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DOI: 10.1055/s-0037-1611551
A Simple Method for the Preparation of Stainless and Highly Pure Trichloroacetimidates
The Ministry of Education, Culture, Sports, Science and Technology (MEXT) in Japan supported the program for the Strategic Research Foundation at Private Universities (Grant No. S1311046), and the Japan Society for the Promotion of Science (JSPS) (KAKENHI) (Grant No. JP16H01163 in Middle Molecular Strategy, and Grant No. JP16KT0061) partly supported this work.Publication History
Received: 10 April 2019
Accepted after revision: 29 April 2019
Publication Date:
15 May 2019 (online)
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Abstract
We describe a method for obtaining various allylic, benzylic, and glucosyl 2,2,2-trichloroacetimidates (TCAIs) as stainless liquids or solids at the crude stage. The general synthetic method for the preparation of TCAIs often leads to stained products, and further purification of crude TCAIs causes decomposition due to their instability. In the described method, we use a solvent that barely dissolves the reactant, providing stainless and sufficiently pure TCAIs without requiring a purification step. Furthermore, the reaction mixture is turbid at the beginning and clear at the end, allowing us to monitor the progress of the reaction visually.
Key words
preparation - 2,2,2-trichloroacetimidates - stainless - solvent optimization - visual detectionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611551.
- Supporting Information
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References and Notes
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- 20 p-Methoxybenzyl 2,2,2-Trichloroacetimidate [PMB-TCAI (2)]; Typical Procedure To a suspension of PMBOH (1.00 g, 7.24 mmol) and Cl3CCN (1.15 g, 7.97 mmol) in heptane (18 mL) was added DBU (110 mg, 723 μmol) at 0 °C. After the suspension became a solution (actual reaction time = 25 min), heptane (18 mL) and saturated aq NH4Cl (18 mL) were added to the reaction mixture. The separated heptane layer was washed with saturated aq NH4Cl (18 mL) and dried over Na2SO4. Filtration of the Na2SO4 and concentration of the filtrate under reduced pressure gave PMB-TCAI (2) (2.01 g, 99%) as a colorless oil. The 1H and 13C NMR spectra of 2 were in good agreement with the literature data.22 1H NMR (400 MHz, CDCl3, 24 °C): δ = 8.36 (br s, 1 H), 7.37 (d, J = 8.7 Hz, 2 H), 6.91 (d, J = 8.7 Hz, 2 H), 5.28 (s, 2 H), 3.82 (s, 3 H). 13C NMR (101 MHz, CDCl3, 24 °C): δ = 162.8, 159.9, 129.9 (2 C), 127.7, 114.1 (2 C), 91.6, 70.8, 55.4.
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For Bn-TCAI, see:
For PMB-TCAI, see:
For examples of the preparation of Bn-TCAI, see:
For examples of the preparation of PMB-TCAI, see:
For examples of the preparation of allylic TCAIs, see:
In the case of preparing glycosyl TCAIs, the mainly used base/solvent combination is NaH/CH2Cl2. For examples, see:
For the preparation of Bn-TCAI, see:
For the preparation of PMB-TCAI, see:
For examples of the preparation of allylic TCAIs, see:
For examples of the preparation of glycosyl TCAIs, see: