Orthoamide, VI. Über die Umsetzung von Aminalestern mit sekundären Aminen zu Tris‐amino‐methanen

Bredereck, Hellmut; Simchen, Gerhard; Schenck, Hans Uwe

doi:10.1002/cber.19681010914

Cited by 16 publications

(3 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The commercially available compounds, tert -butoxybis(dimethylamino)methane ( 3 , also known as Bredereck's reagent) and tris(dimethylamino)methane 4 , − were investigated for the ROP of LA because they are reminiscent of other protected forms of N -heterocyclic carbenes (NHCs) − and were expected to show similar reactivities. The ROP of LA with commercially available Bredereck-type reagents in the presence of or absence of alcohol initiators is an efficient method for the synthesis of PLAs of controlled molecular weight and narrow PDIs.…”

Section: Anionic Ring-opening Polymerizationmentioning

confidence: 99%

Organocatalytic Ring-Opening Polymerization

Kamber¹,

Jeong²,

Waymouth³

et al. 2007

Chem. Rev.

1,338

1,010

View full text Add to dashboard Cite

Section: Anionic Ring-opening Polymerizationmentioning

confidence: 99%

Organocatalytic Ring-Opening Polymerization

Kamber¹,

Jeong²,

Waymouth³

et al. 2007

Chem. Rev.

1,338

1,010

View full text Add to dashboard Cite

“…With secondary amines the substitution of the alkoxy group is accompanied by a transamination to give tris(dialkylamino)methanes (eq 25). 95 The alcoholysis of aminal esters proceeds very similarly, giving rise to the formation of DMF acetals, 4,84 whereas phenols are formylated in the 4-position. N-Monosubstituted formamides are converted by t-BAE to N,N , N -trisubstituted formamidines (eq 26).…”

Section: Willi Kantlehner Universität Stuttgart Stuttgart Germanymentioning

confidence: 99%

t-Butoxybis(dimethylamino)methane

Kantlehner

Bowers

2007

Encyclopedia of Reagents for Organic Synthesis

View full text Add to dashboard Cite

1 tert-Butoxybis(dimethylamino)methane 1 CH RO NMe 2 NMe 2 (1; R = t-Bu) (t-BAE) [5815-08-7] C 9 H 22 N 2 O (MW 174.33) InChI = 1/C9H22N2O/c1-9(2,3)12-8(10(4)5)11(6)7/h8H,1-7H3 InChIKey = HXRAMSFGUAOAJR-UHFFFAOYAR (2; R = Me) (MAE) [1186-70-5] C 6 H 16 N 2 O (MW 132.24) InChI = 1/C6H16N2O/c1-7(2)6(9-5)8(3)4/h6H,1-5H3 InChIKey = NCIMAYPZWJQYGN-UHFFFAOYAO (aminal esters reactive as aminomethylenating reagents (formylating reagents) for CH 2 -and NH 2 -acidic compounds. The t-butyl analog is somewhat more reactive than the methyl derivative; bis(dimethylamino)carbene can be generated from both compounds) Alternate Name: Bredereck's reagent. Physical Data: (1) bp 50-52 • C/12 mmHg; n 20 D = 1.4250. (2) bp 128 • C/760 mmHg; 32-33 • C/25 mmHg; n 20 D = 1.4158. Solubility: miscible with nonpolar aprotic waterfree solvents (benzene, toluene, cyclohexane, diethyl ether, etc.); react with protic solvents like water (hydrolysis to DMF) or alcohols (alcoholysis affords DMF acetals). Even common solvents like acetonitrile or acetone which are weakly CH-acidic react with the aminal esters on heating. Form Supplied in: colorless to weak yellow, strong aminesmelling liquids. Analysis of Reagent Purity: the best method is 1 H NMR spectroscopic examination of a neat sample. Handling, Storage, and Precautions: both compounds should be handled in a fume hood, with strict exclusion of atmospheric moisture. They should be stored in tightly sealed containers in a refrigerator under an atmosphere of dry nitrogen or argon.Introduction. Alkoxybis(dimethylamino)methanes can be obtained in good yields from N,N,N ,N -tetraalkylformamidinium salts and alcohol-free alkoxides. 2 The reactions have to be conducted in inert, strictly anhydrous solvents like cyclohexane, hexane, ether, or THF, in which unfortunately both reagents are insoluble. As a consequence it is necessary to use relatively large amounts of the solvent and long reaction times (eq 1). In the patent literature it is claimed that by the use of a mixture of DMF and mesitylene as solvent, the yields can be improved to about 95%. 3 In another method, 4 bis(dimethylamino)acetonitrile is used as the starting compound. Alcohol-free alkoxides suspended in absolute ether substitute the cyano group to give the corresponding aminal ester (eq 2). In contrast to the aforementioned method,

show abstract

“…The temperature of the mixture was kept at 5-10°d uring the addition and for an additional 2 hr afterward. The mixture was filtered and the filtrate was distilled to obtain 25.0 g (73%) of vinylidenebisdimethylamine (3), bp 9¿5-105°( 745 mm), identical (vpc and nmr) with authentic material.1 During the addition of the methyllithium, gas was evolved which was collected; mass spectroscopy indicated 95% of methane, 1.5% of methyl chloride, and minor (<1%) components.…”

Section: Experimental Section11mentioning

confidence: 99%

Reactions of formamidinium salts with organolithium reagents

Hobbs¹,

Weingarten²

1971

J. Org. Chem.

View full text Add to dashboard Cite

Reaction of tetramethylchloroformamidinium chloride (1) with methyllithium gave vinylidenebisdimethylamine (3) in good yield. Extension of this reaction to higher alkyllithiums was unsuccessful. Reactions of 1 with íerí-butyllithium and phenyllithium proceeded by radical processes. The mechanisms of these reactions, which probably involve substit uted bis (dimethylamino )methyl radicals and possibly bis (dimethylamino) carbene, are discussed.In connection with our study of the chemistry of alkyhdenebisdialkylamines (enediamines) we have been interested in developing new synthetic routes to these compounds. Two such routes have previously been(1) H.

show abstract

Orthoamide, VI. Über die Umsetzung von Aminalestern mit sekundären Aminen zu Tris‐amino‐methanen

Cited by 16 publications

References 6 publications

Organocatalytic Ring-Opening Polymerization

Organocatalytic Ring-Opening Polymerization

t-Butoxybis(dimethylamino)methane

Reactions of formamidinium salts with organolithium reagents

Contact Info

Product

Resources

About