Supplementarymaterial

Supported CuCl/γ-Al2O3 inhibitors for Friedel-Crafts acylation with fluorobenzene

Yanhong Wang,a Jiahong Wang,aZhongzhu Long,b Shuihong Cai,cQiaochun Wang*a

aKey Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science & Technology

bCollege of pharmacy, East China University of Science & Technology

cShanghai Dongyue Biochem. Co. Ltd.

Shanghai 200237, P.R. China.

* Correspondence author: .

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1. Experimental section:

1.1 Preparation of the CuCl/γ-Al2O3 inhibitor

The γ-Al2O3 powder was firstly activated in a tube furnace under nitrogen atmosphere at 500°C for 4h. Then an exact amount of activated γ-Al2O3 powder was added to CuCl2 aqueous solution with vigorous stirring. Stoichiometric Na2SO3 aqueous solution was subsequently added dropwise to the mixture. The obtained mixture was stirred for 2h and then two equiv. of H2SO3 solution was added. The resulting mixture was centrifuged sufficiently and the supernate was removed. The left wet solids were dried for 4h at 50°C in a vacuum oven. The dried CuCl/γ-Al2O3 mixure was finally calcinated at 380°C for 4h in tubefurnace.

1.2 The Characterizations of the CuCl/γ-Al2O3 inhibitor

XRD measurements were recorded on a Rigaku D/max 2550V powder diffractometer. BET specific surface area, pore volume and average pore size were measured by physical adsorption of N2 using Quantachrome autosorb IQ instrument. The copper content was verified by an inductively coupled plasma-atomic emission spectrometer (ICP) which was conducted on a Vanan 710 equipment. Scanning electron microscope (SEM) images of supported catalysts were detected by a JEOL JSM-6360LV instrument. X-ray photoelectron spectrometer (XPS) characterization was carried out in an AXIS Ultra electron spectrometer.

1.3 The defluorination-inhibiting performance and recycling of the CuCl/γ-Al2O3

15.0g aluminiumchloride and an exact amount (the equivalent of 4.48g CuCl, 0.5 equiv. basing on the phenylacetyl chloride added) of CuCl/γ-Al2O3 were added to a flask. 80 mL fluorobenzene was then added and resulting mixture was stirred at 0-5°C. 14.0g phenylacetyl chloride was added dropwise to the above mixture was sequentially operated at 0-5°C for 2h. The co-catalyst was then separated from the solvent by suctionfiltration. The filtrate was added with 90mL hydrochloric acid dropwised under ice water bath and stirred sequentially for 2h. The organic phase was collected and washed successively with saturated sodium bicarbonate and saturatedNaCl aqueous solutions.After being distilled to nearly dryness, the recovered fluorobenzene was dried over anhydrousmagnesiumsulfate and were detected through GC with a Agilent 6890 PLUS; the residue was the raw product of M2, which was purified by the recrystallization with 75% ethyl alcohol and dried. The obtained white solid was weighed, characterized by 1H NMR and analyzed by the HPLC with an Agilent 1100 instrument. The above separated CuCl/γ-Al2O3 cake was washed with fluorobenzene, dried in vacuo, and was used directly for the next turn in the recycling process. In order to make an accurate comparison, 50mL of recovered fluorobenzene was taken out, combined with 30 mL fresh fluorobenzene, and then used for the next run of acylation.

2. Figures

Fig. S1. N2 adsorption isotherms of (a) Cu@Al(2%); (b) Cu@Al (6%);(c) Cu@Al (10%); (d) Cu@Al (13%); (e) Cu@Al (16%); (f) Cu@Al (17%)

Fig.S2. presents the XPS spectrum of the obtained CuCl/γ-Al2O3 that detected the Cu 2p and Cl 2p regions. The peaks located at around 952.7 eV and 932.9 eV can be assigned to the binding energies of Cu 2p1/2 and Cu 2p3/2, respectively; while those at around 199.9 eV and 198.7 eV can be assigned to the binding energies of Cl 2p1/2 and Cl 2p3/2, respectively. Additionally, it can be assumed that the catalysts were partially oxidized due to the weak satellite peaks at 942.4eV and 944.6eV.

Fig.S2. Cu 2p (A) and Cl 2p (B) scanning of (a) Cu@Al (2%), (b) Cu@Al (6%)，(c) Cu@Al (10%), (d) Cu@Al (13%) and (e) Cu@Al(16%).

Fig.S3. HPLC spectra of products with (a) Cu@Al (10%)-run1; (b) Cu@Al (10%)-run2; (c) Cu@Al (10%)-run3; (d) Cu@Al (10%)-run4; (e) Cu@Al (10%)-run5; (f) Cu@Al (10%)-run6; (g) Cu@Al (6%); (h) Cu@Al (13%); (i) blank control; (j) defluoro by-product 2-Phenylacetophenone.

Fig.S4. GC spectra of distilled fluorobenzene with (a) Cu@Al (10%)-run1; (b) Cu@Al (10%)-run2; (c) Cu@Al (10%)-run3; (d) Cu@Al (10%)-run4; (e) Cu@Al (10%)-run5; (f) Cu@Al (10%)-run6; (g) Cu@Al (2%) (h) Cu@Al (6%); (i) Cu@Al (13%); (j) Cu@Al (17%) (k) blank control.

Fig.S5. HPLC spectra of products in blank control: (a) run1; (b) run2; (c) run3; GC spectra of distilled fluorobenzene in blank control: (d) run1 (e) run2; (f) run3.

Fig.S6. 1HNMR spectra of products with (a) Cu@Al (10%)-run1; (b) Cu@Al (10%)-run2; (c) Cu@Al (10%)-run3; (d) Cu@Al (10%)-run4; (e) Cu@Al (10%)-run5; (f) Cu@Al (10%)-run6; (g) Cu@Al (6%); (h) Cu@Al (13%); (i) blank control; (j) defluoro by-product 2-Phenylacetophenone.

Fig.S7. 1HNMR spectra (400MHz, 25°C，DMSO) of (a) M2; (b) 1.

Fig.S8. EI-TOF Mass spectra (a) M2; (b) 1.

2. Tables

Table S1. GC data of the recycled fluorobenzene in the absence (blank control) and the presence ofCuCl. The contents of the starting fluorobenzene are fluorobenzene 99.96% and benzene0.011%.

Samples / Recycled fluorobenzene
Fluorobenzene(%) / Cben(%)
blank control / 99.95 / 0.030
0.5 equiv CuCl / 99.92 / 0.016
1.0 equiv CuCl / 99.90 / 0.013
1.5 equiv CuCl / 99.94 / 0.011

Table S2. The performance of different amount of Cu@Al(10%) added to the acetylation.

Entry / Amount of co-catalysts (equivalent) / Recycled fluorobenzene
Fluorobenzene(%) / Cben(%)
1 / 0.3 / 99.80 / 0.013
2 / 0.4 / 99.73 / 0.010
3 / 0.5 / 99.96 / 0.008
4 / 0.8 / 99.88 / 0.008