541-16-2

Usage

Uses

1. Used in Pharmaceutical Industry:
Di-tert-Butyl malonate is used as a pharmaceutical intermediate for the synthesis of various drugs and active pharmaceutical ingredients. Its stability and reactivity make it a preferred choice in the development of new medications.
2. Used in Chemical Synthesis:
Di-tert-Butyl malonate is used in the preparation of ketones, which are essential building blocks in the synthesis of a wide range of organic compounds, including pharmaceuticals, agrochemicals, and specialty chemicals.
3. Used in Diazomalonsaeure-di-tert-butylester Production:
Di-tert-Butyl malonate is used to produce Diazomalonsaeure-di-tert-butylester at ambient temperature. This process requires reagents such as cesium carbonate, p-toluenesulfonyl azide, and the solvent tetrahydrofuran, with a reaction time of 1 hour.
4. Used in Total Synthesis of (+/?)-Actinophyllic Acid:
Di-tert-Butyl malonate is employed as a precursor in the total synthesis of (+/?)-actinophyllic acid, a naturally occurring compound with potential biological activities.
5. Used in Metal-Organic Chemical Vapor Deposition (MOCVD) of HfO2 and ZrO2 Thin Films:
Di-tert-Butyl malonate is utilized as a precursor in the MOCVD process for the deposition of HfO2 and ZrO2 thin films, which are essential materials in the semiconductor industry for the fabrication of advanced electronic devices.

InChI:InChI=1/C11H20O4/c1-10(2,3)14-8(12)7-9(13)15-11(4,5)6/h7H2,1-6H3

Upstream product

• 141-82-2 malonic acid 
• 115-11-7 isobutene 
• 1663-67-8 malonoyl dichloride 
• 75-65-0 tert-butyl alcohol 
• 504-64-3 carbon suboxide 
• 35207-75-1 di-tert-butyl diazomalonate 
• 14630-40-1 Bis(trimethylsilyl)ethyne 
• 111-90-0 ethoxyethoxyethanol 
• 1204142-47-1 2-(hydroxy-phenylmethyl)-malonic acid di-tert-butyl ester 
• 15960-79-9 di-tert-butyl 2-bromomalonate 

Downstream Products

• 108299-76-9 trans-2-(3-methylphenyl)-3-oxo-1-cyclohexaneacetic acid 
• 57350-39-7 (+/-)-[2t-(3-methoxy-phenyl)-3-oxo-cyclohex-r-yl]-acetic acid 
• 33184-79-1 3t-(4-chloro-phenyl)-2-methyl-5-oxo-isoxazolidine-4r-carboxylic acid tert-butyl ester 
• 56877-40-8 Z-γ,γ,-di-tert-butyl-D,L-carboxyglutamic acid methyl ester 
• 56877-43-1 N-(benzyloxycarbonyl)-γ,γ-di-tert-butyl-D-γ-carboxyglutamic acid 
• 56877-44-2 γ,γ'-Di-tert-butyl-DL-γ-carboxyglutamic acid 
• 56926-92-2 2-(2-Benzyloxycarbonylamino-2-hydrazinocarbonyl-ethyl)-malonic acid di-tert-butyl ester 
• 35207-75-1 di-tert-butyl diazomalonate 
• 86633-09-2 di-tert-butyl methylenemalonate 
• 621-84-1 O-benzyl carbamate 
• 87376-40-7 2,4-Bis-tert-butoxycarbonyl-3-methoxycarbonyl-pentanedioic acid di-tert-butyl ester 
• 87376-41-8 2-Benzyloxycarbonylamino-3-tert-butoxycarbonyl-succinic acid 4-tert-butyl ester 1-methyl ester 
• 117407-47-3 Bis(t-butyl) 2-iodo-3,4,5-trimethoxybenzylpropanedioate 
• 133608-96-5 (S)-2-tert-Butoxycarbonyl-3-methyl-succinic acid 1-tert-butyl ester 4-ethyl ester 

Relevant academic research and scientific papers

Methanofullerene Molecular Scaffolding: Towards C60-Substituted Poly(triacetylenes) and Expanded Radialenes, Preparation of a C60-C70 Hybrid Derivative, and a Novel Macrocyclization Reaction

