Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol†

doi:10.7503/cjcu20140420

Abstract

Abstract:

Titanyl acetate was prepared through the solvothermal reaction between titanium(Ⅳ) n-butoxide, acetic anhydride and distilled water. Titanyl acetate was firstly used in the transesterification reaction of dimethyl carbonate and phenol to diphenyl carbonate and exhibited excellent performance. When titanyl acetate amount is 0.10 g, the phenol conversion reaches to 47.8% and transesterification selectivity is 99.9% with trace anisole. Based on the results of FTIR, solid state ¹³C NMR, titanyl acetate reacts firstly with phenol. The acetate group of titanyl acetate is replaced by phenoxy group and generates phenoxy titanium complex. It could be considered that phenoxy titanium complex is the real catalyst for the transesterification of dimethyl carbonate and phenol with good resuability.

Key words: Titanyl acetate, Diphenyl carbonate, Phenol, Transesterification, Heterogeneous catalyst, Phenoxytitanium complex

CLC Number:

TrendMD:

TANG Rongzhi, WANG Songlin, ZHANG Yuanzhuo, CHEN Tong, WANG Gongying. Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2418.

Figures/Tables 14

Fig.1 Monodentate(A), Bidentate chelating(B) and Bidentate bridging(C) modes occurring in metal and carboxylates[21]

Fig.2 FTIR spectrum of titanyl acetate sample

Scheme 1 Structure of titanyl acetate(structure Ⅰ)

Fig.3 Solid state 13C NMR spectrum of titanyl acetate sample

Fig.4 TG(a), DTG(b) and DTA(c) curves of titanyl acetate sample

Table 1 Catalytic performance of titanyl acetate on the transesterification of DMC and phenol*

Mass of catalyst/g	Conversion of phenol (%)	Selectivity of transesterification (%)	Yield (%)
Mass of catalyst/g	Conversion of phenol (%)	Selectivity of transesterification (%)	MPC	DPC	AN
0.05	42.2	99.9	22.3	19.9	trace
0.10	47.8	99.9	25.6	22.2	trace
0.15	47.7	99.9	25.3	22.4	trace
0.20	48.4	99.9	24.7	23.7	trace
0.40	47.1	99.9	23.3	23.8	trace

Fig.5 Effect of calcined temperature on catalytic performance of titanyl acetate Reaction condition: 160 mmol phenol, 160 mmol DMC, 0.10 g catalyst, 9 h, 150—180 ℃.

Fig.6 XRD patterns of titanyl acetate calcined at different temperatures a. 200 ℃; b. 250 ℃; c. 300 ℃; d. 400 ℃.

Table 2 Reusability of catalyst*

Running time	Conversion of phenol (%)	Selectivity of transesterification (%)	Yield (%)
Running time	Conversion of phenol (%)	Selectivity of transesterification (%)	MPC	DPC	AN
1	47.8	99.9	25.6	22.2	trace
2	47.5	99.9	23.2	24.3	trace
3	45.0	99.9	22.7	22.3	trace

Fig.7 FTIR spectra of used catalyst a. 1st run; b. 2nd run; c. 3rd run.

Fig.8 Solid state 13C NMR spectrum of used catalyst

Scheme 2 Structure of used catalyst(structure Ⅱ)

Scheme 3 Reactions equations between titanyl acetate and phenol

Scheme 4 Reaction mechanism over phenoxy titanium complex on the transesterification of DMC and phenol

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