Orthoamides and iminium salts, LXXXIX. Reactions of N,N,N′,N′,N″,N″,N′″,N′″-octamethyl-acetylene-bis(carboxamidinium) tetrafluoroborate with nucleophilic reagents – new methods for the preparation of amidinium salts and ketene aminalsa

2015 ◽  
Vol 70 (4) ◽  
pp. 225-241 ◽  
Author(s):  
Konstantin Drandarov ◽  
Ioannis Tiritiris ◽  
Willi Kantlehner
Keyword(s):  
Ethyl Cyanoacetate ◽  
Diels Alder ◽  
Ring Closure ◽  
Secondary Amines ◽  
Mercaptoacetic Acid ◽  
Iminium Salts ◽  
Hydroxy Compounds ◽  
Acidic Compounds ◽  
Derivatives Of

AbstractThe acetylene-bis(carboxamidinium) salt 4 dehydrates carboxylic acids to the corresponding anhydrides, as the byproduct 2-oxo-but-2-en-amidinium salt 6b was isolated. Aromatic hydroxy compounds and 2-furyl-methylmercaptan add to the triple bond of the salt 4 to give 2-aryloxy- and 2-alkylmercapto-but-2-ene-bis(amidinium) salts 7–9. According to this reaction principle, 2-organoamino-buten-2-ene-bis(amidinium) salts 10 and 11 were prepared from 4 and primary and secondary amines, whereas 4-chlorobenzhydrazide reacted with 4 to give the imidazole-3-carboxamidinium salt 13. The reaction of CH2-acidic compounds as malononitrile or ethyl cyanoacetate with the bis(amidinium) salt 4 affords 2-cyanomethylene-but-3-enamidinium salts 15. With the CH-acidic diethyl 2-bromomalonate, compound 4 undergoes a Michael-initiated ring closure cyclopropenation reaction with further ring opening by the released Br– to the corresponding 2-diethoxycarbonylmethylene-3-bromo-but-3-enamidinium salt 18. Unlike cyclopentadiene and furane, the reaction of N-methylpyrrole and bis(amidinium) salt 4 does not lead to Diels–Alder [4 + 2] cycloadduct but to the Michael-type 1:1 adduct 20. Pyrrole- and thiophene-2-carboxamidinium salts 23–25 can be prepared from compound 4 and esters of glycine, N-methylglycine (sarcosine), and mercaptoacetic acid, respectively. The derivatives of quinoxaline-2-carboxamidinium salts 29 are accessible from aromatic 1,2-diamines and compound 4. The reaction of the CH2/NH-acidic cyanoacetamide with the bis(amidinium) salt 4 produced the 3-pyrroline-2-on derivatives 33.

scholarly journals Cycloadditionen, XX Thermisch induzierte intramolekulare Reaktionen bei 2-Methyl-2,3-butadienamiden / Cycloadditions, XX Thermally Induced Intramolecular Reactions of 2-Methyl-2,3-butadienamides

1992 ◽  
Vol 47 (12) ◽  
pp. 1785-1794 ◽  
Author(s):  
Gerhard Himbert ◽  
Hans-Jürgen Schlindwein
Keyword(s):  
Double Bond ◽  
Alder Reaction ◽  
Diels Alder ◽  
Secondary Amines ◽  
Thermally Induced ◽  
Methyl Group ◽  
Diels Alder Reaction ◽  
Intramolecular Reactions ◽  
Derivatives Of ◽  
Allenic Acid

The 2-methyl-2,3-butadienamides 4a—m are directly synthesized by the reaction of the corresponding allenic acid chloride 2 with the secondary amines 3. At heating, 4a—j undergo the intramolecular Diels-Alder reaction, by using their ω-standing double bond and the π-system of the directly bonded phenyl groups or of the “methylenic” bonded arenes or furans. Thereby the tricycles 6a—g (bearing five-membered lactam moreties) and/or the tricycles 7-9 (bearing six-membered lactam moreties) are formed. The influence of the geminai methyl group on the chemoselectivity and on the velocity of the IMDA reactions is investigated. The N-allyl derivatives of 4 (s. 41 and m) form the bicycles 10 by intramolecular [2+2]-Cycloaddition.

One-pot, Three-component Synthesis of 7H-[1,3,4]Thiadiazolo[ 3,2-a]pyridines from 2-Phenacyl-[1,3,4]thiadiazole Derivatives and Arylmethylene-cyanoacetic Acid Derivatives

2007 ◽  
Vol 62 (10) ◽  
pp. 1298-1304 ◽  
Author(s):  
Imran Ali Hashmi ◽  
Wolfgang Frey ◽  
Ivo C. Ivanovc ◽  
Willi Kantlehner
Keyword(s):  
Ring Closure ◽  
The Novel ◽  
Pyridine Derivatives ◽  
Cyanoacetic Acid ◽  
One Pot ◽  
X Ray ◽  
Thiadiazole Ring ◽  
Thiadiazole Derivatives ◽  
Hydroxy Compounds ◽  
Derivatives Of

Generally, arylmethylene-cyanoacetic acid derivatives react with enols and aromatic or heteroaromatic hydroxy compounds to afford 2-amino-4H-pyran derivatives of type 6. In contrast, a ring closure with the nitrogen atom of the thiadiazole ring occurs when 2-phenacyl-1,3,4-thiadiazoles (1a - d) act on derivatives of arylmethylene-cyanoacetic acid giving rise to the formation of 7H- [1,3,4]thiazolo[3,2-a]pyridine derivatives 5a - r. The same products are obtained if 2-phenacyl-1,3,4- thiadiazoles react with aromatic or heteroaromatic aldehydes and cyanoacetic acid derivatives. The constitution of the novel compounds 5 has been confirmed by an X-ray analysis of 5a.