The synthesis of (E)-hex-3-ene-1,5-diynes and 3-methylidenepenta-1,4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2,3-dialkynylbut-2-ene-1,4-diyl bis(2-bromopropanedioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10, as well as during the reaction of C60 with the desilylated analogue 16 (Scheme 5), were the macrocyclic products 11, 12, and 17, respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N,N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2,3-diethynylbut-2-ene-1,4-diol (18, Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methano C-atom in carboxymethyl ethyl 1,2-methano[60]fullerene-61,61-dicarboxylate (28, Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1,3-diol (33). The first mixed C60-C70 fullerene derivative 49, consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxyethoxy)ethyl] 1,2-methano[70]fullerene-71,71-dicarboxylate (46) with an excess of the C60-carboxylic acid 28. The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49, and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers.

Ball-Milling-Enabled Reactivity of Manganese Metal**

Efforts to generate organomanganese reagents under ball-milling conditions have led to the serendipitous discovery that manganese metal can mediate the reductive dimerization of arylidene malonates. The newly uncovered process has been optimized and its mechanism explored using CV measurements, radical trapping experiments, EPR spectroscopy, and solution control reactions. This unique reactivity can also be translated to solution whereupon pre-milling of the manganese is required.

Size-selective mesoporous silica-based Pt(II)complex as efficient and reusable photocatalytic material

The grafting of a Pt(II)photocatalyst into three different mesoporous silica-based materials with different particle sizes and pore sizes was easily achieved through an amide bond formation. The analysis and results of the different characterization techniques showed that the catalyst is immobilized inside the pores of the materials and the photophysical properties of the catalyst are preserved after the covalent anchoring. The photocatalytic material catalyzed efficiently the debromination reaction of different substrates and is reused without detriment in its catalytic activity. In addition, the incorporation of the catalyst into mesoporous silica materials with different pore size allows the selective debromination of substrates by size discrimination.

Synthesis of β-hydroxymalonates: the direct aldol addition of malonates to aldehydes in the presence of SiCl4 and i-Pr2EtN

The direct aldol addition of malonates to aromatic, hetero-aromatic and unsaturated aldehydes leading to β-hydroxymalonates is described. The stability of these products, the trimethyl silyl protection of the hydroxyl group as well as the role of both SiC

Process for preparing C5 products and their use for Atorvastatin synthesis

The present invention relates to a process for preparing C5 intermediates and their use in the preparation of pyrrole derivatives of a class that is effective at inhibiting the biosynthesis of cholesterol in humans, and more particularly to improved synthetic methods for preparing 3,5-dihydroxy-7-pyrrol-1-yl heptanoic acids from 1,4-diketo starting materials. The invention further relates to intermediates in this process

Acylation through ketene intermediates

Carboxylic acids possessing a strong electron-withdrawing group in the α-position undergo facile dehydration upon reaction with carbodiimides to form the corresponding substituted ketenes that can react in situ with alcohols providing esters in a high yield. The ketene formed by the treatment of ethyl 2-methylmalonate with DCC was trapped in situ by a [4+2] cycloaddition with a second DCC molecule. The chemoselectivity of the acylation through the ketene intermediates was found to be substantially different from that of conventional acylation reagents showing a very low sensitivity toward the steric bulk of alcohols. A comparison of the sensitivity of the acylation to the steric bulk of alcohols supports the presence of a pseudopericyclic pathway for the nucleophilic addition of alcohols to ketenes derived from ethyl malonic and diethylphosphonoacetic acid.

Unexpected catalyst for Wittig-type and dehalogenation reactions

A novel catalyst 2 for Wittig-type and dehalogenation reactions was developed. In the presence of triphenyl phosphite, a wide variety of aldehydes could react with α-bromoacetates to afford α,β-unsaturated esters or ketones in high yields with excellent E-stereoselectivity when 1-2 mol % of compound 2 was used. Compound 2 was also an effective catalyst for reductive dehalogenation of α-bromocarbonyl compounds. The mechanisms for the above reactions were also proposed.

