Orthoamide Derivatives Research Articles

Orthoamide und Iminiumsalze, CV. Umsetzungen von Orthoamiden der Alkincarbonsäuren mit Carbonsäureamiden

Abstract The reaction of an orthoamide derivative of phenylpropiolic acid (22a) with primary and secondary amides gives rise to the formation of a wide spectrum of reaction products. The reaction of 22a with formamide delivers a N-carbamoyl-cinnamic acid amidine, wheras the analogous reaction with methylene-diformamide leads to a ketenaminal, which is substituted in β-position by a N-formylimino group. From the orthoamide 22a and phthalimide a phthalic acid amide amidine is obtained. In contrast the reaction of diformamide with 22a affords a β-imino enamine. 2,6-Diaminopyridines can be obtained from 22a with acetamide, propionamide and butyramide in low yields. The pyridines are characterized as perchlorates. From 22a and benzamide a 4-amino-2,6-diphenylpyrimidine is obtained in low yield. In the reaction of the closely related orthoamide derivative of 4-Cl-phenylpropiolic acid 22b with benzamide are isolated as a further products two pyrimidine derivatives. A pyrimidinone and a vinylogous thiourea can be obtained from 22a and urea and thiourea, respectively.

Orthoamide und Iminiumsalze, CII. Umsetzungen eines Orthoamids der Phenylpropiolsäure mit tertiären CH-aciden Verbindungen

AbstractThe orthoamide derivative of phenylpropiolic acid reacts with tertiary CH-acidic compounds as alkylmalonic acid dialkylesters under formation of 1,1-diamino-allenes wich rearrange to give 2-alkoxycarbonyl-1,1-diamino-1,3-butadienes by migration of an alkoxycarbonyl group. Perchloric acid transforms these butadienes to amidinium perchlorates. The crystal structure of an amidinium perchlorate derived from cinnamic acid has been determined.

Orthoamide und Iminiumsalze, CII. Umsetzungen eines Orthoamids der Phenylpropiolsäure mit tertiären CH-aciden Verbindungen

Abstract The orthoamide derivative of phenylpropiolic acid reacts with tertiary CH-acidic compounds as alkylmalonic acid dialkylesters under formation of 1,1-diamino-allenes wich rearrange to give 2-alkoxycarbonyl-1,1-diamino-1,3-butadienes by migration of an alkoxycarbonyl group. Perchloric acid transforms these butadienes to amidinium perchlorates. The crystal structure of an amidinium perchlorate derived from cinnamic acid has been determined.

Orthoamide und Iminiumsalze, C. Vinyloge Guanidiniumsalz-basierte ionische Flüssigkeiten sowie phenyloge Guanidiniumsalze und Orthoamide

Abstract Cyclopropylacetylene and N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride (1a) react to give the orthoamide derivative 8c, in the presence of sodium hydride. 8c is transformed by elemental iodine to the vinylogous guanidinium salt 6f. Anion metathesis with the salts 5a, 5e, 6g delivers vinylogous guanidinium salts 5e–5i, 12a with counter ions derived from carbon acids (tricyanomethane, 1,1,3,3-tetracyano-propene). Phenylogous amidinium salts 15 guanidinium salts 19, 21 and the phenylogous orthoamide derivatives of formic acid 18 and carbonic acid 33 have been prepared.

Orthoamide und Iminiumsalze, IIICa. Weitere Ergebnisse bei der Umsetzung von Orthoamiden der Alkincarbonsäuren mit CH2- und CH2/NH-aciden Verbindungen

Abstract The 1,1-bis(dimethylamino)-1,3-butadienes (keten aminals) 11a–l are prepared from orthoamide derivatives of alkyne carbonxylic acids 9b, d, e, i and CH2-acidic compounds 10a–c, f–h, k, o. The C-silylated orthoamide derivative 9c shows an ambivalent behaviour towards CH-acidic compounds. Reactions of 9c with strong CH2-acidic compounds like the nitro alkanes 10m, n and strongly enolized carbonyl compounds as methyl acetoacetate, cyanoacetamide, dibenzoylmethane, 1,3-dimethylbarbituric acid proceed under desilylation to give the ketene aminals 11u–z. In contrast to these reactions, the C-silylated ketene aminals 11o–t are obtained from 9c and weaker CH2-acidic compounds as dimethyl malonate, cyanoacetic acid derivatives and benzylcyanides. CH2/NH2-acidic compounds [cyanoacetamide (10d) and N-ethyl-cyanoacetamide (10f)] react with the orthoamide derivatives 9b, e–g at the acidic carbon-hydrogen bond to give the ketene aminals 11ac, ad, af, ag, ai, which cyclize to the pyridones 14a–d, d–g on heating. From the reaction of the orthoamide 9d with cyanoacetamide the pyridone 14c results directly. The persubstituted pyridone derivative 19 is formed by the reaction of cyanoacetamide with a mixture of the isomeric orthoamides 15 and 16. The 5,5-diamino-2,4-pentadienamide 11v attacks the orthoamide 9a at C3/C1. In the product 20 a cross conjugated multiple bond system is formed which contains an 1-aza-2,3-diamino function and a further ketene aminal function.

Orthoamide und Iminiumsalze, XCII. Synthese und Reaktionen von Orthoamiden aus ethinylierten Terpenderivatena

Abstract β-Ionone and camphor were ethynylated to give the alkynols 14, 16, 17 which can be transformed to the alkynolethers 5b, 5i, 5j, 5k, 5l, 5m by treatment with dimethylsulfate and chlorotrimethylsilane, respectively. From the alkynolethers 5h, 5i, 5j/5k, 5l/5m the orthoamide derivatives 4h, 4i, 4j/4k, 4l/4m can be prepared by treatment with N,N,N′,N′,N″,N″-hexamethylguanidinium chloride (8) in the presence of sodium hydride. The orthoamides 4h, 4i react with the sulfonamide 30 under condensation yielding the N-sulfonylated acrylamidines 31, 32. From the orthoamide 4h and p-nitroaniline the propiolamidine 29 could be obtained. The orthoamides 4j/4k and 4l/4m, react with benzamidine to give the pyrimidines 33, 34, respectively. In the reaction of malonodinitrile (9a) with the orthoamides 4i and 4j/4k, mixtures of 1,1-diamino-1,3-butadienes 36, 38 and 1,3-diamino-1,3-butadienes 37 and 39 are produced, respectively. From CH2-acidic compounds as ethylcyanacetate (9b), diethyl-malonate (9c) and nitromethane (9d) and the orthoamide 4i the 1,1-diamino-1,3-butadienes 36b–d were produced. The pyridone derivative 40 can be prepared from cyanoacetamide (9e) and the orthoamide 4i. The condensation of the orthoamides 4j/4k with cyanoacetamide (9e) affords a mixture of the pyrimidone 41 and the nicotinonitrile 42.

Orthoamide und Iminiumsalze, LXXXI [1]. Orthoamid-Derivate der 1,3-Dimethylparabansäure / Orthoamides and Iminium Salts LXXXI [1]. Orthoamide Derivatives of 1,3-Dimethylparabanic Acid

1,3-Dimethyl-5-imino-imidazolidine-2,4-dione (7a) undergoes thiolysis (H2S) to give the corresponding imidazolidine-2,4-dione-5-thione derivative 6. The 5-N-methylimino analogue 7b can be obtained from 7a by methylation. Further methylation of 7b affords the crude iminium salt 8c from which the heterocyclic orthoamide derivatives 10, 11 can be prepared. The heterocyclic amide acetal 9a can be obtained from 7a and dimethyl sulfate in methanol and subsequent addition of sodium methanolate in a one-pot reaction. The aminal ester 10 is converted to the amide acetal 9a on treatment with hydrogen chloride in methanol

