53561-63-0

Upstream product

• 3377-20-6 diethyl methylenemalonate 
• 38442-51-2 tert-butylmercury chloride 
• 17085-89-1 diethyl 2-(2,2-dimethylpropylidene)malonate 
• 96-10-6 diethylaluminium chloride 
• 630-17-1 2,2-dimethylpropyl bromide 
• 105-53-3 diethyl malonate 
• 630-19-3 pivalaldehyde 
• 15673-05-9 4,4-dimethylvaleronitrile 
• 2855-08-5 1-chloro-3,3-dimethylbutane 
• 10228-99-6 ethyl 4,4-dimethylpentanoate 
• 105-58-8 Diethyl carbonate 
• 64-17-5 ethanol 
• 88319-38-4 2-cyano-4,4-dimethylpentanoic acid 

Downstream Products

• 561-83-1 5-allyl-5-(2,2-dimethyl-propyl)-pyrimidine-2,4,6-trione 

Relevant academic research and scientific papers

A amide alkaloid fully synthetic method

The invention discloses a total synthesis method of amides alkaloid, and belongs to the technical field of the chemistry of natural products. The total synthesis method comprises the following steps: carrying out the synthesis by adopting malonate and 2-bromopropane or 2-bromopropane derivative as raw materials, thereby obtaining isopropyl malonate; (2) carrying out the synthesis by adopting 2-aminopyrrolidine as a raw material, thereby obtaining mid-body 2-amino tetralin pyrrolidine; and (3) synthesizing amides alkaloid 3-isopropyl-nafoxidine[1,2-alpha]pyrimidine-2,4(1H,3H)-diketone and a derivative by adopting the isopropyl malonate and the 2-2-amino tetralin pyrrolidine as a raw material. By adopting the total synthesis method, the defect that the extraction separation process in the natural product is complicated and the yield is low can be overcome, and the demand of perople for further researching the natural product can be satisfied; moreover, the synthesis method is simple in route, raw materials are cheap and easy to obtain, and the yield is relatively high.

Bridged metallocene catalysts

A solid, particulate catalyst comprising: (i) a complex of formula (I) wherein M is zirconium or hafnium; each X is a sigma ligand; L is a divalent bridge selected from —R′2C—, —R′2C—CR′2—, —R′2Si—, —R′2Si—SiR′2—, —R′2Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; each R1 is a C4-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring, optionally containing one or more heteroatoms belonging to groups 14-16, or is a C3-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring where the β-atom is an Si-atom; each R18 is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; each R4 is a hydrogen atom or a C1-6-hydrocarbyl radical; each W is a 5 or 6 membered aryl or heteroaryl ring wherein each atom of said ring is optionally substituted with at least one R5 group; each R5 is the same or different and is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; and optionally two adjacent R5 groups taken together can form a further mono or multicyclic ring condensed to W optionally substituted by one or two groups R5; and each R7 is a C1-C20 hydrocarbyl radical; and (ii) a cocatalyst, preferably comprising an organometallic compound of a Group 13 metal.

Conjugate addition of dialkylaluminum chlorides to alkylidenemalonic acid derivatives

Complete regioselectivity is achieved in conjugate addition reactions of dialkylaluminum chlorides with alkylidenemalonic esters, alkylidenecyanoacetates, and alkylidenemalonodinitrile to give β-branched carboxylic acid derivatives. Sterically demanding products containing quaternary carbon atoms are obtained in good yields. In the case of diethylaluminum chloride, accompanying reductions of the substrates can be suppressed by application of boron trifluoride as an assisting Lewis acid.

Reductive alkylation of electronegatively-substituted alkenes by alkylmercury halides

Photolysis of alkylmercury halides in the presence of electronegatively-substituted 1-alkenes yields adduct radicals [RCH2CH(EWG).] that in some cases react with RHgX to form RCH2CH(HgX)(EWG), e.g., EWG = (EtO)2PO or PhSO2. When the EWG is carbonyl or cyano, the resonance stabilized adduct radicals fail to react with the alkyl mercury halide. In these cases photolysis with RHgCl/KI in Me2SO leads to the adduct mercurial via reaction of the adduct radicals with RHgI2-. The reactions of tertiary-enolyl adduct radicals are inefficient with RHgX/KI, and disproportionation of the adduct radicals is the major reaction pathway. For secondary- or tertiary-adduct radicals the reductive alkylation products are formed in excellent yield by reaction with RHgCl and silyl hydrides in Me2SO solution in a process postulated to involve RHgH as an intermediate. The relative reactivities of a number of α,β-unsaturated systems toward t-Bu. have been measured by competitive techniques. The results demonstrate a high reactivity of s-cis enones relative to the s-trans conformers.

The Influence of Acetoxy Substituents on the Nucleophilicity of Alkyl Radicals

Reduction of the organomercuric salt 3 with NaBH4 yields the acetoxy-substituted radical 4.Using competition techniques the rel. rates of addition of 4 to alkenes 5 can be measured.The rate data show that radical 4 is a nucleophile (table 1) but the nucleophilicity is slightly smaller than that of the sec. cyclohexyl radical (figure 1).The acetoxy group, therefore, acts as an electron withdrawing substituent that reduces the nucleophilic reactivity and the nucleophilic selectivity of alkyl radicals.