Cryptands perfluoro

Under carefully controlled conditions even complex molecules can be fluorinated. For example, the preparation of perfluoro-crown ethers (85CC1350) and perfluoro(2.2.2.)-cryptand (90JOC5933) has been described. Branched morpholines and piperazines have been directly fluorinated to their perfluoro analogues [90JFC(50)15],... 

Positively charged or neutral electron-deficient groups may serve as interaction sites for anion binding. Ammonium and guanidinium units, which form +N-H" X bonds, have mainly been used, but neutral polar hydrogen bonds (e.g., with -NHCO- or -COOH functions), electron-deficient centers (boron, tin, mercury, [3.6, 3.7] as well as perfluoro crown ethers and cryptands [3.8], etc.), or metal-ion centres in complexes also interact with anions. 

Perfluorinations of many ethers [155], cryptands [156], polyethers [119, 157], including the largest perfluoro-macrocycle [158], perfluoro [60]-crown-20 [123, 159], and the first perfluorinated sugar [160], orthocarbonates [161, 162], ketones [163, 164], esters [124, 165], phosphanes [166] and alkyl halides [167, 168] have been successfully accomplished by the LaMar or aerosol processes (Table 2.4). 

A recent breakthrough in our laboratory has involved the synthesis of perfluorinated crown ethers and cryptands. We have previously reported the synthesis of the first perfluoro crown ethers, perfluoro [18]crown-6, perfluoro [15]crown-5 and perfluoro [12]crown>4 (1),... 

We have also reported the first perfluorocryptand molecule, the perfluoro-cryptand[2.2.2] (see Figure 9) (11), The perfluorocryptand is a very stable, inert, high boiling clear oil. While hydrocarbon crown ethers coordinate cations, both the perfluoro crown ethers and the new perfluorocryptand coordinate anions. Two manuscripts have recently appear in collaboration with Professor Jennifer S. Brodbelt in which both perfluoro crown ethers and perfluorocryptands tenaciously encapsulate 02and F" (77-72). 

---