Oxidation Reactions with
Aliphatic Peracids T
formed (12): tlic sy-tem reached T h e eaSe of preparation of concentrated equilibrium in :ipprosiin:iteIy 4 hours phatic peracids (peracetic, peraliphatic peracids from commerciall? :it -kL??; peracetic acid arid C c i ;113'formic) has long tieen k n o ~ \ - n(3, 5, 6, a\ailable concentrated h:drogeii perdrogen peroside. lllieti 1.5 nioles of 16, 1 1 , 19, 14, 15). Econoniic:il oxide stimulated interest in the general preparation of concentrated peracid reactions of the peracids. Seieral reac00'; hydrogen perosidc re:cted simisolutions became feasible with the tions of general applicabilit? in the larly with 1 mole of acetic :icid, ?quicommercial availability of highly conorganic qnthesia field w e r e studied. lilirium was reached nt :il)prosirn:itely centrated hydrogen peroside (12). Procedures are gi\en for the oxidation -@-; perxetic acid :ilitl 18'; hyThis resulted in renewed interest in of aniline to azoxqbenzene, $-naphthol drogen peroxide. The e,luilil)rium the aliphatic peracids. This paper to o-carboxycinnamic acid, and anthram i s t u r e c o n t R i lied :ip 1)r o si "?at el y describes several oxidation reactions cene to anthraquinone and the hldroxyl1 5 5 water. of the peracids which should find ation of unsaturated fatt? materials. general application ill tlic organic en peroxide i-. :I poiveragent : i d m u a t be synthesis field. ider certaiii cotiditions it handled q j t l i approprint Osidations n-ith aliphatic peracids can be conducted ( u ) by rials :md form shockcan cause Ignition of c preparatidn in situ of tlie peracid by the action of 90% hydrogen sensitive mixtures with s peroxide on an a1iph:itic x i d solution of the subdance t o he osiofconcentration. By its dized, in the p r c m i w of a 1;' mineral acid catalyst, or (b'i by use sensitive. All attempts of prepared concentr:itcd per:icid solutions. I n thi.q w i y aniline was oxidized t o azosyhenzene, &naphthol to o-carboxycinnamic both 90yc hydrogen peroxide acid, anthracene t o anthr:rquiiione, and unsaturated fatty acids cident'. It is recommended that, in t o the corresponding dihydrosy compounds. Re:lctions are the extension of any reaction of gOco hydrogen peroside and peracetic acid to new materials, the work be initially conducted with characterized b y liigli reaction efficiency, minimum by-product :\mounts of approsimately 3 ml. formation, lack of metallic contamination, and general solubility
HE osidizing action of the ali-
of the oxidizing ngcnt in the reaction medium. Concentrated peracids generally -1ioiv increased yields and shorter reaction
OXIDATION O F ANILINE T O AZOXYBESZESE
time for those reactions to n-liich dilute peracid and dilute hydrogen peroside solution:: linve lieen previously applied. Hithertu of :icntieniic interrst as :in oxidant, per;ieetic acid noTv becomes a readily :ivnilable osidizing agent of priictical importance for indurtri:il orpunic rextions. The reactions described in this pnper :ire significmt not only 1xx:iuse many of the product-. themselves 111 e of commcrci:il interest but 1)ecnui;e they are class reactioiis c;ip:ihle of wide inc1ustri:il npplicntion. Quinone forniation in the benzene, iiapthalene, Lind anthr:icene iei,ies, a > \\-ell as oxidation of aromatic amine. t o :i7o and azosy compoundsj are of practical import:ince in the dyestuff and p1i:irniaceutical fields. Noten-orthy arid outstxiding as cliwicteriitic arid specific reactions of tlie diphatic per:icids are the hydrosylntion and eposidation ( 1 1 ) of double bonds niid the ring-splitting action obt:iined with aromatic hydrocar\>onsand derivatives. Thus, hydroxylation of mono unsaturated fatty acids yields useful dihydrosy fatty acids, high melting materials of interwt in the prep:tratioii of modified alkyd-type resins ( 7 ) and pl:\.-tickers (8). This same reaction applied t o the hydroxylation of unsaturated oils, terpenes (I), and rubbers ( 2 ) gives rise to commercially interesting hydroxylated derivative.
