Orthoamide und Iminiumsalze, IIC. Darstellung von N-(ω-Ammonioalkyl)-N,N′,N′,N″,N″-peralkylierten Guanidiniumsalzen und N-(ω-Aminoalkyl)-N′,N′,N″,N″-tetramethylguanidinen

2020 ◽  
Vol 75 (6-7) ◽  
pp. 665-684
Author(s):  
Willi Kantlehner ◽  
Ioannis Tiritiris ◽  
Markus Vettel ◽  
Wolfgang Frey
Keyword(s):  
Dimethyl Sulfate ◽  
Benzyl Bromide ◽  
Aqueous Sodium Hydroxide ◽  
Molar Ratio ◽  
Ethyl Bromoacetate ◽  
Strong Base ◽  
Quaternary Salts ◽  
Alkylating Reagents ◽  
Guanidinium Salt ◽  
Guanidinium Salts

AbstractN,N,N′,N′-Tetraalkylchlorformamidiniumchlorides 1a, b react with ω-dimethylaminoalkylamines 19, 20 to give mixtures of N-(ω-dimethylammonioalkyl)-guanidinium salts 12, 13 and N-(ω-dimethylaminoalkyl)-guanidinium salts 21, 22. These mixtures are transformed to mixtures of the ureas 15, 17 and N-(ω-dimethylaminoalkyl)-guanidines 23, 25 on treatment with aqueous sodium hydroxide. The reaction of N-(3-dimethylammoniopropyl)-guanidin 25a with dimethylsulfate in a molar ratio of 1:1 delivers a mixture of the N-(3-dimethylaminopropyl)-N,N,N′,N′,N″,N″-pentamethyl-guanidinium salt 29a and the N-(3-dimethylammoniopropyl)-N,N′,N′,N″,N″-pentamethyl-guanidinium-bis (methylsulfate) 33a. The action of dimethylsulfate on the guanidines 23a, 25a in a molar ratio of 2:1 affords the bisquarternary salts 32a, 33a. Alkylating reagents as methyliodide, benzylbromide, allylbromide and chloroacetonitrile attack N-(2-dimethylaminoethyl)-N′,N′,N″,N″-tetraethylguanidine (23b) in a molar ratio of 1:1 cleanly at the dimethylaminoethylgroup to give the ammonium salts 30a–d. As a strong base the guanidine 23b dehydrochlorinates β-Chlorpropionitrile and chloroacetone under formation of the guanidinium salt 21c. In contrast to this the reaction of ethyl bromoacetate with the N-(2-dimethylaminoethyl)guanidine 23b occurs at the guanidinogroup giving the guanidinium salt 28c. The methylation of the guanidinium chlorides 21a, 22a with dimethyl sulfate affords the bis-quaternary salts 35b, 36b with mixed anions. From the heterocyclic guanidines 14, 16 and the alkylating reagents benzylbromide and ethyl bromoacetate the heterocyclic guanidinium salts 37a, b, 39a, b can be obtained. The reactions with ethyl chloroformiate proceed in an analogous way giving the guanidinium salts 37c, 39c. The N-alkyl-N,N,N′,N′-tetramethyl-(3-ureidopropyl)guanidinium salts 41a, b can be prepared from the N′,N′,N″,N″-tetramethyl-N′′-(3-ureidopropyl) guanidine 17a and the alkylating compounds dimethyl sulfate and benzyl bromide. Several compounds obtained that way were transformed to the corresponding tetraphenyloborates and bis(tetraphenylborates), respectively.

Orthoamide, LXIX [1]. Beiträge zur Synthese N,N,N´,N´,N´´-peralkylierter Guanidine und N,N,N´,N´,N´´䞲,N´´-persubstituierter Guanidiniumsalze / Orthoamides, LXIX [1]. Contributions to the Synthesis of N, N, N´, N´, N´-peralkylated Guanidines and N, N, N´, N´, N´´, N´´-persubstituted Guanidinium Salts

2010 ◽  
Vol 65 (7) ◽  
pp. 873-906 ◽  
Author(s):  
Willi Kantlehner ◽  
Jochen Mezger ◽  
Ralf Kreß ◽  
Horst Hartmann ◽  
Thorsten Moschny ◽  
...  
Keyword(s):  
Sodium Hydroxide ◽  
Allyl Chloride ◽  
Dimethyl Sulfate ◽  
Benzyl Bromide ◽  
Ethyl Acrylate ◽  
Secondary Amines ◽  
Butyl Bromide ◽  
Modified Method ◽  
Alkyl Groups ◽  
Guanidinium Salts

