Methods for preparing arene-BIS (dicarboximide)-based semiconducting materials and related intermediates for preparing same

A method for preparing a compound having formula II:

• the method comprising reacting a compound having formula Ia:
• with an amine of the formula R1NH2, or
• reacting a compound having formula Ib:
• with a compound having the formula R1-LG,
• wherein:
• Q is a fused ring moiety;
• Ra, at each occurrence, is selected from a) —CN, b) —NO2, c) —C(O)Rb, d) —C(O)NHRb, e) —C(O)ORb, f) —S(O)Rb, g) —S(O)2Rb, h) —S(O)2OH, i) —(CF2)tRb, j) —[C(CF3)2]tRb, k) oxo, and 1) a 5-14 membered heteroaryl group substituted with 1-5 Rc groups;
• Rb, at each occurrence, is selected from a) H, b) a C1-20 alkyl group, c) a C3-10 cycloalkyl group, d) a C6-14 aryl group, e) a C7-20 arylalkyl group, f) a 3-12 membered cycloheteroalkyl group, and g) a 5-14 membered heteroaryl group, wherein each of the C1-20 alkyl group, the C3-10 cycloalkyl group, the C6-14 aryl group, the C7-20 arylalkyl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 Rc groups;
• Rc, at each occurrence, is selected from a) a halogen, b) —CN, c) —NO2, d) —C(O)H, e) —C(O)—C1-20 alkyl, f) —C(O)NH2, g) —C(O)NH—C1-20 alkyl, h) —C(O)N(C1-20 alkyl)2, i) —C(O)OH, j) —C(O)—OC1-20 alkyl, k) —S(O)H, l) —S(O)—C1-20 alkyl, m) —S(O)2H, n) —S(O)2—C1-20 alkyl, and o) —S(O)2OH;
• n is 1, 2, 3, 4, 5, 6, 7, or 8;
• t, at each occurrence, is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;
• R1, at each occurrence, is -L-R2 or -L-Ar1—R2;
• L, at each occurrence, is Y or (CH2CH2O)p;
• Y, at each occurrence, is a divalent C1-20 alkyl group, a divalent C1-20 haloalkyl group, or a covalent bond;
• Ar1 is a C6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, a C1-20 alkyl group, a C2-20 alkenyl group, a C1-20 alkoxy group, and a C1-20 haloalkyl group;
• R2, at each occurrence, is selected from a) —ORd, b) —C(O)ORd, c) C(O)Re, d) —C(O)NReRf, e) —C(S)ORd, f) —C(S)Re, g) —C(S)NReRf, h) —SRd, i) —S(O)2ORd, j) —S(O)2Re, k) —S(O)2NReRf, l) a C1-20 alkyl group, m) a C2-20 alkenyl group, n) a C2-20 alkynyl group, o) a C3-10 cycloalkyl group, p) a C6-14 aryl group, q) a 3-12 membered cycloheteroalkyl group, and r) a 5-14 membered heteroaryl group, wherein each of the C1-20 alkyl group, the C2-20 alkenyl group, the C2-20 alkynyl group, the C3-10 cycloalkyl group, the C6-14 aryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5-L-R3 or -L-Ar2—R3 groups;
• Rd, at each occurrence, is selected from a) H, b) —C(O)Re, c) —C(O)NReRf, d) —C(S)Re, e) —C(S)NReRf, f) a C1-20 alkyl group, g) a C2-20 alkenyl group, h) a C2-20 alkynyl group, i) —Y—C3-10 cycloalkyl group, j) —Y—C6-14 aryl group, k) —Y-3-12 membered cycloheteroalkyl group, and l) —Y-5-14 membered heteroaryl group, wherein each of the C1-20 alkyl group, the C2-20 alkenyl group, the C2-20 alkynyl group, the C3-10 cycloalkyl group, the C6-14 aryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5-L-R3 groups;
• Re and Rf, at each occurrence, independently are selected from a) H, b) —OH, c) —SH, d) —S(O)2OH, e) —C(O)OH, f) —C(O)NH2, g) —C(S)NH2, h) —OC1-20 alkyl, i) —O—Y—C6-14 aryl, j) —C(O)—C1-20 alkyl, k) —C(O)—OC1-20 alkyl, l)—C(S)N(C1-20 alkyl)2, m) —C(S)NH—C1-20 alkyl, n) —C(O)NH—C1-20 alkyl, o) —C(O)N(C1-20 alkyl)2, p) —S(O)m—C1-20 alkyl, q) —S(O)m—OC1-20 alkyl, r) —C(O)—Y—C6-14 aryl, s) —C(O)—O—Y—C6-14 aryl, t) —C(S)N(—Y—C6-14 aryl)2, u) —C(S)N(C1-20 alkyl)-Y—C6-14 aryl, v) —C(S)NH—Y—C6-14 aryl, w) —C(O)NH—Y—C6-14 aryl, x) —C(O)N(C1-20 alkyl)-Y—C6-14 aryl, y) —C(O)N(Y—C6-14 aryl)2, z) —S(O)m—Y—C6-14 aryl, aa) —S(O)m—O—Y—C6-14 aryl, ab) a C1-20 alkyl group, ac) a C2-20 alkenyl group, ad) a C2-20 alkynyl group, ae) —Y—C3-10 cycloalkyl group, af) —Y—C6-14 aryl group, ag) —Y-3-12 membered cycloheteroalkyl group, and ah) —Y-5-14 membered heteroaryl group, wherein each of the C1-20 alkyl groups, the C2-20 alkenyl group, the C2-20 alkynyl group, the C3-10 cycloalkyl group, the C6-14 aryl groups, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5-L-R3 groups;
