54527-68-3

Usage

Synthesis Reference(s)

Tetrahedron Letters, 37, p. 233, 1996 DOI: 10.1016/0040-4039(95)02136-1

InChI:InChI=1/C6H9ClO3/c1-5(8)4-6(9)10-3-2-7/h2-4H2,1H3

Upstream product

• 674-82-8 4-methyleneoxetan-2-one 
• 107-07-3 2-chloro-ethanol 
• 2911-21-9 2,4-dioxo-6-methyl-3,4-dihydro-2H-1,3-oxazine 
• 105-45-3 acetoacetic acid methyl ester 
• 541-50-4 2-acetoacetic acid 
• 107-06-2 1,2-dichloro-ethane 
• 96-24-2 3-monochloro-1,2-propanediol 
• 691-45-2 acetylketene 
• 141-97-9 ethyl acetoacetate 

Downstream Products

• 130370-22-8 3-Oxo-2-[1-(2-trifluoromethyl-phenyl)-meth-(E)-ylidene]-butyric acid 2-chloro-ethyl ester 
• 75206-24-5 2-[1-(2-Cyano-phenyl)-meth-(E)-ylidene]-3-oxo-butyric acid 2-chloro-ethyl ester 
• 54851-30-8 2,6-dimethyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 3-β-chloroethyl ester 5-isopropyl ester 
• 108337-97-9 6,2',6'-Trimethyl-1',4'-dihydro-[2,4']bipyridinyl-3',5'-dicarboxylic acid 5'-[2-(benzyl-methyl-amino)-ethyl] ester 3'-methyl ester 
• 58371-98-5 3, 5-dichloro-2-pentanone 
• 933782-12-8 2-cyclohexyl-4-ethoxycarbonyl-4-methyl-1,3-oxazole 
• 79851-62-0 ethyl 2-isopropyl-4-methyloxazole-5-carboxylate 
• 925675-85-0 5-chloromethyl-3-cyano-7-hydroxypyrazolo[1,5-a]pyrimidine 
• 62760-02-5 2-chloroethyl 2-methyl-4-(2-nitrophenyl)-5-ethoxycarbonyl-6-diethoxymethyl-1,4-dihydropyridine-3-carboxylate 
• 85396-59-4 4-(3-nitrophenyl)-2-hydroxymethyl-6-methyl-3-methoxycarbonyl-5-(β-chloroethoxy)carbonyl-1,4-dihydropyridine 
• 54527-89-8 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 3-(2-chloroethyl)ester-5-methyl ester 
• 75091-01-9 2-Cyano-6-methyl-4-(3-nitro-phenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid 5-{2-[(3,4-dichloro-benzyl)-methyl-amino]-ethyl} ester 3-ethyl ester 
• 75091-05-3 2-Cyano-6-methyl-4-(2-trifluoromethyl-phenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid 5-{2-[(3,4-dichloro-benzyl)-methyl-amino]-ethyl} ester 3-ethyl ester 
• 75091-04-2 2-Cyano-6-methyl-4-(2-trifluoromethyl-phenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid 5-{2-[(4-chloro-benzyl)-methyl-amino]-ethyl} ester 3-ethyl ester 

Relevant academic research and scientific papers

Synthesis method for preparing 3,5-dichloro-2-pentanone from methyl acetoacetate

The invention discloses a synthesis method for preparing 3,5-dichloro-2-pentanone from methyl acetoacetate. The method comprises the following steps: S1: reactor preparation: preparing two reactors, namely a first reactor and a second reactor; S2, reactor cleaning: putting the first reactor and the second reactor into clear water for cleaning, flushing the first reactor and the second reactor after cleaning is completed, and drying the first reactor and the second reactor after flushing is completed; and S3, hydrolysis for salt formation: adding methyl acetoacetate into the first reactor, dropwise adding 30% caustic soda liquid under cooling of circulating water, and continuing to conducting a reaction for 6 hours after dropwise adding so as to obtain a hydrolyzed material. According to the synthesis method for preparing 3,5-dichloro-2-pentanone from methyl acetoacetate, working steps are rigorous, flammable and explosive materials are prevented from being used, safety is improved, reaction operations are reduced, reaction efficiency is improved, and cost is effectively reduced.

Process for the transesterification of keto esters using solid acids as catalysts

A process for the transesterification of keto esters and alcohols in approximately stoichiometric amounts using a solid acid catalyst. Solid acid catalysts may be sulfated zirconia, sulfated tin oxide, sulfated titania, sulfated iron oxide, heteropoly acids, acidic clays, acidic zeolites, or any other solid acids with high acidity or super acidity, with or without dopants. One equivalent or more of keto ester, one equivalent or more of alcohol, the solid acid catalyst, and an appropriate solvent are mixed and heated to 70 to 120° C. at atmospheric or reduced pressure to furnish the keto transester in high yields.