Orthoamide und Iminiumsalze, LXXVI [1]. Ein weiterer Beitrag zur Chemie der Trialkoxyacetonitrile/ Orthoamides and Iminium Salts LXXVI [1]. A Further Contribution to the Chemistry of Trialkoxyacetonitriles

An improved procedure for the preparation of trimethoxyacetonitrile (3a) starting from trichloroacetonitrile and sodium methanolate is described. Carbanions, obtained by the action of sodium hydride on nitriles, ethyl acetate and methylketones, react with trialkoxyacetonitriles 3 to give α- imino-orthocarboxylic acid trialkylesters 12, 14 and 20, which form an equilibrium with the tautomeric enamines 13, 15 and 21. The enamines 21 react with N,N-dimethylformamide dimethylacetal (24) to give amidines 25 which are cyclized to pyridinium salts 28 and 29 on treatment with benzyl bromide and acetyl chloride, respectively. The reaction of the enaminonitrile 13a with the orthoamide derivative of phenylpropiolic acid 30 affords the pyridine-2-orthocarboxylic acid trimethylester 31. The N,O-protected 4-hydroxy-piperidine 35 can be deprotonated by means of sec-butyl lithium. The carbanions thus formed are trapped with D2O, dimethyl sulfate, phenylisocyanate, CO2, and dimethyl carbonate delivering the piperidine derivatives 37 - 41. The heterocyclic orthoester 43 can be prepared analogously from 35 and 3a. The piperidine derivatives 44, 46 and 47 are prepared from the N,O-protected piperidines 39 and 41.

ChemInform Abstract: A Convenient Synthesis and Some Characteristic Reactions of Novel Propiolamidinium Salts.

AbstractThe reaction of alkynes such as (I) with hexaalkylguanidinium chlorides (II) provides novel orthoamide derivatives which are converted into propiolamidinium halides, triflates, and tetraphenylborates.

A Convenient Synthesis and Some Characteristic Reactions of Novel Propiolamidinium Salts

Starting from N,N,N′,N′,N′′,N′′-hexaalkylguanidinium chlorides and terminal alkynes, a series of new orthoamide derivatives of alkynecarboxylic acids were prepared. The orthoamides were converted into propiolamidinium chlorides by reaction with benzoyl chloride and into propiolamidinium triflates by reaction with triethylsilyl trifluoromethanesulfonate. Propiolamidinium salts undergo conjugate addition reactions with sec-amines and thiols­. Treatment of terminal alkyne chlorides with silver(I) oxide afforded a silver complex, which can apparently adopt the composition of either a bisalkynyl silver complex [Ag(CCC(NMe2)2)2]AgCl2 or a monoalkynyl silver complex [ClAgCCC(NMe2)2].

Orthoamide, LXV [1]. Kondensationsreaktionen von Amidinen, Guanidinen, Hydrazin und Hydrazin-Derivaten mit Orthoamiden von Alkincarbonsäuren / Orthoamides,LXV [1]. Condensation Reactions of Amidines, Guanidines, Hydrazine and Hydrazine Derivatives with Orthoamides of Alkyne Carboxylic Acids

The orthoamide derivatives 4 react with amidines 10 and guanidines 11 to give 4-dimethylaminopyrimidines 12. The 3-dimethylamino-pyrazoles 13a - c can be prepared from orthoamides 4 and hydrazine. The hydrazine derivative 14, whose constitution was established by crystal structure analysis, is obtained in low yield when hydrazine is added dropwise to a boiling solution of 4d in THF. Methyl- and phenylhydrazine, undergo reaction with the orthoamides 4a, c yielding mixtures of the isomeric pyrazoles 19 and 20. The reaction of 4c with acylhydrazines 21a - e affords the pyrazole 13b. The pyrazole 26 is produced in the reaction of 4a and acet-hydrazide according to this scheme, whereas 4a reacts with aromatic acid hydrazides 21c - e to give condensation products, which are presumably amidrazones 28. The 4,5-diaza-octatetraene derivative 30 results from the reaction of 4c with p-toluenesulfonylhydrazide. Ketene aminals 34a - c are the products of the reaction of the orthoamides 4b - d with 4,4-dimethylthiosemicarbazide 34, which cyclize on heating to give highmelting pyrazolethiones 35a - c. According to the crystal structure analysis of 35c the compounds have zwitterionic character and are associated via hydrogen bridges in the solid state.

Orthoamide. Part 41. A New, Efficient Procedure for the Synthesis of Orthoamide Derivatives of Alkyne Carboxylic Acids.

ChemInformVolume 36, Issue 26 Preparative Organic Chemistry Orthoamide. Part 41. A New, Efficient Procedure for the Synthesis of Orthoamide Derivatives of Alkyne Carboxylic Acids. Willi Kantlehner, Willi Kantlehner Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorRalf Kress, Ralf Kress Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorJochen Mezger, Jochen Mezger Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorSebastian Ladendorf, Sebastian Ladendorf Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this author Willi Kantlehner, Willi Kantlehner Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorRalf Kress, Ralf Kress Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorJochen Mezger, Jochen Mezger Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this authorSebastian Ladendorf, Sebastian Ladendorf Fachbereich Chem., Fachhochsch. Aalen, D-73430 Aalen, GermanySearch for more papers by this author First published: 31 May 2005 https://doi.org/10.1002/chin.200526043Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume36, Issue26June 28, 2005 RelatedInformation

Orthoamide, LVIII . Kondensationsreaktionen von CH2-aciden Verbindungen mit Orthoamiden von Carbonsäuren und Alkincarbonsäuren / Orthoamides, LVIII . Condensation Reactions of CH2-Acidic Compounds with Orthoamides of Carboxylic Acids and Alkyne Carboxylic Acids

The orthoamide derivatives 1s and 2e were prepared from the guanidinium salt 7a and the appropriate carbanions. Cleavage of the orthoamide 2e with benzoyl chloride affords the amidinium salt 10a, which can be transformed into the amidinium salt 10b by an anion exchange reaction. The enamines 11a-i, 12a-c, 13a, b, 14a-c, 15a, b, 16, 17a, b, 18a, b, 19a, b, 20 were prepared by condensation of CH2-acidic compounds with the carboxylic acid orthoamides 2a-j. The orthoamide 2d reacts with 1-nitropropane to give the amidinium salt 27a which is transformed into the salt 27b. From benzyl cyanide and orthoamides 2g, i the enamines 30 and 32 were obtained. Similar condensation reactions were performed with the orthoamides of alkyne carboxylic acids 1b, 1c, 1d, 1e, 1p, 1s, giving the push-pull-butadiene derivatives 35a-f, 36a-f, 37a-j, 38a, b, 39a, b, 40a, b. Crystal structure analyses of the butadiene derivatives 37a, 39a, b, 40a, b and 42 were performed, showing that in 37a, 39b, 40a, b by far the shortest bond distance is between C-2 and C-3 of the butadiene system. In 39a the bonds between C1-C2, C2-C3 and C3-C4 are nearly of equal length, whereas in the 1,3-diene unit of 42 the shortest bonds are between C1-C2 and C3-C4.

Metal complex-substituted polysiloxanes as novel coatings for capillary electrophoresis and capillary electrochromatography

Two novel polysiloxane-based polymers, which contain metal complexes, have been prepared. To prepare the Co(TACN) 2 3+ (TACN=1,4,7-triazacyclononane) based polymers, an orthoamide derivative of TACN was added to bromobutane-substituted methylpolysiloxane and hydrolyzed with base. Co(II) was then coordinated to the TACN, followed by cobalt oxidation to make polymer A or followed by N-octyl TACN coordination and cobalt oxidation to make polymer B. In both materials, TACN forms thermodynamically and kinetically stable Co(TACN) 2 3+ complexes in which the six coordination sites of the Co(III) are occupied by nitrogens from the TACN. The polymers were coated on fused-silica capillary columns and spherical silica particles, which were used for capillary electrophoresis and capillary electrochromatography, respectively. The open and packed columns showed strong and pH-independent reversed electroosmotic flow.