• Ar2, at each occurrence, is a C6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, a C1-20 alkyl group, a C2-20 alkenyl group, a C1-20 haloalkyl group, and a C1-20 alkoxy group;
• R3, at each occurrence, is selected from a) halogen, b) —CN, c) —NO2, d) oxo, e) —ORg, f) —SRg, g) —NRgRh, h) —N(O)RgRh, i) —S(O)mRg, j) —S(O)mORg, k) —S(O)mNRgRh, l) —C(O)Rg, m) —C(O)ORg, n) —C(O)NRgRh, o) —C(S)NRgRh, p) —SiH3, q) —SiH(C1-20 alkyl)2, r) —SiH2(C1-20 alkyl), s) —Si(C1-20 alkyl)3, t) a C1-20 alkyl group, u) a C2-20 alkenyl group, v) a C2-20 alkynyl group, w) a C3-10 cycloalkyl group, x) a C6-14 aryl group, y) a 3-12 membered cycloheteroalkyl group, or z) a 5-14 membered heteroaryl group, wherein each of the C1-20 alkyl groups, the C2-20 alkenyl group, the C2-20 alkynyl group, the C3-10 cycloalkyl group, the C6-14 aryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5-L-R4 groups;
• Rg and Rh, at each occurrence, independently are selected from a) H, b) —OH, c) —SH, d) —S(O)2OH, e) —C(O)OH, f) —C(O)NH2, g) —C(S)NH2, h) —OC1-20 alkyl, i) —O—Y—C6-14 aryl, j) —C(O)—C1-20alkyl, k) —C(O)—OC1-20alkyl, l) —C(S)N(C1-20 alkyl)2, m) —C(S)NH—C1-20 alkyl, n) —C(O)NH—C1-20 alkyl, o) —C(O)N(C1-20 alkyl)2, p) —S(O)m—C1-20 alkyl, q) —S(O)m—OC1-20 alkyl, r) —C(O)—Y—C6-14 aryl, s) —C(O)—O—Y—C6-14 aryl, t) —C(S)N(—Y—C6-14 aryl)2, u) —C(S)N(C1-20 alkyl)-Y—C6-14 aryl, v) —C(S)NH—Y—C6-14 aryl, w) —C(O)NH—Y—C6-14 aryl, x) —C(O)N(C1-20 alkyl)Y—C6-14 aryl, y) —C(O)N(Y—C6-14 aryl)2, z) —S(O)m—Y—C6-14 aryl, aa) —S(O)m—O—Y—C6-14 aryl, ab) a C1-20 alkyl group, ac) a C2-20 alkenyl group, ad) a C2-20 alkynyl group, ae) —Y—C3-10 cycloalkyl group, af) —Y—C6-14 aryl group, ag) —Y-3-12 membered cycloheteroalkyl group, and ah) —Y-5-14 membered heteroaryl group, wherein each of the C1-20 alkyl groups, the C2-20 alkenyl group, the C2-20 alkynyl group, the C3-10 cycloalkyl group, the C6-14 aryl groups, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5-L-R4 groups;
• R4, at each occurrence, is selected from a) halogen, b) —CN, c) —NO2, d) oxo, e) —OH, f) —NH2, g) —NH(C1-20 alkyl), h) —N(C1-20 alkyl)2, i) —N(C1-20 alkyl)-Y—C6-14 aryl, j) —N(—Y—C6-14 aryl)2, k) —S(O)mH, l) —S(O)mC1-20 alkyl, m) —S(O)2OH, n) —S(O)n, —OC1-20 alkyl, o) —S(O)m—O—Y—C6-14 aryl, p) —CHO, q) —C(O)—C1-20 alkyl, r) —C(O)—C6-14 aryl, s) —C(O)OH, t) —C(O)—OC1-20 alkyl, u) —C(O)—O—Y—C6-14 aryl, v) —C(O)NH2, w) —C(O)NH—C1-20 alkyl, x) —C(O)N(C1-20 alkyl)2, y) —C(O)NH—Y—C6-14 aryl, z) —C(O)N(C1-20 alkyl)-Y—C6-14 aryl, aa) —C(O)N(—Y—C6-14 aryl)2, ab) —C(S)NH2, ac)—C(S)NH—C1-20 alkyl, ad)—C(S)N(C1-20 alkyl)2, ae) —C(S)N(—Y—C6-14 aryl)2, af) —C(S)N(C1-20 alkyl)-Y—C6-14 aryl, ag)—C(S)NH—Y—C6-14 aryl, ah) —S(O)mNH2, ai) —S(O)mNH(C1-20 alkyl), aj) —S(O)mN(C1-20 alkyl)2, ak) —S(O)mNH(—Y—C6-14 aryl), al)—S(O)mN(C1-20 alkyl)-Y—C6-14 aryl, am) —S(O)mN(—Y—C6-14 aryl)2, an) —SiH3, ao) —SiH(C1-20 alkyl)2, ap) —SiH2(C1-20 alkyl), ar) —Si(C1-20 alkyl)3, as) a C1-20 alkyl group, at) a C2-20 alkenyl group, au) a C2-20 alkynyl group, av) a C1-20 alkoxy group, aw) a C1-20 haloalkyl group, ax) a C3-10 cycloalkyl group, ay) a C6-14 aryl group, az) a 3-12 membered cycloheteroalkyl group, and ba) a 5-14 membered heteroaryl group;
• m, at each occurrence, is 0, 1, or 2;
• and
• p, at each occurrence, is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20;
• and
• LG is selected from Cl, Br, I, N3, OTs, OMs, NO2, SCN, and CN.