Succinic anhydrides from epoxides

摘要

Catalysts and methods for the double carbonylation of epoxides are disclosed. Each epoxide molecule reacts with two molecules of carbon monoxide to produce a succinic anhydride. The reaction is facilitated by catalysts combining a Lewis acidic species with a transition metal carbonyl complex. The double carbonylation is achieved in single process by using reaction conditions under which both carbonylation reactions occur without the necessity of isolating or purifying the product of the first carbonylation.

主权项

1. A process for the double carbonylation of an epoxide to succinic anhydride in a reaction which comprises reacting an epoxide, where the epoxide is ethylene oxide, with carbon monoxide in a solvent in the presence of a catalytically effective amount of a catalyst, where the catalyst comprises a Lewis acid in combination with a transition metal carbonyl complex, where the Lewis acid is of the following formula:where:
M is aluminum; Rd at each occurrence is independently selected from the group consisting of: —H; C1-C12 alkyl; C2-C12 alkenyl; C2-C12 alkynyl; halogen; —OR10; —OC(O)R13; —OC(O)OR13; —OC(O)NR11R12; —CN; —CNO; —C(O)R13; —C(R13)zH(3-z); —C(O)OR13; —C(O)NR11R12; —NR11R12; —NR11C(O)R10; —NR11C(O)OR13; —NR11SO2R13; —NCO; —N3; —NO2; —S(O)xR13; —SO2NR11R12; —C(R13)zH(3-z); —(CH2)kR14; —(CH2)k-Z-R16—; and —(CH2)k-Z-(CH2)m-R14, and
R10 at each occurrence is independently selected from the group consisting of: —C(R13)zH(3-z); C1 to C12 alkyl; C2 to C12 alkenyl; C2 to C12 alkynyl; up to a C12 carbocycle; —S(O)2R13; —Si(R15)3; —H; and a hydroxyl protecting group,R11 and R12 at each occurrence are independently selected from the group consisting of: —H; C1 to C12 alkyl; C2 to C12 alkenyl; C2 to C12 alkynyl; and —C(R13)zH(3-z);where R11 and R12; when both present, can optionally be taken together with the atom to which they are attached to form a 3- to 10-membered ring,R13 at each occurrence is independently selected from the group consisting of: —H; C1 to C12 alkyl; C2 to C12 alkenyl; C2 to C12 alkynyl; and up to a C12 carbocycle,R14 at each occurrence is independently selected from the group consisting of: halogen; —OR10; —OC(O)R13; —OC(O)OR13; —OC(O)NR11R12; —CN; —CNO; —C(R13)zH(3-z); —C(O)R13; —C(O)OR13; —C(O)NR11R12; —NR11C(O)R13; —NR11C(O)OR10; —NR11SO2R13; —NCO; —N3; —NO2; —S(O)xR13; —SO2NR11R12; and up to a C12 carbocycle,R15 at each occurrence is independently selected from the group consisting of: C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 alkynyl; and up to a C12 carbocycle,R16 at each occurrence is independently selected from the group consisting of: C1 to C12 alkyl; C2 to C12 alkenyl; C2 to C12 alkynyl; up to a C12 carbocycle; and —C(R13)zH(3-z),Z is a divalent linker selected from the group consisting of:
—(CH═CH)a—; —(CH≡CH)a—; —C(O)—; —C(═NOR11)—; —C(═NNR11R12)—; —O—; —N(R11)—; —N(C(O)R13)—; and —S(O)x—,a is 1, 2, 3, or 4,k is an integer from 1 to 8 inclusive,m is an integer from 1 to 8 inclusive,x is 0, 1, or 2,z is 1, 2, or 3; andwhere the solvent includes a Lewis base and the crude yield of succinic anhydride is at least 10 percent.