6802-75-1

Usage

Uses

Used in Pharmaceutical Industry:
Diethyl isopropylidenemalonate is used as a key intermediate in the synthesis of retinoids, which are essential for maintaining healthy skin, vision, and immune function. Diethyl isopropylidenemalonate is particularly useful in the synthesis of retinoids with functional groups at the side-chain terminus, allowing for the development of novel therapeutic agents with improved pharmacological properties.
Used in Agrochemical Industry:
Diethyl isopropylidenemalonate is also employed in the synthesis of agrochemicals, such as insecticides and herbicides. Its unique structure and reactivity make it a valuable component in the development of new and effective compounds for pest control and crop protection.

InChI:InChI=1/C10H16O4/c1-5-13-9(11)8(7(3)4)10(12)14-6-2/h5-6H2,1-4H3

Upstream product

• 4441-90-1 isopropylidenemalonic acid 
• 64-17-5 ethanol 
• 594-71-8 2-chloro-2-nitro-propane 
• 996-82-7 sodium diethylmalonate 
• 126750-05-8 2,2-dimethyl-1,1,3,3-tetraethoxycarbonylpropane 
• 876480-71-6 4-methyl-4,5-dihydro-pyrazole-3,3-dicarboxylic acid diethyl ester 
• 108-24-7 acetic anhydride 
• 67-64-1 acetone 
• 105-53-3 diethyl malonate 
• 38214-19-6 bromo-isopropyl-malonic acid diethyl ester 
• 121-69-7 N,N-dimethyl-aniline 
• 67-63-0 isopropyl alcohol 
• 15681-48-8 lithium dimethylcuprate 
• 19723-88-7 diethyl (1,3-dithian-2-ylidene)-1-propanedioate 

Downstream Products

• 861537-98-6 3-cyano-2,2-dimethyl-4,6-dioxo-cyclohexanecarboxylic acid ethyl ester 
• 408511-89-7 2,2,3-trimethyl-4,6-dioxo-cyclohexanecarboxylic acid ethyl ester 
• 759-36-4 diethyl isopropylmalonate 
• 92320-12-2 (1,1-dimethyl-pentyl)-malonic acid diethyl ester 
• 759-24-0 tert-butylmalonic acid diethyl ester 
• 859820-52-3 2,2-dimethyl-4,6-dioxo-cyclohexane-1,3-dicarboxylic acid diethyl ester 
• 621-10-3 N,N'-diphenylmalonamide 
• 78775-63-0 diethyl α-(1-methyl-1-phenylethyl)malonate 
• 92723-42-7 2-Methyl-4-isopropenyl-4-carbomethoxy-1.3-cyclohexandion 
• 35194-19-5 ethyl 3,3-dimethyl-7-octenoate 
• 82004-45-3 β-methoxyaminoisopropylmalonic acid diethyl ester 
• 105-53-3 diethyl malonate 
• 64770-16-7 ethyl 2-ethoxycarbonyl-2-methyl-3-butenoate 
• 72727-33-4 Diethyl 4,4-dimethyl-t-2,3-diphenylcyclobutane-1,1-dicarboxylate 

Relevant academic research and scientific papers

Racemic synthesis and solid phase peptide synthesis application of the chimeric valine/leucine derivative 2-amino-3,3,4-trimethyl-pentanoic acid

The synthesis of non natural amino acid 2-amino-3,3,4-trimethyl-pentanoic acid (Ipv) ready for solid phase peptide synthesis has been developed. Copper (I) chloride Michael addition, followed by a Curtius rearrangement are the key steps for the Ipv synthesis. The racemic valine/leucine chimeric amino acid was then successfully inserted in position 5 of neuropeptide S (NPS) and the diastereomeric mixture separated by reverse phase HPLC. The two diastereomeric NPS derivatives were tested for intracellular calcium mobilization using HEK293 cells stably expressing the mouse NPS receptor where they behaved as partial agonist and pure antagonist.

