Oxidation Mechanism of A Peroxide reacting with a sulfide to form Anthracene

I have the following reaction: A peroxide reacting with a sulfide to form anthracene, sulfoxide and water or sulfoxide and water depending on the reactant. The reaction is from a paper discussing the oxygen indused oxidation of bitumen (asphalt binder).


[![fdgbrtb](https://i.stack.imgur.com/PmMe9.png)](https://i.stack.imgur.com/PmMe9.png)


[1](https://i.stack.imgur.com/PmMe9.png)


  

The paper cites another paper for the reaction mechanism which is of interest to me and is shown below:
  

  

  

![enter im](https://i.stack.imgur.com/RsqWe.png)


[2](https://i.stack.imgur.com/RsqWe.png)


In my opinion the two reactions differ greatly in their products and the mechanism doesn't make sense.
  
1. In the first step the why would the sulphur atom attack the negative oxygen atom?
  
2. Is the reaction even possible with hydrogen peroxide?


  

Edit: I have also found another paper which somewhat changes the initial from the sulphur attacking the oxygen to the oxygen attacking the sulphur. I assume either the oxygen is attacking or the sulphur is attacking. Who could be right?
  
J. Am. Chem. Soc. 2004, 126, 3, 900–908
  

  

[1](https://i.stack.imgur.com/PmMe9.png) Claine Petersen, J. “A Dual, Sequential Mechanism for the Oxidation of Petroleum Asphalts.” Petroleum Science and Technology, vol. 16, no. 9–10, 1998, pp. 1023–1059, <https://doi.org/10.1080/10916469808949823>.
  
  

[2](https://i.stack.imgur.com/RsqWe.png) Hargrave, R. “Oxidation of Organic Sulphides - VI. Interaction of Hydroperoxides with Unsaturated Sulphides.” Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, vol. 235, no. 1200, 1956, pp. 55–67, <https://doi.org/10.1098/rspa.1956.0064>.




Bobsburger: If I am understanding you correctly, you are proposing a reaction scheme wherein the hydroperoxide **1** forms anthracene via the loss of water. Pathway **1** $\rightarrow$ **2** $\rightarrow$ **3** $\rightarrow$ etc. does not provide anthracene but rather anthrone **4**. There is no role for dimethyl sulfide (DMS) because hydroperoxide **1** and anthrone **4** are of the same oxidation level. This process is merely an acid-catalyzed rearrangement and not a redox reaction.  

On the other hand and following the red arrows, attack of DMS on the terminal oxygen of hydroperoxide **1** affords an intermediates alkoxide **5** and the protonated form of dimethyl sulfoxide (DMSO) **6**. A neutralization of these two species provides alcohol **7** and DMSO. This alcohol in acid medium forms carbocation **9** via the protonated alcohol **8**. Loss of a proton from carbocation **9** provides anthracene **10**. Accordingly, hydroperoxide **1** is reduced by two electrons and DMS is oxidized by two electrons.  

Now, if this reaction were run in some sort of aqueous acid medium, then one might argue that protonation of the inner oxygen of **1** leads to a solvolysis to alcohol **7** via carbocation **8**, both of which lead to anthracene **10**. With or without water, hydrogen peroxide would also be formed. If this pathway were viable, then there is no need for the presence of DMS.


![](https://i.stack.imgur.com/2BC0Z.jpg)
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