1462-35-7Relevant articles and documents
New azomycin acyclonucleosides. Synthesis and biodistribution of radiohalogenated analogues in tumor-bearing mice [1]
Hasan,Knapp Jr.,Kilbourn,Buchsbaum
, p. 1351 - 1355 (1993)
The design, synthesis and biological activities of several acyclonucleoside analogues related to misonidazole are described. The hydroxy-5, bromo-6, iodo-7, and fluoro-8 derivatives of ethoxymethylazomycin and iodopropenyloxymethylazomycin (12) have been prepared. Alkylation of silylated azomycin with haloethoxy-methylene chloride gave the corresponding acyclonucleosides. Similarly, propargyloxymethylene chloride gave propargyloxymethylazomycin (10), which after hydrostannylation and subsequent iododestannylation yielded iodopropenyloxymethylazomycin (12). The radiolabeled [125I] or [18F] compounds were prepared from the corresponding substrates. Biodistribution results of the radiolabeled analogues in mice showed that compound 7 had good tumor uptake (2.0% injected dose/g at 1 hour). The high radioactive levels in blood and stomach, however, were perhaps due to in vivo deiodination or metabolism. Compound [125I]- 12 showed the highest tumor uptake (4.8 and 3.6% injected dose/g at 1 and 4 hours respectively) of all of the compounds tested. Relatively low thyroid uptake of radioactivity in mice dosed with compound [125I]-12 indicates significantly reduced in vivo deiodination in comparison to compound [125I]-7.
Synthesis of 2,2,2-Trinitroethyl and 2-Cyano-2,2-dinitroethyl Ethers
Kim, Kyung Eun,Adolph, Horst G.
, p. 1029 - 1030 (1987)
It was found that 2,2,2-trinitroethoxy and 2-cyano-2,2-dinitroethoxy compounds can be prepared in modest to good yields by reaction of alkali metal salts of trinitromethane and cyanodinitromethane with chloromethyl ethers.The effects of varying the reaction solvent are discussed briefly.
A simple synthetic method of SEM-CI, an important intermediate of anti-myelofibrosis ruxolitinib
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Paragraph 0008; 0034; 0037-0040, (2019/05/08)
The invention discloses a simple synthetic method of SEM-CI, an important intermediate of anti-myelofibrosis ruxolitinib. A chloromethylation intermediate is synthesized by taking 2-bromoethanol as amain raw material, petroleum ether as a solvent, polyformaldehyde and hydrogen chloride as chloromethylation reagents and concentrated sulfuric acid as a water absorbing agent; A complex of Grignard reagent and butyllithium is used as base extraction bromide and reacts with trimethylchlorosilane to synthesize the target product in two steps. The simple synthetic method of the invention has the advantages of easily available raw materials, low cost, simple and convenient operation, high yield, less ''three wastes '', reasonable process and stable quality.
Synthetic method of 2-(trimethylsilyl)ethoxymethyl chloride
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Page/Page column 5-7, (2018/09/11)
The invention provides a synthetic method of 2-(trimethylsilyl)ethoxymethyl chloride, comprising the steps: (1) allowing chloromethylation, to be specific, adding bromoethanol, n-hexane, paraformaldehyde, and concentrated sulfuric acid into a reaction bottle, starting stirring, cooling the temperature to -5-DEG C, introducing HCL gas until the raw material is less than 5%, stopping gas introduction, and performing reacting to obtain a chloromethylation intermediate; (2) carrying out substitution, to be specific, taking tetrahydrofuran, adding into the reaction bottle, opening, stirring, cooling to 15 DEG C, taking butylmagnesium chloride and n-butyllithium sequentially, adding into a reaction liquid, maintaining the inner temperature to 25 DEG and below, holding the temperature at 20-25 DEG C, stirring, dropwise adding the chloromethylation intermediate of step (1) slowly into the reaction liquid, holding the temperature to 30 DEG C and below, holding the temperature to 20-30 DEG C forreaction, concentrating the reaction liquid under reduced pressure, recycling organic solvents and the crude product, and distilling via a crude water pump. The synthetic method is low in cost, highin yield and good in post-treatment convenience and stability.
A 2 - (tri-silyl) b oxygen methyl chloride synthesis method
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Paragraph 0021-0024, (2017/01/12)
The invention discloses a synthetic method of 2-(trimethylsilyl)-ethoxymethyl chloride. The reaction equation in the method is shown in the specification. According to the synthetic method of 2-(trimethylsilyl)-ethoxymethyl chloride disclosed by the invention, reactions are performed in normal pressure states and easy to control. Raw materials are products easily obtained massively in the market. The raw materials are low in cost and high in purity. Finally, reaction is performed in an alkaline condition, and the product is stable and long in retention time in the alkaline condition.
Concise enantioselective synthesis of diospongins A and B Dedicated to Paul A. Wender, an inspirational teacher and scholar and a generous mentor, on receipt of the 2013 Tetrahedron Prize
Stefan, Eric,Nalin, Ansel P.,Taylor, Richard E.