Transesterification of ketoesters using Amberlyst-15

A facile one-to-one transesterification of ketoesters by Amberlyst-15 is described.

Selective Catalytic Transesterification, Transthiolesterification, and Protection of Carbonyl Compounds over Natural Kaolinitic Clay

Transesterification and transthiolesterification of β-keto esters with variety of alcohols and thiols and selective protection of carbonyl functions with various protecting groups catalyzed by natural kaolinitic clay are described. The clay has been found to be an efficient catalyst in transesterifying long chain alcohols, unsaturated alcohols, and phenols to give their corresponding β-keto esters in high yields. For the first time, transthiolesterification of β-keto esters with a variety of thiols has been achieved under catalytic conditions. Clay also catalyzes selective transesterification of β-keto esters by primary alcohols in the presence of secondary and tertiary alcohols giving corresponding β-keto esters. A systematic study involving the reactivity of different nucleophiles (alcohols, amines, and thiols) toward β-keto esters is also described. Sterically hindered carbonyl groups as well as α,β-unsaturated carbonyl groups underwent protection without the deconjugation of the double bond. Chemoselective protection of aldehydes in the presence of ketones has also been achieved over natural kaolinitic clay.

Asymmetric N-(3,3-diphenylpropyl)aminoalkyl esters of 4-aryl-2,6- dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acids with antihypertensive activity

A series of asymmetric 4-aryl-1,4-dihydropyridine-3,5-dicarboxylates characterized by the presence of a 3,3-diphenylpropylamino moiety in one of the ester groups were synthesized. They exhibited remarkable antihypertensive activity in spontaneously hypertensive rats as well as affinity for the 1,4- dihydropyridines binding site labelled by 3H-nitrendipine in the calcium channel. Introduction of this bulky and lipophilic amine confers to the whole series an elevated level of antihypertensive activity and a long duration of action, a structure-dependent modulation of the activity being found only in the subset characterized by the presence of a branched propylene bridge between the ester and the amino groups. The presence of the amino group is essential for oral activity. Out of this series, compound 9u (Rec 15/2375- lercanidipine) was selected for clinical development and obtained marketing authorization as an antihypertensive in several countries.

Studies on nilvadipine. II. Synthesis and structure-activity relationships of 2-hydroxymethyl- and 2-cyano-1,4-dihydropyridines containing heteroatom-substituted ester at the 5-position

The synthesis of new 2-hydroxymethyl- and 2-cyano-1,4-dihydropyridines possessing a heteroatom-substituted alkyl ester group at the 5-position of the nucleus is described. The esters were introduced via a suitable method selected from the modified Hantzsch method (method A), the hydrolysis of a chloroethyl ester obtained by method A (method B) or the replacement of the chlorine atom with various kinds of amino groups (method C). Hydroxymethyl and cyano groups at the 2-position were prepared in a similar manner to that described in a previous paper. The hypotensive activities of the compounds prepared in this paper were compared with the corresponding alkyl ester at the 5-position reported previously. It was found that N-benzylmethylaminoethyl esters, especially N-(4-chlorobenzyl)and N-(3,4-dichlorobenzyl)-N-methylaminoethyl esters, were suitable substituents at the 5-position of the 1,4-dihydropyridine nucleus and that these substituents were somewhat more effective for hypotensive activity than simple alkyl esters in a series of 2-hydroxymethyl-1,4-dihydropyridine derivatives. But it was found that the effect was reversed in a series of 2-cyano-1,4-dihydropyridine derivatives. Both of them were found to be inferior to nilvadipine (1c), accepted in clinical use for the treatment of hypertension.

Five membered ring formation of 2-hydroxyalkyl malonate and acetoacetate derivatives the problem of O-versus C-alkylation

The cyclization reactions of type 32, 34, 36, 37/38 compounds have been studied with the aim of achieving a carbon-carbon bond forming reaction at C-2 of optically active glycerol derivatives as indicated in Scheme 1. In all cases O-alkylation at the proximal CO group has been observed.

Pharmaceutically useful dihydropyridinyldicarboxylate amides and esters incorporating arylpiperazinylalkyl moities

A series of 1,4-dihydropyridin-3,5-yl dicarboxylic acid amides and esters incorporating an arylpiperazinylalkyl moiety have been prepared possessing the general formula STR1 wherein R4 is cycloalkyl, aryl or hetaryl, generally with electronwithdrawing substituents; R2 and R6 are lower alkyl, alkanol, alkoxyalkyl, or alkylaminoalkyl; R5 is R2 or arylpiperazinylalkyl; X is 0 or NH; Y is lower alkylene, alkoxyalkylene, alkylaminoalkylene; and Z is phenyl, substituted phenyl, pyridinyl, substituted pyridinyl, or pyrimidinyl. Compounds of this series demonstrate activity as calcium and alphaadrenergic blockers in in vitro testing and antihypertensive, antiischemic, and platelet function inhibiting actions in in vivo screens.