Methods of making organic compounds by metathesis

摘要

Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

主权项

1. A method of making a dicarboxylic acid alkene, dicarboxylate ester alkene, or dicarboxylate salt alkene, the method comprising the steps of:
(a) providing a starting composition comprising one or more unsaturated fatty acids, unsaturated fatty esters, or unsaturated fatty acid salts, which comprise a residue selected from the group consisting of —C(O)—(CH2)7CH═CH—(CH2)7-CH3, —C(O)—(CH2)7CH═CH—CH2-CH═CH—(CH2)4-CH3, and —C(O)—(CH2)7CH═CH—CH2-CH═CH—CH2-CH═CH—CH2-CH3; (b) cross-metathesizing the composition of step (a) with 1-butene in the presence of a first metathesis catalyst, to form cross-metathesis products comprising: (i) one or more olefins having a terminal carbon-carbon double bond; and (ii) one or more acid-, ester-, or carboxylate salt-functionalized alkenes comprising a —C(O)—(CH2)7-CH═CH—CH2-CH3 residue; (c) separating at least a portion of one or more of the acid-, ester-, or carboxylate salt-functionalized alkenes of step (b) from the one or more olefins of step (b); and (d) self-metathesizing the separated acid-, ester-, or carboxylate salt-functionalized alkenes of step (c) in the presence of a second metathesis catalyst to form a composition comprising: (i) one or more dicarboxylic acid alkenes, dicarboxylate ester alkenes, or dicarboxylate salt alkenes, which comprise a —C(O)—(CH2)7-CH═CH—(CH2)7-C(O)— residue, and (ii) 3-hexene; wherein the first metathesis catalyst is a 2nd Generation Grubbs-type catalyst having the structure of formula (V):wherein:
M is a Group 8 transition metal; L2 and L3 are independently neutral electron donor ligands; n is 0 or 1; m is 0, 1, or 2; X1 and X2 are independently anionic ligands; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; X and Y are independently heteroatoms selected from N, O, S, and P; p and q are independently 0 or 1; Q1, Q2, Q3, and Q4 are independently linkers selected from the group consisting of hydrocarbylenes and substituted heteroatom-containing hydrocarbylenes; w, x, y, and z are independently zero or 1; and R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl.