本发明公开了一种催化合成氨基甲酸羟烷基酯的方法。该方法在催化剂的作用下，使环氧化合物、CO2和有机胺进行反应，一步生成相应氨基甲酸羟烷基酯，产物 选择性在95%以上。本发明反应条件温和，操作过程简单，反应选择性高，原料易于循环使用，催化剂容易回收并且重复使用性好，产物纯度高，属清洁工艺，有 实际应用价值。

邓友全,郭晓光,石峰,等. 催化合成氨基甲酸羟烷基酯的方法. 201010234184.x. 2013.

本发明公开了一种合成环己氨基甲酸酯的方法。本发明选择一种担载型金属氧化物固体催化剂，催化碳酸二烷基酯和N，N’-二环己基脲得到产物。该方法的主要特点是反应条件相对温和、催化剂易于回收和重复使用性好、反应为原子经济、分离所得产品纯度高。

邓友全,郭晓光,尚建鹏,等. 合成环己氨基甲酸酯的方法. Cn101759602a. 2012.

A practical method for the synthesis of carbamates from ureas and organic carbonates was developed with 100% atom economy using La2O3/SiO2 as catalyst without any additional solvent. The scope of the protocol is demonstrated in the synthesis of 14 carbamates with various functional groups in excellent yields (76–95%).

Keywords Atom economy; carbamates; carbonates; clean synthesis; lanthana; urea derivatives

Guo XG,Shang JP,Li J,et al. Green And Practical Synthesis Of Carbamates From Ureas And Organic Carbonates[J]. Synthetic Communications,2011,41:1102-1111.

A series of silica gel immobilized lanthanum catalysts were prepared for the atom-economy synthesis of N-substituted carbamates from urea derivatives and dimethyl carbonate. The La/SiO2 catalysts with lanthanum loadings varied from 1.3 wt% to 8.5 wt% were characterized by AES, BET, XRD, TEM, FT-IR, XPS and TPD. According to the characterization, lanthanum species with particle sizes of 5—10 nm on the surface of silica gel were formed. The catalysts were all amorphous and the surface areas were 336.5—530.2 m2/g. NH3-TPD analysis showed that all samples exhibited similar acid strength with different acid amounts. FT-IR measurement indicated that the component of lanthanum speci es on the catalyst surface were La(OH)3, LaOOH and hydrated La2O3. Also, the peak value of the absolute amount of LaOOH was obt ained with 4.3 wt% lanthanum loading. The BET surface area decreased dramatically when the lanthanum loading was above 4.3 wt%. In consideration of the results ob-tained from the catalytic reactions, it could be concluded that LaOOH was the possible active species and high sur-face area was important for the high catalytic activity.

Keywords N-substituted carbamate, urea derivative, dimethyl carbonate, lanthanum, green chemistry

★★☆☆☆ Guo XG,Shang JP,Li J,et al. Atom-economy Synthesis Of N-substituted Carbamate From Urea Derivative And Dimethyl Carbonate Catalyzed By La/sio2: Characterization And Activity[J]. Chinese Journal Of Chemistry,2010,28:164-170.

A series of catalysts (e.g. FeCl3, Zn(OAc)2, Pb(NO3)2, etc.) were tested for the trans-esterification reaction of 1,6-hexamethylenediamine (HDA) with methyl carbamate (MC), ethyl carbamate (EC), and butyl car-bamate (BC) to afford dialkyl hexamethylene-1,6-dicarbamate (AHDC). By applying the optimized condi-tion, 100% conversion of HDA and 93% yield to diethyl hexamethylene-1,6-dicarbamate (EHDC) could be obtained using FeCl3 as catalyst. The desired products could be precipitated by adding water into the resulting mixture, and the activity of recovered catalyst could be maintained.

Keywords: Non-phosgene; Carbamate; Carbonylation; 1,6-Hexamethylenediamine; Isocyanate

★★★☆☆ Guo XG,Shang JP,Ma XY,et al. Synthesis Of Dialkyl Hexamethylene-1,6-dicarbamate From 1,6-hexamethylenediamine And Alkyl Carbamate Over Fecl3 As Catalyst[J]. Catalysis Communications,2009,10:1248-1251.