Malonic amides

A synthesis of the prostaglandin analogue TEI-9826 is presented in Scheme 9.40 as an example of the use of an Ir-catalyzed aUyUc alkylation [44]. The allylic alkylation with a malonic amide of the Weinreb type as pronucleophile gave the substi-... 

Mahajan, G.R. Prabhu, D.R. Manchanda, V.K. Badheka, L.P. Substituted malon-amides as extractants for partitioning of actinides from nuclear waste solutions, Waste Management 18 (1998) 125-133. 

Dozol, H., Berthon, C. 2007. Characterization of the supramolecular structure of malon-amides by application of pulsed field gradients in NMR spectroscopy. The Royal Society of Chemistry. Physical Chemistry Chemical Physics 9 5162-5170. 

L. Lefrancois, J. J. Delpuech, M. Hebrant, J. Chrisment, and C. Tondre. Aggregation and protonation phenomena in third phase formation An NMR study of the quaternary malon-amide/dodecane/nitric acid/water system. J. Phys. Chem. B, 105(13) 2551-2564, 2001. 

Polymers 20 containing covalently bound moieties of amide groups 2 mmol of 3,6-diaza-l,8-octanediamine (Aldrich) and 0.96 g (5 mmol) triiso-propanolamine were dissolved in 30 mL of pyridine. 100 mg of the malonic ester polymer (0.178 mmol of malonic ester groups) were added and the mixture was refluxed for 24 h. After the mixture had cooled, the resin was filtered, washed with methanol and water and then treated with acetone in a Soxhlet apparatus for 2 h. The products were dried at 80 °C in vacuo. According to N analysis, the polymers 20 eontain 1.71 mmol malonic amide groups per g polymer. IR (KBr) 1670 cm" (v C=0 amide), weaker absorption 1736 cm" (v C=0 ester). 

Amide [107-91-5]. Cyanoacetamide. Malonic amide nitrile C3H4N2O M 84.077... 

Reactions. The chemical properties of cyanoacetates ate quite similar to those of the malonates. The carbonyl activity of the ester function is increased by the cyano group s tendency to withdraw electrons. Therefore, amidation with ammonia [7664-41-7] to cyanoacetamide [107-91-5] (55) or with urea to cyanoacetylurea [448-98-2] (56) proceeds very easily. An interesting reaction of cyanoacetic acid is the Knoevenagel condensation with aldehydes followed by decarboxylation which leads to substituted acrylonitriles (57) such as (29), or with ketones followed by decarboxylation with a shift of the double bond to give P,y-unsaturated nitriles (58) such as (30) when cyclohexanone [108-94-1] is used. 

Condensation of m-fluorobenzaldehyde with malonic acid leads to the trans cinnamic acid 96 acylation of the acid chloride with cyclopropylaminc leads to amide 97 (cinflumide), a muscle relaxant [24]. 

N-Phenyl-N-(2-emino5malonic acid ethyl ester amide... 

The Michael reaction occurs with a variety of a,/3-unsaturated carbonyl compounds, not just conjugated ketones. Unsaturated aldehydes, esters, thio-esters, nitriles, amides, and nitro compounds can all act as the electrophilic acceptor component in Michael reactions (Table 23.1). Similarly, a variety of different donors can be used, including /3-diketones, /3-keto esters, malonic esters, /3-keto nitriles, and nitro compounds. 

A more general method for preparation ofa-amino acids is the amidotnalmatesynthesis, a straightforward extension of the malonic ester synthesis (Section 22.7). The reaction begins with conversion of diethyl acetamidomalonate into an eno-late ion by treatment with base, followed by S 2 alkylation with a primary alkyl halide. Hydrolysis of both the amide protecting group and the esters occurs when the alkylated product is warmed with aqueous acid, and decarboxylation then takes place to vield an a-amino acid. For example aspartic acid can be prepared from, ethyl bromoacetate, BrCh CCHEt ... 

Calcium-binding proteins, 6, 564, 572, 596 intestinal, 6, 576 structure, 6, 573 Calcium carbonate calcium deposition as, 6, 597 Calcium complexes acetylacetone, 2, 372 amides, 2,164 amino acids, 3, 33 arsine oxides, 3, 9 biology, 6, 549 bipyridyl, 3, 13 crown ethers, 3, 39 dimethylphthalate, 3, 16 enzyme stabilization, 6, 549 hydrates, 3, 7 ionophores, 3, 66 malonic acid, 2, 444 peptides, 3, 33 phosphines, 3, 9 phthalocyanines, 2,863 porphyrins, 2, 820 proteins, 2, 770 pyridine oxide, 3,9 Schiff bases, 3, 29 urea, 3, 9... 

Chiral phosphinous amides have been found to act as catalysts in enantio-selective allylic alkylation. Horoi has reported that the palladium-catalyzed reaction of ( )-l,3-diphenyl-2-propenyl acetate with the sodium enolate of dimethyl malonate in the presence of [PdCl(7i-allyl)]2 and the chiral ligands 45 gave 46 in 51-94% yields and up to 97% ee (Scheme 38). It is notorious that when the reaction is carried out with the chiral phosphinous amide (S)-45a, the product is also of (S) configuration, whereas by using (R)-45b the enantiomeric (R) product is obtained [165]. 

AU these results indicate that silylated amides and, in particular, silylated lactams such as 388 will react with methyl or ethyl cyanoacetate or malonate and malodinitrile in the presence of HMDS 2 (to convert the leaving group MeaSiOH 4 into HMDSO 7) via the O-silylated forms such as 384b or 389 to give similar products such as 385 and HMDSO 7 (Scheme 4.54). 

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