Synthesis and acidity of conformationally constrained 1,3-oxathiane S-oxides

Conformationally constrained 5-tert-butyl 1,3-oxathiane was synthesized and oxidation led to the diastereoisomeric sulfoxides and the respective sulfone. Stereoelectronic effects are discussed for these compounds and their corresponding 2-carbanions. pKavalues are calculated for these compounds and compared with the respective 1,3-dithiane-derived sulfide, the sulfoxides, and the sulfone.

Metal bridging for directing and accelerating electron transfer as exemplified by harnessing the reactivity of AIBN

A new strategy for tuning the electron transfer between radicals and enolates has been developed. This method elicits the innate reactivity of AIBN with a copper catalyst and enables a cascade reaction with cinnamic acids. Electron paramagnetic resonance studies and control experiments indicate that the redox-active copper species not only activates the radical by coordination, but also serves as a bridge to bring the radical and nucleophile within close proximity to facilitate electron transfer. By exploiting possible combinations of redox-active metals and radical entities with suitable coordinating functional groups, this strategy should contribute to the development of a broad range of radical-based reactions.

Synthesis of nitrogen heterocycles via α-aminoalkyl radicals generated from α-silyl secondary amines under visible light irradiation

We have succeeded in the visible light-mediated synthetic use of α-aminoalkyl radicals derived from α-silyl secondary amines toward addition to α,β-unsaturated carbonyl compounds. The resulting γ-aminocarbonyl compounds are converted into γ-lactams and pyrroles in a one-pot process. This journal is the Partner Organisations 2014.

Selective sulfenylative desulfonylation or decarbalkoxylation of α-sulfonyl malonates with DABCO or Bu3N: Reactivity and conformational analysis

The study on reactivity of severalαsubstituted αsulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu3N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the-substituent, because of sterical hindrance around the electrophilic centers (SO2 and CO2R). The derivatives with crowded α-substituents suffer selective desulfonylation, and a novel and efficient desulfonylation method can be proposed. The dependence of the reactivity ofα-sulfonyl malonates on the sterical hindrance around the electrophilic centers is confirmed by conformational analysis (Macromodel/MM2* and Mopac/MP3). The carbanionic mechanism is proved because the corresponding protonated, deuterated, and sulfenylated products were obtained by addition of the corresponding electrophilic agents. Bu3N showed itself to be a novel selective decarbalkoxylation agent for any-substituted-sulfonyl malonate.

Bronsted base-modulated Regioselective Pd-catalyzed intramolecular aerobic oxidative amination of alkenes: Formation of seven-membered amides and evidence for allylic C-H activation

A novel palladium-catalyzed intramolecular aerobic oxidative allylic C-H amination of olefins has been developed. Bronsted base can modulate the regioselectivity, favoring the formation of 7-membered rings. Mechanistic studies using deuterium-labeled substrates as probes support a rate-determining allylic C-H activation/irreversible reductive elimination pathway.

2,2-bis-(hydroxymethyl)cyclopropylidenemethyl-purines and pyrmindines as antiviral agents

Compounds which are active against viruses have the following formulas: wherein B is a purine or pyrimidine heterocyclic ring or base. In a preferred embodiment, the purine include 6-aminopurine (adenine), 6-hydroxypurine (hypoxanthine), 2-amino-6-hydroxypurine (guanine), 2,6-diamino-purine, 2-amino-6-azidopurine, 2-amino-6-halo substituted purines such as 2-amino-6-chloropurine, 2-amino-6-fluoropurine, 2-amino-6-alkoxypurines such as 2-amino-6-methoxypurine, 2-amino-6-cyclopropylaminopurine, 2-amino-6-alkylamino or 2-amino-6-dialkylamino substituted purines, 2-amino-6-thiopurine, 2-amino-6-alkylthio substituted purines, 3-deazapurines, 7-deazapurines and 8-azapurines. The pyrimidine incorporates cytosine, uracil and thymine, 5-halo substituted cytosines and uracils, 5-alkyl substituted cytosines and uracils including derivatives with a saturated or unsaturated alkyl group and 6-azapyrimidines.

