, 1 reacts with malononitrile in the presence of triethylamine to give ethyl 5-amino-4-cyanofuran-2-acetate (8) and ethyl 3-amino-2, 4, 4-tricyano-2-cyclopenten-1-ylideneacetate (9).

Studies on tertiary amine oxides. LXII. A novel formation of quinolinium methylides by the reaction of quinoline 1-oxides with active methylene compounds in the presence of an acylating agent.

The reaction of quinoline 1-oxide with ethyl cyanoacetate and acetic anhydride in dimethylformamide (DMF) or dimethylsulfoxide (DMSO) at low temperatures was found to give quinolinium-ethoxycarbonylcyanomethylide as the main product besides the normal 2-substituted and 4-substituted products. This novel formation of N-ylide was examined under various conditions, and the following features were revealed. Acetic anhydride was most effective as acylating agent, and DMF and DMSO seemed most suitable media for the N-ylide formation. In addition to ethyl cyanoacetate, malonodinitrile, methyl cyanoacetate and benzoylacetonitrile also produced the corresponding N-ylides, but other active methylene compounds such as malonates, ethyl acetoacetate and cyanoacetamide gave no ylide, only 2-substituted or/and 4-substituted products being formed. As for aromatic N-oxide, pyridine and isoquinoline N-oxides were inert to the N-ylide formation. On the other hand, quinoline 1-oxides bearing an electrondonating group at the 4-position, i.e., lepidine, 4-methoxy-and 4-amino-quinoline 1-oxides, were highly reactive toward this type of N-ylide formation. A likely reaction mechanism was proposed.

The structure of the condensation product of methyl cyanoacetate and 2,4‐dimethoxy‐6‐chloro‐l,3,5‐triazine

AbstractFrom NMR and IR measurements it appeared that the title compound occurs in solution in two tautomeric forms, a predominant NH, and an enolised ester form. Both forms are in rapid equilibrium. The structure (I) expected for this type of condensation does not occur. A second exchange process involves breaking of an intramolecular H‐bond combined with rotations about the triazinyl side chain bond.

MONOALKYLATION OF METHYL CYANOACETATE AND ACETYLACETONE USING 1,8-DIAZA-BICYCLO[5.4.0]UNDECENE-7

Abstract A simple method for selective monoalkylation of methyl cyanoacetate and acetylacetone using 1,8-diaza-bicyclo[5.4.0]undecene -7(DBU) as a base is described.

�ber einige Kondensationsreaktionen von dimerem Malonitril, dimerem Cyanessigs�ure�thyl- bzw.-methylester mit aromatischen Aldehyden

Aromatic aldehydes (1 a-g) yield linear condensation products (3 a-1) with dimeric ethyl and methyl cyanoacetate, resp., and dimeric malonitrile. Reduction of the condensation product of o-nitrobenzaldehyde with dimeric methyl cyanoacetate leads to methyl (3-methoxycarbonyl-1,2-dihydro-2-chinolinylidene)-cyanoacetate (4), with o-aminobenzaldehyde a carbostyril derivative5 a is obtained. In the presence of ammonium acetate aromatic aldehydes react with dimeric methyl and ethyl cyanoacetate, resp. to hexahydro-pyrimidinylidene cyanoacetates (8).

Introduction of cyclic dithioacetal functions into activated methylene compounds by treatment with 2-alkoxy-1,3-benzodithioles

2-Alkoxy-1,3-benzodithioles reacted with a wide variety of active methylene compounds in acetic acid to give products in which the 1,3-benzodithiol-2-yl group had been introduced at the activated carbon atom. In the reactions with malononitrile, methyl cyanoacetate, cyanoacetamide, and rhodanine, products with two 1,3-benzodithiol-2-yl substituents at the activated carbon atom were obtained in excellent yields.

Reactions of 1-arylpyridinium ions with anions of methyl acetoacetate, cyanoacetate and malonate

Reactions of 1-arylpyridinium ions with anions of methyl acetoacetate, cyanoacetate and malonate

Kinetics of reaction of 2,4-dinitrochlorobenzene with methyl malonate, cyanoacetate and acetoacetate

Kinetics of reaction of 2,4-dinitrochlorobenzene with methyl malonate, cyanoacetate and acetoacetate