Self-Polyaddition of Six-Membered Cyclic Carbonate Having Fmoc-Protected Amino Group:  Novel Synthetic Method of Polyhydroxyurethane

Abstract

This article deals with the self-polyaddition of 3-(1,3-dioxan-2-one-5-yl)propyl 2-(9-fluorenylmethoxycarbonylamino)ethyl thioether by the deprotection of the 9-fluorenylmethyoxycarbonyl (Fmoc) group with N,N-diisopropylethylamine, 4-(dimethylamino)pyridine, or triethylamine as a novel synthetic method of a polyhydroxyurethane. The polymer with higher yields and M n's was obtained by using N,Ndiisopropylethylamine and 4-(dimethylamino)pyridine than triethylamine. Fmoc deprotection and stability of the cyclic carbonate group were elucidated to optimize the condition by using the model compounds, 3-cyclohexylpropyl 2-(9-fluorenylmethoxycarbonylamino)ethyl thioether and 3-(1,3-dioxan-2-one-5-yl)propyl ethyl thioether.

Aminolysis Reaction of Glycerol Carbonate in Organic and Hydroorganic Medium

“…In the literature, the ratio of a versus b hydroxyurethanes is generally established in a post-reactional phase by spectroscopic methods more particularly by 1 H NMR [9,10,22]. The structures of the compounds and the ratio of a versus b hydroxyurethanes were determined by zgig 13 C NMR.…”

“…Cyclic carbonates have been explored to develop various carbonyl compounds and polymers [5][6][7][8][9][10][11][12][13][14]. Glycerol carbonate is one of the glycerol derivatives that, at present, captures more academic and industrial attention.…”

“…In the presence of organic solvents, some authors indicated a somewhat higher ratio of b versus a hydroxyl [9,20,21]. However, the relative isomer ratio is insensitive to the reaction temperature and only slightly dependent on solvent polarity [9][10][11]. One study investigated the condensation reaction of glycerol carbonate with butylamine in the presence and absence of a solvent in stoichiometric amounts [22].…”

Synthesis, characterization and ring-opening polymerization of a novel six-membered cyclic carbonate bearing pendent allyl ether group

“…Moreover, the pendent functional groups can facilitate covalent pro-drug attachment as well as other modifications. Recently, many polycarbonates with functional groups have been synthesized, such as carboxyl [7], hydroxyl [8], amino [9], vinyl [10,11], benzyl [12], etc. The synthesis of novel cyclic monomers containing a variety of functionalities has become an important method for the development of new biodegradable polymer materials with special properties for different applications.…”

An efficient nonisocyanate route to polyurethanes via thiol‐ene self‐addition

“…The development of nonisocyanate chemistries is one of the major challenges in the field. Thus, various nonisocyanate polymerization routes have been attempted for PUs, the two most used including the widely reported ring opening of cyclic carbonates by amines [3][4][5][6][7][8][9][10][11][12][13][14][15] and the self-condensation approach from AB-type monomers containing hydroxyl and acyl azide end-groups. [16][17][18][19][20][21] It is worth noting that the synthesis of hetero-complementary monomers is still challenging for most functional groups and scarce approaches to AB polyaddition have been described earlier.…”