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Symmetric pyrimidyl iodonium salt and preparation method thereof

A kind of base iodonium salt, symmetrical technology, applied in the field of iodonium salt and its preparation, can solve the problems of low yield, poor selectivity, difficult separation, etc., to achieve the effect of high yield and avoid poor selectivity

Active Publication Date: 2016-01-13
DONGHUA UNIV
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  • 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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  • Symmetric pyrimidyl iodonium salt and preparation method thereof
  • Symmetric pyrimidyl iodonium salt and preparation method thereof
  • Symmetric pyrimidyl iodonium salt and preparation method thereof

Examples

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Embodiment 1

[0040] The preparation of two (5-(2,4-dibenzyloxy) pyrimidinyl) iodonium hexafluorophosphates (bis(2,4-bis(benzyloxy)pyrimidin-5-yl)iodoniumhexafluorophosphates), the structure is as follows:

[0041]

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

[0043] 19.1 g (100 mmol) of 5-bromouracil was mixed with 60 ml of phosphorus oxychloride, stirred and reacted 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 120ml ether, and the organic phases were combined and distilled off under reduced pressure to remove 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, react with 2.9gNaH (60mmol) under the protection of 50°C under nitrogen until no gas is generated, cool the resulting suspension to room temperature, and slowly add 5 -Bromo-2,4-dichloropyrimidine 4.5g (2...

Embodiment 2

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

[0052]

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

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

[0055] In a Schlenk flask, 2.91 g (10 mmol) of 2,4-dibenzyloxypyrimidine was dissolved in 50 ml of anhydrous tetrahydrofuran, and 6.5 ml of tert-butyllithium n-hexane solution (1.7 M, 1.12 equivalents) 4.5ml, kept at -78°C and continued to stir for 30 minutes, slowly added 2.26 grams (12 mmol) of triisopropyl borate dropwise to the reaction solution, heated to room temperature and continued to stir for 8 hours, adding 0.2mol / L of hydrochloric acid was stirred for two hours. The reaction solution was extracted three times with 90ml of dichloromethane, the organic phase w...

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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, in particular to a symmetrical pyrimidinium iodonium salt and a preparation method thereof. Background technique [0002] Diaryliodonium salts (Wang, B., et al., Fluoride-promoted ligandexchange indiaryliodonium salts. Journal of Fluorine Chemistry, 2010.131 (11): p. 1113-1121) have received many chemists in recent decades due to their unique reactivity. their attention. As arylation reagents, diaryliodonium salts can undergo electrophilic arylation reactions with various nucleophiles directly (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 reactions (Zhu, S.; MacMillan, D.W.C.J. Am. Chem. Soc. 2012, 134, 10815). when 18 When F fluoride ion is use...

Claims

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Application Information

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