ChemInform Abstract: Orthoamides. Part 49. Reactions of Orthoamide Derivatives with Sulfur and Selenium, Syntheses of 1,3‐Thiazole and 1,3‐Selenazole Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Orthoamide. IL. Umsetzungen von Orthoamid-Derivaten mit Schwefel und Selen, Synthesen von 1,3-Thiazol- und 1,3-Selenazolderivaten

Orthoamides. IL. Reactions of Orthoamide Derivatives with Sulfur and Selenium, Syntheses of 1,3-Thiazole- und 1,3-Selenazole Derivatives N,N-Dimethylformamide acetal reacts with elemental selenium to give a mixture of selenocarbonic acid derivatives 2 and 3, which can be converted to the pure N,N-dimethylcarbamidic acid Se-methylester 2 by treatment with methyl iodide. Analogously from the orthoformic acid derivatives 5 and 6 and selenium the N,N,N′,N′-tetramethyl-selenurea 7 can be prepared. In the reaction of 12 with elemental sulfur and selenium the amidines 14 and 15, respectively, are formed. By treatment of 14 and 15 with α-halogenated carbonyl compounds and triethylamine the 1,3-thiazoles 18 and 1,3-selenazoles 19 can be prepared. The synthesis of the propynoic acid orthoamide 26b is described. 26b reacts with the guanidinium salt 24b to give the bis-orthoamide of butynedioic acid 20b. Other orthoamides of butynedioic acid 20b–20e can be synthesized from the orthoamide 20a by transamination. The thiolation of the orthoamides affords the bisamidinium-dithiolates 21a–c, which can be alkylated to give the bisamidinium salts 27. By treatment with α-halogene carbonyl compounds and triethylamine the dithiolates 21a–c are cyclized to give thieno [3,2b] thiophenes 28a–n. The quadrupoles 21 undergo cycloadditions with dimethyl-butynedioate which afford the bis(3H-thiophene-2-ylidenes) 29a–c. Treatment of 29a with methyl tosylate gives rise to the dithiophene 30a. The dithiophene 30b can be obtained by heating 21b with dimethylbutynedionate.

ChemInform Abstract: Orthoamides. Part 42. Reactions of Dinitriles with Orthoamide Derivatives of Formic and Carbonic Acid.

AbstractDie Reaktion zwischen den Dinitrilen (I) und dem Orthokohlensäurederivat (II), welches meist im Überschuß (bis zu 2 mol) zugesetzt werden muß, ergibt in Abhängigkeit von n in (I) die im Formelschema aufgeführten Produkte.

Studies on imidazole derivatives and related compounds. 4. Synthesis of O‐glycosides of 4‐carbamoylimidazolium‐5‐olate

AbstractRibosylation of trimethylsilyl derivative of 1‐(4‐nitrobenzyl)‐5‐carbamoylimidazolium‐4‐olate (5) with 1,2,3,5‐tetra‐O‐acetyl‐β‐D‐ribofuranose in the presence of stannic chloride and trimethylsilyl trifluoromethanesulfonate afforded no 5‐O‐glycosides but N‐1 ribosylated compound (6). However, 5‐O‐riboside (7a) and its orthoamide derivative (8) were given by glycosylation of tri‐n‐butylstannyl derivative of 5 with 2,3,5‐tri‐O‐acetyl‐β‐D‐ribofuranosyl chloride in the presence of silver trifluoromethanesulfonate. This procedure was successfully applied to other sugars and 5‐O‐glucuronide (11), a possible metabolite of 1 in vivo, was obtained as one of the 5‐O‐glycoside derivatives.