Phenanthrene diozonide

Phenanthrene Diozonide. Ct 4 Hj 0 (03 )2, colorl crysts, very expl. Prepd by passing ozone thru a cooled chioroformic phenanthrene soln Refs 1) Beil 5,670 [583] 2) C.D. Harries... 

Phenanthrene Diozonide.C14H102O3. Harries and Weiss in 1905 reported that the ozonolysis of phenanthrene in chlf soln produced a crystn, expl diozonide (Refs 2 4). Subsequently, very detailed studies of the ozonolysis reaction of phenanthrene by three different groups of investigators failed to confirm the existence... 

Phenanthrene has also a reactive 9,10-double bond, in agreement with the Clar structure having two aromatic sextets and a C=C fixed double bond in the median ring. On co-ozonolysis with formaldehyde, acetyl cyanide, or benzoyl cyanide, phenanthrene reacted accordingly, affording an aldehydic ozonide 112, which in a separate co-ozonolysis with vinyl acetate that produced formaldehyde oxide (H2C-0-0) gave rise to a diozonide 113 (Scheme 35 and Table 14). 

In the case of pyrene, there are two sextets and two fixed double bonds similar to the phenanthrenic double bond. In agreement with this argument and with the result for phenanthrene, co-ozonolysis of pyrene with formaldehyde or acetyl cyanide afforded the expected normal ozonide 114 and the cross-ozonide 115 with an aldehydic group. In a separate co-ozonolysis of 115 with vinyl acetate, diozonides 116 were prepared. No cross-ozonide was obtained in the presence of benzoyl cyanide, which afforded only the normal mono-ozonide 114 (Scheme 36 and Table 15). 

The final polycyclic aromatic hydrocarbon that was investigated <2000EJ0335> is benzo[fixed double bond like phenanthrene. Its cross-ozonolysis with formaldehyde gave none of the normal ozonide 120, but mainly the aldehydic ozonide 117. At room temperature, a substantial amount of opening of the ozonide ring occurred with the formation of the acid aldehyde 121. Both products 117 and 121 could be stabilized by treatment with O-methylhydroxylamine, yielding products 118 and 122, respectively. The separate co-ozonolysis of compound 117 with vinyl acetate afforded the diozonide 119 (Scheme 37 and Table 16). The cross-ozonolysis with acetyl cyanide followed by treatment of the crude reaction mixture with O-methylhydroxylamine yielded the O-methyloxime of the cross-product. Cross-ozonolysis with benzoyl cyanide was not successful, and only the normal mono-ozonide 120 was formed. 

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See also in sourсe #XX -- [ , ]

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