N, N, N´, N´-Tetraalkyl-chloroformamidinium chlorides 6 are prepared from N, N, N´, N´-tetraalkylureas 5 and phosgene in acetonitrile. The iminium salts 6 react with primary and secondary amines in the presence of triethylamine to give N, N, N´, N´, N´´-pentasubstituted and N, N, N´, N´, N´´, N´´- hexasubstituted guanidinium salts 7 and 8, respectively, Treatment of the guanidinium salts 7 with sodium hydroxide in excess affords the N, N, N´N´, N´´-pentasubstituted guanidines 9a - 9aa. Additionally, the N, N, N´, N´, N´´-pentasubstituted and N, N, N´, N´, N´´, N´´-hexasubstituted guanidinium salts 7l´, 7p´ and 8a - c can be obtained from the reaction mixtures by addition of stoichiometric amounts of sodium hydroxide. A modified method is described for the preparation of guanidinium salts possessing dialkylamino substituents consisting of two long-chain alkyl groups (>C14). Some guanidines 9 were alkylated with allyl chloride and bromide, ethyl bromide, butyl bromide, benzyl bromide and chloride, dimethyl sulfate, diethyl sulfate, and methyl methansulfonate to give the corresponding guanidinium salts 11 - 15. By alkylation of the N, N, N´, N´, N´´-pentasubstituted guanidine 9v with triethyloxonium tetrafluoroborate the guandinium tetrafluoroborate 16a is accessible. N-Functionalized guanidinium salts 17 - 18a - c result from the reaction of N, N, N´, N´, N´´-pentasubstituted guanidines with ethyl bromoacetate and bromoacetonitrile, respectively, and subsequent anion exchange with sodium tetraphenylborate. N, N, N´, N´-Tetramethylguanidine (21) adds to ethyl acrylate to give the labile guanidine 22, which forms the guanidinium salt 23a on treatment with methyl iodide. Zwitterionic guanidinium salts 25 result, when N, N, N´, N´, N´´-pentasubstituted guanidines are treated with sultones 24.

Orthoamide und Iminiumsalze, IC. Synthese und Reaktionen von N,N,N′,N′,N′′-Pentaalkyl-N′′-[2-(N,N,N′,N′,N′′-pentaalkylguanidinio)ethyl]-guanidiniumsalzen

2020 ◽  
Vol 75 (6-7) ◽  
pp. 685-695
Author(s):  
Willi Kantlehner ◽  
Ioannis Tiritiris ◽  
Wolfgang Frey ◽  
Ralf Kreß
Keyword(s):  
Crystal Structure ◽  
Guanidinium Salt ◽  
Guanidinium Salts

AbstractBis[bis(dibutylamino)methylen]hydrazine 8 is prepared from N,N,N′,N′-tetrabutylchloroformamidinium chloride (4c) and hydrazine. Bromine transforms 8 to the heterocyclic guanidinium salt 15a which is isolated as tetraphenylborate. From N,N,N′,N′-tetraalkylchloroformamidiniumchlorides and ethylendiamine the diguanidines are prepared which are alkylated to give diguanidinium salts, From these salts guanidinium salts can be prepared by anion metathesis with tetraphenylborate-, iodide-, hexafluorphosphate-, trifluoromethansulfonat-, bis(trifluormethansulfonyl)imide and tricyanmethanide as counteranions. The structure of the compounds 15 and 17b is confirmed by crystal structure analyses.

The N-Alkylation and N-Arylation of Unsymmetrical Pyrazoles

1979 ◽  
Vol 32 (10) ◽  
pp. 2203 ◽  
Author(s):  
MR Grimmett ◽  
KHR Lim ◽  
RT Weavers
Keyword(s):  
Dimethyl Sulfate ◽  
Steric Effects ◽  
Basic Medium ◽  
Alkyl Aryl ◽  
Quaternary Salts ◽  
Electronic And Steric Effects

