76513-69-4Relevant articles and documents
A simple synthetic method of SEM-CI, an important intermediate of anti-myelofibrosis ruxolitinib
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Paragraph 0019; 0034; 0044-0047, (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 0020; 0021; 0025, (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.
METHOD OF PRODUCING SILYLALKOXYMETHYL HALIDE
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Page/Page column 6; 7, (2008/06/13)
A method for making a silylalkoxymethyl halide at good yield represented by the formula: R1R2R3Si-R4-O-CH2X wherein R1, R2, and R3 are an alkyl, cycloalkyl, aryl group, or a halogen atom, R4 is a divalent hydrocarbyl group having 1 to 10 carbon atoms, and X is a halogen atom, by reacting: (a) a silyl alcohol compound with the formula R1R2R3Si-R4-OH wherein R1, R2, R3 and R4 are defined as above, with (b) formaldehyde or a polymer thereof, and (c) a halosilane.
Synthesis of Orelline
Hasseberg, Hans-Albrecht,Gerlach, Hans
, p. 957 - 963 (2007/10/02)
Orelline (1), a metabolite of the toadstool Cortinarius Orellanus Fries with 2,2'-bipyridine structure, has been synthesized by the following method.The easily accessible 2-bromo-3-hydroxypyridine (3) was converted into the corresponding methyl (SEM) ether 4 and coupled with Zn and NiCl2/Ph3P to form the bipyridine derivative 5 in 79percent yield.Due to the chelating effect of the two SEM-ether groups in 5, it was possible to form selectively the dilithium compound 6 by an exchange reaction with BuLi at -50 deg C in Et2O.Reaction of 6 with electrophiles at -20 deg C afforded the 4- and 4,4'-substituted bipyridines 7-14 in excellent-to-reasonable yield.Oxidations of 6 with 2-(phenylsulfonyl)-3-phenyloxaziridin and with bis(trimethylsilyl)peroxide gave the 4,4'-diol 9 in 22 and 10percent yield, respectively.Methanolysis of 9 directly afforded crystalline 1 in high yield, with properties identical with those of natural orelline.Formylation of 6 with N-formylmorpholine gave 45percent of the dicarbaldehyde 13.Removal of the SEM groups in 13 by hydrolysis afforded the dihydroxydicarbaldehyde 15 that could be oxidized to 1 with alkaline H2O2.Attempts to oxidize 1 to orellanine (2) with 35percent H2O2 according to a known procedure were unsuccessful (cf.Exper.Part).Compound 7 with two Me3Si groups in 4,4'-position gave after methanolysis the fluorescence dye 16 with an appreciable Stokes shift in cyclohexane.
An easy access to homopropargylic ethers
Guedin-Vuong, Denis,Nakatani, Yoichi
, p. 245 - 252 (2007/10/02)
Chloromethyl ethers, obtained from alcohols, formaldehyde and HCl, react regioselectively, as shown previously in one case by L.Miginiac, with allenyl aluminium reagents derived from propargyl bromides and aluminium, to give homopropargyl ethers.No evidence for the presence of allenyl ethers was obtained in the cases described.This condensation is used to obtain a protected acetylenic synthon 1, required for the synthesis of an ecdysteroid analogue (1).
β-(Trimethylsilyl)ethoxymethyl chloride. A new reagent for the protection of the hydroxyl group
Lipshutz, Bruce H.,Pegram, Joseph J.
, p. 3343 - 3346 (2007/10/02)
Reactions of β-(trimethylsilyl)ethoxymethyl chloride with alcohols afford the corresponding ethers in high yield. Deprotection using n-Bu4NF in THF or HMPA cleanly regenerates the hydroxyl function.
