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A kind of symmetrical pyrimidyl iodonium salt and preparation method thereof

A technology of pyrimidinyl and iodonium salts, which is applied in the field of iodonium salts and its preparation, can solve problems such as poor selectivity, low yield, and difficult separation, and achieve the effect of avoiding poor selectivity and high yield

Active Publication Date: 2018-04-20
DONGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The technical problem to be solved by the present invention is to provide a symmetrical pyrimidinium iodonium salt and its preparation method. The oxidation method used in the preparation method is acid-free, efficient and mild; the post-reaction treatment is easy to operate and has a high yield; the symmetrical Pyrimidinium iodonium salt as 18 The precursor of F-uracil PET drug synthesis, and 18 F fluoride ion reaction, deprotection, two-step preparation of high radiation yield 18 F-5-fluorouracil PET tracer, avoiding the problems of poor selectivity, low yield, and difficult separation

Method used

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  • A kind of symmetrical pyrimidyl iodonium salt and preparation method thereof
  • A kind of symmetrical pyrimidyl iodonium salt and preparation method thereof
  • A kind of symmetrical pyrimidyl iodonium salt and preparation method thereof

Examples

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Embodiment 1

[0040] The preparation of bis(5-(2,4-bis(2,4-dibenzyloxy)pyrimidinyl)iodonium hexafluorophosphates), the structure is shown below :

[0041]

[0042] (1) Preparation of 5-bromo-2,4-dioxypyrimidine

[0043] 19.1 g (100 mmol) of 5-bromouracil was mixed with 60 ml of phosphorus oxychloride, and the reaction was stirred at 125° C. for five days, and 100 ml of ice water was added to quench the reaction. The reaction solution was extracted three times with 120 ml of diethyl ether, the organic phases were combined and distilled under reduced pressure to remove diethyl ether and excess phosphorus oxychloride to obtain 19.4 g (87%) of 5-bromo-2,4-dichloropyrimidine. Dissolve 6.7ml (65mmol) of benzyl alcohol in 70ml of anhydrous toluene, and react with 2.9g of NaH (60mmol) under the protection of nitrogen at 50°C until no gas is generated. The resulting suspension is cooled to room temperature and slowly added dropwise under stirring. 5-Bromo-2,4-dichloropyrimidine 4.5g (20mmol), the dripp...

Embodiment 2

[0051] Preparation of bis(5-(2,4-bis(2,4-dibenzyloxy)pyrimidinyl)iodonium tosylate) (bis(2,4-bis(benzyloxy)pyrimidin-5-yl)iodonium tosylate), the structural formula is as follows:

[0052]

[0053] (1) Preparation of 5-bromo-2,4-dioxypyrimidine: same as the first step (1) in Example 1.

[0054] (2) Preparation of 5-(2,4-dibenoxy-pyrimidinyl) potassium difluoroborate and 5-iodo-2,4-dibenoxypyrimidine

[0055] In a Schlenk flask, 2.91g (10mmol) of 2,4-dioxypyrimidine was dissolved in 50ml of anhydrous tetrahydrofuran, and 6.5ml of tert-butyllithium n-hexane solution (1.7 M, 1.12 equivalent) 4.5ml, keep -78℃ and continue to stir for 30 minutes, slowly add 2.26g (12mmol) of triisopropyl borate to the reaction solution dropwise, warm to room temperature, continue to stir and react for 8 hours, add 0.2mol / L hydrochloric acid was stirred for two hours. The reaction solution was extracted three times with 90ml of dichloromethane. The organic phases were combined and dried to remove the so...

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Abstract

The invention relates to symmetric pyrimidyl iodonium salt and a preparation method thereof. The structural formula of the symmetric pyrimidyl iodonium salt is shown in the description. The preparation method comprises the steps that alcohol reacts with sodium hydride, then the reaction product drips into the reaction product of 5-bromouracil and phosphorus oxychloride, the reaction product reacts with a butyl lithium reagent after reaction and then reacts with simple substance iodine and organic metal halide respectively to obtain a 5-iodine-2,4-dialkoxyl pyrimidine and a metal pyrimidine derivative; the 5-iodine-2,4-dialkoxyl pyrimidine reacts with a nitrogen-fluorine reagent and TMSX-1 to obtain a 2,4-dialkyl pyrimidyl trivalent iodine intermediate and then reacts with TMSX-2 and the metal pyrimidine derivative, then anionic sodium or potassium salt is added to perform extraction, and the symmetric pyrimidyl iodonium salt is obtained. The oxidation method adopted by the preparation method of the symmetric pyrimidyl iodonium salt is acid-free, efficient and moderate. The symmetric pyrimidyl iodonium salt is used for efficient preparation of PET tracer agent <18>F-5-fluorouracil, and the poor problems of poor selectivity, low productivity, difficult separation and the like are avoided.

Description

Technical field [0001] The invention belongs to the field of iodonium salts and preparation methods thereof, and particularly relates to a symmetrical pyrimidinyl iodonium salt and a preparation method thereof. Background technique [0002] Diaryliodonium salts (Wang, B., et al., Fluoride-promoted ligand exchange indiaryliodonium salts. Journal of Fluorine Chemistry, 2010.131(11): p.1113-1121), due to its unique reaction properties, have been It has attracted the attention of many chemists in the past ten years. As an aromatizing agent, diaryliodonium salts can directly undergo electrophilic arylation reactions with various nucleophiles (Umierski, N.; Manolikakes, G. Org. Lett. 2012, 14, 188.), or through transition Metal-catalyzed cross-coupling reactions (Gigant, N.; Chausset-Boissarie, L.; Belhomme, M.-C.; Poisson, T.; Pannecoucke, X.; Gillaizeau, I. Org. Lett. 2012, 14, 278) Or tandem cyclization reaction (Zhu, S.; MacMillan, DWCJAm. Chem. Soc. 2012, 134, 10815). when 18 W...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D239/52
CPCC07D239/52
Inventor 王碧佳李成龙
Owner DONGHUA UNIV
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