Selective reactions of free radicals with olefins in the presence of an ion of Mn, V, or Ce
AssigneeMobil Oil Corporation
InventorsEl Ahmadi I. Heiba, Ralph M. Dessau
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Abstract
An olefin is reacted with a source of X free radical in the presence of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form derivatives of the olefin that contain one or more functional groups. The free radical X is one that is resistant to substantial oxidation by the ion of the metal and is obtained from ketones, aldehydes, esters, nitriles, nitroparaffins, sulfoxides, thiosulfonic acid esters, alkanesulfonic acids, alkanesulfinic acids, and thiols.
Claims58
Method of selectively reacting a free radical X with an olefin, said free radical X being selected from the group consisting of ##STR111## Where R is an alkyl group and R' is a hydrocarbyl or substituted hydrocarbyl group, and said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol, comprising reacting said olefin, a compound selected from the group consisting of ketones, aldehydes, esters, nitriles, sulfoxides, nitroparaffins, thiosulfonic acid esters, alkanesulfonic acids, allkanesulfinic acids, and thiols, and a stoichiometric quantity of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure ##STR112##
Method of reacting a free radical .sup.. X with an olefin comprising heating said olefin with a source of said free radical .sup.. X in the presence of a stoichiometric amount of manganic acetate and in the presence of acetic acid for a time sufficient to form an addition product comprising said olefin and said free radical, said free radical .sup.. X being selected from the group consisting of ##STR122## where R is an alkyl group, and R' is a hydrocarbyl or substituted hydrocarbyl group, said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitorparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol.
Method of selectively reacting a free radical .sup.. X with an olefin, said free radical .sup.. X being selected from the group consisting of ##STR123## where R is an alkyl group and R' is a hydrocarbyl or substituted hydrocarbyl group, and said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide a thiosulfonic acid ester, and a thiol, comprising reacting said olefin with a compound selected from the group consisting of ketones, aldehydes, esters, nitriles, sulfoxides, nitroparaffins, thiosulfonic acid esters, and thiols, in the presence of a stoichiometric amount of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure, ##STR124##
Method of selectively reacting a free radical .sup.. X with an olefin, said free radical .sup.. X being selected from the group consisting of >C-SO.sub.3 H, and said free radical being derived respectively from an alkanesulfonic acid and an alkanesulfinic acid, comprising reacting said olefin with a compound selected from the group consisting of alkanesulfonic acids and alkanesulfinic acids, in the presence of a stoichiometric amount of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure, ##STR125##
Method of reacting a free radical .sup.. X with an olefin comprising heating said olefin with a source of said free radical .sup.. X in the presence of a stoichiometric amount of manganic propionate and in the presence of propionic acid for a time sufficient to form an addition product comprising said olefin and said free radical, said free radical .sup.. X being selected from the group consisting of ##STR126## where R is an alkyl group, and R' is a hydrocarbyl or substituted hydrocarbyl group, said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol.
Method of reacting a free radical, ##STR127## derived from a ketone with an octene comprising heating said ketone and said octene in the presence of a stoichiometric amount of manganic acetate and in the presence of acetic acid for a time sufficient to form an unsaturated ketone product of said octene and said free radical and a keto-ester product of said octene, said free radical, and the acetate portion of said manganic acetate.
Dependencies are inferred from the claim text.