Unsymmetrical pyrazoles with alkyl, aryl, nitro and carboxyl substituents at C3 or C5 have been methylated with dimethyl sulfate in methanol, dimethyl sulfate in basic medium, and with diazomethane. The ratios of the isomeric N-methylpyrazoles have been determined by N.M.R. and g.l.c. analysis. The modified Ullmann phenylation has also been applied to these pyrazoles. Explanations for the observed product orientations involve considerations of electronic and steric effects, the possible intermediacy of quaternary salts, and, in some instances, the likelihood that the dominant tautomer is reacting.

scholarly journals 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

2012 ◽  
Vol 67 (4) ◽  
pp. 373-388
Author(s):  
Willi Kantlehner ◽  
Markus Vettel ◽  
Bernhard Eppinger
Keyword(s):  
Ethyl Acetate ◽  
Acetyl Chloride ◽  
Dimethyl Carbonate ◽  
Dimethyl Sulfate ◽  
Benzyl Bromide ◽  
Sodium Hydride ◽  
Pyridinium Salts ◽  
Dimethylformamide Dimethylacetal ◽  
Butyl Lithium ◽  
Iminium Salts

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.

Preparation and characterization of sugarcane bagasse hemicellulosic derivatives containing quaternary ammonium groups in various media

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Ren Jun-Li ◽  
Liu Chuan-Fu ◽  
Sun Run-Cang ◽  
She Diao ◽  
Liu Jian-Chao
Keyword(s):  
Dimethyl Sulfoxide ◽  
Sodium Hydroxide ◽  
Sodium Hydroxide Solution ◽  
Aqueous Sodium Hydroxide ◽  
Molar Ratio ◽  
Aqueous Sodium ◽  
Ft Ir ◽  
Thermal Stability Of ◽  
C Nmr

AbstractTo increase the solubility and produce cationic or ampholytic polymers as beater additives in papermaking from native hemicelluloses, quaternization of hemicelluloses were performed by reacting hemicelluloses with 3-chloro-2- hydroxypropyltrimethylammonium chloride (CHMAC) and preferably with 2,3- epoxypropyltrimethylammonium chloride (ETA) in aqueous sodium hydroxide, homogenously in dimethyl sulfoxide (DMSO), and completely heterogeneously in ethanol/water, respectively. The extent of modification was measured by degree of substitution (DS), and its value of up to 0.55 can be controlled by adjusting the molar ratio of reagent to hydroxyl functionality in hemicelluloses and the concentration of sodium hydroxide. The characterization of hemicellulosic derivatives was performed by elemental analysis, GPC, FT-IR and 13C NMR spectroscopy as well as thermal analysis. It was found that hemicellulosic polymer was significantly degraded in aqueous sodium hydroxide solution compared with in dimethyl sulfoxide and in ethanol/water systems under the conditions given. The thermal stability of modified hemicelluloses decreased after chemical modification, corresponding to the decreasing Mw of hemicelluloses derivatives.

Concise Synthesis and Displacement Reactions of Model 3-(Alkylthio)- 6-chloro- and 2,6-Dichlorothieno[2,3-e][1,4,2]dithiazine 1,1-Dioxides

2011 ◽  
Vol 66 (7) ◽  
pp. 715-720
Author(s):  
Rajab Abu-El-Halawa ◽  
Mohanad Masad ◽  
Yaser Bathich ◽  
Mahmoud Al-Refai ◽  
Mohammad M. Ibrahim ◽  
...  
Keyword(s):  
Antibacterial Activity ◽  
Carbon Disulfide ◽  
Dimethyl Sulfate ◽  
Alkyl Halides ◽  
Sulfuryl Chloride ◽  
Molar Ratio ◽  
New Approach ◽  
E Coli ◽  
Displacement Reactions