, p. 7706 - 7712 (2013/08/23)
Ether transfer methodology is capable of stereoselectively generating 1,3-diol mono- and diethers in good yield. Surprisingly, allylic and benzylic substrates provide none of the desired products when exposed to previously optimized conditions of iodine monochloride. Herein, second-generation activation conditions for ether transfer have been developed that circumvents undesired side reactions for these substrates. The application of this chemistry to the enantioselective synthesis of diospongins A and B has now been accomplished.
Design and synthesis of some novel oxiconazole-like carboacyclic nucleoside analogues, as potential chemotherapeutic agents
Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Behrouz, Somayeh
body text, p. 1760 - 1774 (2009/12/06)
The syntheses of some novel carboacyclic nucleosides, 17a-17o, containing oxiconazole-like scaffolds, are described (Schemes 1-3). In this series of carboacyclic nucleosides, pyrimidine as well as purine and other imidazole derivatives were employed as an imidazole successor in oxiconazole. These compounds could be prepared in good yields by using two different strategies (Schemes 1 and 2). Due to Scheme 1, the N-coupling of nucleobases with 2-bromoacetophenones was attained for 18a-18e, and their subsequent oximation affording 19a-19e and finally O-alkylation with diverse alkylating sources resulted in the products 17a-17g, 17n, and 17o. In Scheme 2, use of 2-bromoacetophenone oximes 20, followed by N-coupling of nucleobases, provided 19f-19j whose final O-alkylation produced 17h-17m (Scheme 2). For the rational interpretation of the dominant formation of (E)-oxime ethers rather than (Z)-oxime isomers, PM3 semiempirical quantum-mechanic calculations were discussed and the calculations indicated a lower heat of formation for (E)-isomers.
Phosphoramidite building blocks for efficient incorporation of 2′-O-aminoethoxy(and propoxy)methyl nucleosides into oligonucleotides
Bobkov, Georgii V.,Mikhailov, Sergey N.,Van Aerschot, Arthur,Herdewijn, Piet
, p. 6238 - 6251 (2008/09/21)
A simple and efficient method for the preparation of eight phosphoramidite building blocks for incorporation of 2′-O-(2-aminoethoxymethyl)ribonucleosides and 2′-O-(3-aminopropoxymethyl)ribonucleosides into synthetic oligonucleotides has been developed. The synthetic routes are maximally convergent and provide sufficient amounts of phosphoramidites for several solid-phase synthesis coupling reactions. Using acyclic derivatives 17a,b the overall yields of phosphoramidites 2 and 3 were increased up to 50% for pyrimidine nucleosides and up to 30% for purine derivatives with substantial decrease of total reaction steps. The 2′-O-substituent was found to be stable during oligonucleotide synthesis. The resulting oligonucleotides are of particular interest for post-synthetic functionalization and conjugation.
A Convenient One-Pot Method for the Hydroxymethylation of Grignard Reagents
Ogle, C. A.,Wilson, T. E.,Stowe, J. A.
, p. 495 - 496 (2007/10/02)
Grignard reagents and alkynyllithiums can be hydroxymethylated in a two-step one-pot reaction by reaction of a Grignard reagent with 1-chloro-2-(chloromethoxy)ethane (1), followed by treatment with sodium-potassium alloy and aqueous workup.The reaction was found to work for primary, secondary, tertiary, benzylic, allylic and aryl Grignard reagents in yields ranging from 57 - 95 percent.
The Conformation Analysis of Derivatives of Erythromycin A. X-Ray Crystallographic and Nuclear Magnetic Resonance Spectroscopic Studies of (E)-11-O-<2-Dimethylaminoethoxy)methyl-9-deoxo-9-methoxyiminoerythromycin A
Everett, Jeremy R.,Hatton, Ian K.,Hunt, Eric,Tyler, John W.,Williams, David J.
, p. 1719 - 1728 (2007/10/02)
(E)-11-O-(2-Dimethylaminoethoxy)methyl-9-deoxo-9-methoxyiminoerythromycin A (3) has been synthesised from erythromycin A (1) and its crystal structure conformation compared with that of (1).The conformations of the two sugars and their orientation with respect to one another are the same in (1) and (3).The conformations of the aglycones are, however, markedly different.In comparison with (1), the main conformational changes in (3) appear to be a folding in the aglycone about the C-7 methylene and lactone ring oxygen, which moves the C-6 hydroxy and lactone carbonyl away from the substituents at C-9 and C-11, and an inward folding (towards C-11) of the C-3 to C-5 region and the attached sugars.The conformation of (3) in CDCl3 was investigated by measuring 1H vicinal coupling constants, 1H n.O.e.s, and 13C spin-lattice relaxation times.These studies show that in solution (3) exists in a state of fast exchange between conformations of the C-3 to C-5 'folded out' and C3 to C-5 'folded in' types.One of the simplest representations of this would be a rapid equilibrium between conformations similar to those found in the crystal structures of (1) and (3).