Pyridazinone derivatives and processes for preparing the same

Disclosed is a pyridazinone compound represented by the formula (I): STR1 wherein X represents hydrogen atom or the like; Y represents a single bonding arm, oxygen atom or sulfur atom; A represents a straight or branched alkylene group which may have a double bond; B represents carbonyl group or thiocarbonyl group; and R2 represents an alkyl group having 1 to 10 carbon atoms which may be substituted or the like; or B represents sulfonyl group; and R2 represents a lower alkenyl group or the like; R1 represents hydrogen atom or the like; R3 represents hydrogen atom or the like; R4 represents hydrogen atom or the like; and R5 represents hydrogen atom or the like, or a pharmaceutically acceptable salt thereof.

Living cyclopolymerization of 1,6-heptadiyne derivatives using well-Defined alkylidene complexes: Polymerization mechanism, polymer structure, and polymer properties

We report here the living cyclopolymerization of 1,6-heptadiyne derivatives (usually 4,4-disubstituted) using well-defined alkylidene complexes as initiators. Diethyl dipropargylmalonate (2a), di-tert-butyl dipropargylmalonate (2b), optically active di-(1R,2S,5R)-(-)-menthyl dipropargylmalonate (2c(-)), di-(1S,2R,5S)-(+)-menthyl dipropargylmalonate (2c(+)), di-(1R)-endo-(+)-fenchyl dipropargylmalonate (2d), 4,4-bis[[(p-tolylsulfonyl)oxy]methyl]-1,6-heptadiyne (3b), 4,4-bis[(trimethylsiloxy)methyl]-1,6-heptadiyne (3c), the cyclic silyl ether, PhEtSi(OCH2)2C-(CH2C=CH)2 (3d), and N,N-dipropargyl-2,4,6-triisopropylbenzamide (5b) are polymerized to give soluble polymers in high yield using Mo(NAr)(CHCMe2Ph)(ORF6)2 (1a; Ar = 2,6-i-Pr2C6H3, ORF6 = OCMe(CF3)2) as the initiator in 1,2-dimethoxyethane (DME). The polymers show a high degree of conjugation (λmax > 500 nm) and have narrow molecular weight distributions. Poly(2a) is soluble in most organic solvents (THF, C6H6, toluene, CH2Cl2, CHCl3, DME, DMF, MeCN). The mechanism of the polymerization has been investigated by 1H NMR studies and by monomer, initiator, and solvent variations. Symmetric, diphenyl-capped polyenes, "pull-pull" polyenes containing p-cyanophenyl end groups, and "push-push" polyenes containing p-dimethylamino end groups have all been prepared, as have polyenes that contain optically active substituents and "push-pull" polyenes containing p-(dimethylamino)-phenyl and p-cyanophenyl end groups. 4,4-Bis(carboxyethyl)cyclopent-1-ene and 1-vinyl-3-methylene-5,5-bis-(carboxyethyl)cyclohex-1-ene were employed as model compounds in order to quantify five- and six-membered ring structures in the polymer. The substituted polyenes are far more stable at room temperature and in air than unsubstituted polyenes of the same length. Random and block copolymers of 2a, 2,3-dicarbomethoxynorbornadiene (DCMNBD) and 7,8-bis(trifluoromethyl)tricyclo[4.2.2.02,5]deca-3,7,9-triene (TCDT) were prepared and characterized. The solution electrochemistry, thin film electrochemistry, and UV/vis spectroelectrochemistry of several homopolymers and copolymers have been examined.

Intramolecular Cyclopropanation: Stereospecific Synthesis of (E)- and (Z)-1-Aminocyclopropane-1-carboxylic Acids

tert-Butyl-substituted allyl malonates, prepared in two steps from malonic acid, are diazotized in high yields.The diazomalonates 7 undergo a stereospecific copper(I)-catalyzed cyclopropanation to give 1-(tert-butoxycarbonyl)-3-oxa-2-oxobicyclohexanes 8 which can be converted to the protected (E)- or (Z)-1-aminocyclopropane-1-carboxylic acids 10 or 15 via Curtius- or Hoffmann-type rearrangements, respectively.The sequences are short (six steps from malonic acid) and proceed with good overall yields (20-40percent overall from malonic acid).The free amino acids 12 and 13 can be liberated in two steps.