Some 1-substitution derivatives of 4-aryl-2,3-dihalogeno-1-naphthols

1984 ◽  
Vol 49 (1) ◽  
pp. 110-121 ◽  
Author(s):  
Jiří Křepelka ◽  
Drahuše Vlčková ◽  
Milan Mělka
Keyword(s):  
Thionyl Chloride ◽  
Oxirane Ring ◽  
Secondary Amines ◽  
Two Phase ◽  
Lytic Effect ◽  
Primary And Secondary Amines ◽  
Phase Medium ◽  
Chloro Derivatives ◽  
Derivatives Of

Alkylation of derivatives of 4-aryl-1-naphthols (I-V) by 2,3-epoxypropyl chloride in methanolic sodium hydroxide gave epoxy derivatives VI, VIII, IX, XI and XII, apart from products of cleavage of the oxirane ring, VII and X. Analogous alkylation of compounds I, IV and V by 2-(N,N-diethylamino)ethyl chloride hydrochloride in a two-phase medium afforded basic ethers XIII to XV. The cleavage of the oxirane ring in compound VI by the action of primary and secondary amines, piperidine and substituted piperazines led to compounds XVI-XXIV. Reaction of thionyl chloride with compounds XXI, XXII and XXIV gave chloro derivatives XXV-XXVII.Exposure of compound XXII to 4-methylbenzenesulfonyl chloride produced compound XXVIII, retaining the secondary alcoholic group. In an antineoplastic screening in vivo none of the compounds prepared had an appreciable activity. Compound XVII, being an analogue of propranolol, was used in the test of isoproterenolic tachycardia, and showed a beta-lytic effect comparable with that of propranol.

Reactions of 3-cyano-1-methylquinolinium methyl sulphate with some C-acids and with p-nitroaniline

1981 ◽  
Vol 46 (2) ◽  
pp. 503-505 ◽  
Author(s):  
Oldřich Kocián ◽  
Miloslav Ferles
Keyword(s):  
Sodium Methoxide ◽  
Ethyl Cyanoacetate ◽  
Derivatives Of

The action of malononitrile, ethyl cyanoacetate, dibenzoylmethane and/or p-nitroaniline on compound I in the presence of sodium methoxide gives rise to derivatives of 3-cyano-1-methyl-1,4-dihydroquinoline, II and III

Synthesis of azaanthraquinones: homolytic substitution of pyridines

1982 ◽  
Vol 35 (7) ◽  
pp. 1451 ◽  
Author(s):  
DW Cameron ◽  
KR Deutscher ◽  
GI Feutrill ◽  
DE Hunt
Keyword(s):  
Ring Closure ◽  
Pyridine Derivatives ◽  
Derivatives Of ◽  
Substituted 1 ◽  
Homolytic Substitution

Synthesis of specific di- and tri-hydroxyazaanthraquinones by Friedel-Crafts procedures is limited by orientational ambiguity and by the lack of reactivity of pyridine derivatives in electrophilic acylation processes; however, suitable pyridines have been made to undergo radical benzoylation and benzylation at unsubstituted positions 2, 4 and 6. In particular, derivatives of pyridine-3-carbo-nitrile have been benzoylated at positions 2 and 4. Ring closure by intramolecular Houben-Hoesch reaction has then led to specifically substituted 1-and 2-azaanthraquinones and thence to the antibiotic bostrycoidin (1).

Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines — Synthesis, characterization, and X-ray crystal structure

2006 ◽  
Vol 84 (10) ◽  
pp. 1294-1300 ◽  
Author(s):  
Keith Vaughan ◽  
Shasta Lee Moser ◽  
Reid Tingley ◽  
M Brad Peori ◽  
Valerio Bertolasi
Keyword(s):  
Crystal Structure ◽  
Significant Degree ◽  
Ion Trapping ◽  
Published Data ◽  
X Ray ◽  
X Ray Crystallography ◽  
Diazonium Ion ◽  
Derivatives Of ◽  
C Nmr

Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines (1a–1f) in excellent yield. The products have been characterized by IR and NMR spectroscopic analysis, elemental analysis, and X-ray crystallography. The X-ray crystal structure of the p-methoxycarbonyl derivative (1c) establishes without question the connectivity of these novel molecules, which can be described as linear bicyclic oligomers with two imidazolidinyl groups linked together by a one-carbon spacer. This is indeed a rare molecular building block. The molecular structure is corroborated by 1H and 13C NMR data, which correlates with the previously published data of compounds of types 5 and 6 derived from 1,3-propanediamine. The triazene moieties in the crystal of 1c display significant π conjugation, which gives the N—N bond a significant degree of double-bond character. This in turn causes restricted rotation around the N—N bond, which leads to considerable broadening of signals in both the 1H and 13C NMR spectra. The molecular ion of the p-cyanophenyl derivative (1b) was observed using electrospray mass spectrometry (ES + Na). The mechanism of formation of molecules of type 1 is proposed to involve diazonium ion trapping of the previously unreported bisimidazolidinyl methane (13).Key words: triazene, bistriazene, imidazolidine, synthesis, X-ray crystallography, NMR spectroscopy.

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