A series of 3-(alkylthio)-6-chlorothieno[2,3-e][1,4,2]dithiazine 1,1-dioxides (7a - e) were prepared via interaction of deprotonated 2,5-dichlorothiophene-3-sulfonamide with carbon disulfide under reflux, followed by alkylation with alkyl halides. Employment of dimethyl sulfate afforded the isomeric 2-methyl-3-thione derivative 8 together with the expected 3-(methylthio) derivative 7a in a molar ratio of 1 : 4. Treatment of 7a or 10 with ethylamine, aniline or p-chloroaniline produced the corresponding N-ethyl- (or N-phenyl)-6-chlorothieno[2,3-e][1,4,2]dithiazine-3-amine 1,1-dioxides 3a - c. Likewise, interaction of 7a with methylhydrazine (or phenylhydrazine) gave the respective 3-(1-methylhydrazinyl or 2-phenylhydrazinyl) 1,1-dioxides 9a, b. Desulfonation of 6-chloro-3-(methylthio)thieno[ 2,3-e][1,4,2]dithiazine 1,1-dioxide (7a) with sulfuryl chloride produced 3,6-dichlorothieno[2,3- e][1,4,2]dithiazine 1,1-dioxide (10). The latter compound was used as a substrate for the preparation of N-alkyl- (or aryl)-6-chlorothieno[2,3-e][1,4,2]dithiazin-3-amine 1,1-dioxides 3a - c representing a new approach for the synthesis of similar derivatives. Compounds 7a - e showed modest to low antibacterial activity against E. coli and S. aureus.

scholarly journals Synthesis of 1-(2-Methoxybenzyl)-1,10-phenanthrolin-1-ium Bromide from Gandapura Oil

2019 ◽  
Vol 8 (3) ◽  
pp. 239-244
Author(s):  
Muhammad Idham Darussalam Mardjan ◽  
◽  
Dhina Fitriastuti ◽  
Bambang Purwono ◽  
Jumina Jumina ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Benzyl Alcohol ◽  
Substitution Reaction ◽  
Dimethyl Sulfate ◽  
Benzyl Bromide ◽  
Solvent Free ◽  
Alkylation Reaction ◽  
Synthetic Method ◽  
Free Condition ◽  
Solvent Free Condition

This study describes simple synthetic method to prepare 1-(2-methoxybenzyl)-1,10-phenanthrolin-1-ium bromide from gandapura oil. The salt were synthesized in four steps. Initially, commercial gandapura oil was directly subjected to the alkylation reaction under basic condition using dimethyl sulfate to give methyl 2-methxybenzoate in 86% yield. Next, the produced benzoate ester was reduced by LiAlH4 to produce 2-methoxybenzyl alcohol in 67% yield. The treatment of benzyl alcohol with phosphorus tribromide under solvent free condition produced the corresponding benzyl bromide (in 67% yield), which was directly introduced into bimolecular nucleophilic substitution reaction with 1,10-phenantroline monohydrate to finally give the desired product in 63% yield.

Orthoamide und Iminiumsalze, LXXIX [1]. N-[w-(Dimethylamino)alkyl]-N´,N´,N´´,N´´-tetramethylguanidine und davon abgeleitete Guanidiniumsalze: Synthese und Kristallstrukturen/ Orthoamides and Iminium Salts, LXXIX [1]. N-[w-(Dimethylamino)alkyl]-N´,N´,N´´,N´´- tetramethylguanidines and Salts Derived therefrom: Synthesis and Crystal Structures

2012 ◽  
Vol 67 (7) ◽  
pp. 685-698 ◽  
Author(s):  
Ioannis Tiritiris ◽  
Willi Kantlehner
Keyword(s):  
Sodium Hydroxide ◽  
Crystal Structures ◽  
Dimethyl Sulfate ◽  
Aqueous Sodium Hydroxide ◽  
Chloride Ions ◽  
Sodium Tetraphenylborate ◽  
X Ray Diffraction ◽  
Aqueous Sodium ◽  
X Ray ◽  
Iminium Salts

N-(ω-Dimethylammonioalkyl)-N´,N´,N´´,N´´-tetramethylguanidinium-dichlorides 5a, b are obtained from the chloroformamidinium salt 2 and diamines 3a, b. Their crystal structures reveal that the guanidinium ions are associated with the chloride ions via N-H· · ·Cl hydrogen bonds. By deprotonation of 5a, b with one equivalent of sodium hydroxide, the guanidinium chlorides 4a, b are accessible, and a further deprotonation leads to the aminoguanidines 6a, b, which hydrolyze in the presence of excessive aqueous sodium hydroxide to give the aminoalkylureas 7a, b. The salts 9a, b and 10a, b were synthesized from 4a, b and 5a, b, respectively, by anion metathesis by means of sodium tetraphenylborate. 7a reacts with dimethyl sulfate to give the waxy ammonium salt 11a, which was converted to the crystalline tetraphenylborate salt 12a. The crystal structures of all the tetraphenylborates were determined by single-crystal X-ray diffraction analysis.

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