Synthesis and Antiviral Activity of (Z)- and (E)-2,2-[Bis(hydroxymethyl)cyclopropylidene]methylpurines and -pyrimidines: Second-Generation Methylenecyclopropane Analogues of Nucleosides

The second generation of methylenecyclopropane analogues of nucleosides 5a-5i and 6a-6i was synthesized and evaluated for antiviral activity. The 2,2-bis(hydroxymethyl)methylenecyclopropane (11) was converted to dibromo derivative 7 via acetate 12. Alkylation-elimination of adenine (16) with 7 afforded the Z/E mixture of acetates 17 + 18, which was deacetylated to give analogues 5a and 6a separated by chromatography. A similar reaction with 2-amino-6-chloropurine (19) afforded acetates 20 + 21 and, after deprotection and separation, isomers 5f and 6f. The latter served as starting materials for synthesis of analogues 5b, 5e, 5g-5i and 6b, 6e, 6g-6i. Alkylation-elimination of N4-acetylcytosine (22) with 7 afforded a mixture of isomers 5c + 6c which were separated via N4-benzoyl derivatives 23 and 24. Deprotection furnished analogues 5c and 6c. Alkylation of 2,4-bis(trimethylsilyloxy)-5-methylpyrimidine (25) with 7 led to bromo derivative 26. Elimination of HBr followed by deacetylation and separation gave thymine analogues 5d and 6d. The guanine Z-isomer 5b was the most effective against human and murine cytomegalovirus (HCMV and MCMV) with EC50 = 0.27-0.49 μM and no cytotoxicity. The 6-methoxy analogue 5g was also active (EC50 = 2.0-3.5 μM) whereas adenine Z-isomer 5a was less potent (EC50 = 3.6-11.7 μM). Cytosine analogue 5c was moderately effective, but 2-amino-6-cyclopropylamino derivative 5e was inactive. All E-isomers were devoid of anti-CMV activity, and none of the analogues was significantly active against herpes simplex viruses (HSV-1 or HSV-2). The potency against Epstein-Barr virus (EBV) was assay-dependent. In Daudi cells, the E-isomers of 2-amino-6-cyclopropylamino- and 2,6-diaminopurine derivatives 6e and 6h were the most potent (EC50 ≈ 0.3 μM), whereas only the thymine Z-isomer 5d was active (EC50 = 4.6 μM). Guanine Z-derivative 5b was the most effective compound in H-1 cells (EC50 = 7 μM). In the Z-series, the 2-amino-6-methoxypurine analogue 5g was the most effective against varicella zoster virus (VZV, EC50 = 3.3 μM) and 2,6-diaminopurine 5h against hepatitis B virus (HBV, EC50 = 4 μM). Adenine analogues 5a and 6a were moderately active as substrates for adenosine deaminase.

2,5,6,7-tetranor-4,8-inter-m-phenylene PGI2 derivatives

Disclosed herein are novel prostaglandin I2 (PGI2) derivatives exhibiting excellent in vivo duration and activities, said derivatives being represented by the general formula: STR1 wherein R1, X, R2 and R3 are as defined herein.

ANALYSE STRUCTURALE EN SERIE CYCLOBUTANIQUE. Partie 1. Derives monosubstitues et gem disubstitues du cyclobutane

Methylene bending mode analysis of some cyclobutane-d2 molecules reveals that in the dissolved state (solvent CCl4), bromocyclobutane occurs exclusively in a pseudo-equatorial form, whereas, under the same conditions, cyclobutanol and 1-bromocyclobutane carbonitrile exist both in pseudo-axial and pseudo-equatorial conformations.NMR spectroscopy confirms the results obtained for bromocyclobutane and leads to the conclusion that the pseudo-equatorial conformer is predominant in the case of cyclobutanol as well as in that of cyclobutane carbonitrile.A theoretical study of cyclobutanol in the gaseous state by the P.C.I.L.O. method gives results which are consistent with a pseudo-equatorial conformer.