Catalytic Decomposition of Alkyl Hydroperoxides with Ferrous Salt under the Visible Light at Ambient Temperature

doi:10.6023/A25120405

Abstract

Selective oxidation of C—H bond was regarded as the Holy Grail of chemistry. As one of the primary oxygenated products of selective oxidation of hydrocarbon, alkyl hydroperoxides (ROOHs) are necessary to be efficiently decomposed to the higher value-added oxygen-containing compounds such as alcohol and ketone. Usually, strong alkali of NaOH is used to decompose ROOHs to realize a higher selectivity to alcohol and ketone, which inevitably produces a large amount of alkali-containing waste potential destroying the environment. It is a challenge to develop a green method to catalytically decompose ROOHs especially under the mild conditions. In the present work, at the absence of any alkali and under the irradiation of blue light, specific ferrous salt of FeCl₂•4H₂O was found to be able to act as an efficient catalyst to decompose various ROOHs in ethanol. Decomposition of ROOHs were all conducted in a quartz tubes (10 mL) under the photonic irradiation of the LED lamp. Typically, tert-butyl hydroperoxide (TBHP) aqueous solution (70% (w), 0.8 mmol), metal salt (0.08 mmol), and solvent (1 mL) was added to the quartz tube. Then, the quartz tube was sealed with a sealing film and exposed to the LED lamp for 5 h under stirring. Modulating anionic and cationic species, wavelength of the light, and species of solvent showed obvious effect on the catalytic efficiency. At the ambient temperature under the photonic irradiation with the blue light of 400 nm and 3 W, high conversion of 82.3%~96.8% could be obtained with the selectivity of 85.2%~97.1% to the oxygenated product of high value-added alcohol or ketone for a series of ROOHs. Characterization results of FT-IR and UV-Vis spectra indicated that the interaction happening between the ferrous ions, chloride ion, and the solvent molecules improved the visible light absorption ability and then played an important role to improve the catalytic activity under the blue light irradiation.

Key words: alkyl hydroperoxides, ferrous salt, catalytic decomposition, ambient temperature, photonic irradiation

Cite this article

Fengkuan Ma, Yuxi Li, Dezhong Xie, Shuangshuang Zhang, Chen Chen, Qiaohong Zhang. Catalytic Decomposition of Alkyl Hydroperoxides with Ferrous Salt under the Visible Light at Ambient Temperature[J]. Acta Chimica Sinica, 2026, 84(4): 471-475.

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Fig. & Tab. 6

Figure 1. Effect of metal salts on the catalytic decomposition of TBHP a Reaction conditions: Catalytic decomposition of TBHP by different metal salts under dark (a) and light (b). 0.8 mmol of TBHP, 0.08 mmol of metal salt, ambient temperature, 1 mL of ethanol, irradiated by a LED lamp (465 nm and 3 W)

Figure 2. Effect of solvents on the catalytic decomposition of TBHP a Reaction conditions: Catalytic decomposition of TBHP by different solvents under dark and light conditions, 0.8 mmol of TBHP, 0.08 mmol of FeCl2•4H2O, ambient temperature, 1 mL of solvent, LED lamp (465 nm and 3 W), reaction for 30 h

Figure 3. Effect of light wavelength on the decomposition of TBHP a Reaction conditions: 0.8 mmol of TBHP, 0.08 mmol of FeCl2•4H2O, ambient temperature, 1 mL of ethanol, LED lamp (3 W), reaction for 5 h

Entry	Radical inhibitors	Conditions	Types of inhibition	Conversion of TBHP/%
1	None	hv	—	96.8
2	TBA	hv	•OH	91.3
3	BA	hv	Cl•	87.9
4	BHT	hv	RO•/ROO•	38.5
5	None	dark	—	31.2
6	TBA	dark	•OH	29.7
7	BA	dark	Cl•	27.3
8	BHT	dark	RO•/ROO•	10.1

Table 1. Results comparison with the addition of different inhibitors on the catalytic decomposition of TBHP

Figure 4. Proposed photocatalytic decomposition mechanism for TBHP with FeCl2•4H2O in EtOH

Entry	Catalyst	Temperature/℃	Substrate	Conversion/%	Selectivity of alcohol or ketone/%
1^a			CHHP	82.3	CyOH/85.2
2	FeCl₂•4H₂O	Ambient temperature	CHP	96.2	CA/94.5
3			PEHP	95.5	AcPO/88.2
4			TBHP	96.8	TBA/97.1
5^b	α-Co(OH)₂	60	CHHP	89.7	CyOH/61
6^c	[Bmim]Br	70	CHP	33.9	CA/100
7^d	Manganese oxide	65	TBHP	96	TBA/100

Table 2. Catalytical decomposition of various ROOH with FeCl2•4H2O/EtOH

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