HETEROAROMATIC COMPOUNDS FOR ORGANIC ELECTRONICS
20170365791 · 2017-12-21
Assignee
Inventors
- Hitoshi YAMATO (Takarazuka-shi, JP)
- Takuya Tsuda (Amagasaki, JP)
- Chao Wu (Mannheim, DE)
- Thomas WEITZ (Muenchen, DE)
- Michael Eustachi (Walldorf, DE)
- Maximilian Hemgesberg (Kaiserslautern, DE)
Cpc classification
H10K10/486
ELECTRICITY
International classification
Abstract
The present invention provides compounds of formula (I) wherein X is O, S or NR.sup.10, wherein R.sup.10 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl or C(0)-OR, R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, and substituted C.sub.5-8-cycloalkenyl, and an electronic device comprising the compounds as semiconducting material.
##STR00001##
Claims
1: A compound of formula (1): ##STR00043## wherein: X is O, S or NR.sup.10, R.sup.10 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl or C(O)—OR.sup.11, R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl, substituted S—C.sub.1-30-alkyl, C.sub.6-14-aryl, substituted C.sub.6-14-aryl, 5 to 15 membered heteroaryl, substituted 5 to 15 membered heteroaryl and halogen, or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 to 10 membered aromatic ring system, substituted 6 to 10 membered aromatic ring system, 5 to 12 membered heteroaromatic ring system or a substituted 5 to 12 membered heteroaromatic ring system, substituted C.sub.1-30-alkyl, substituted C.sub.2-30-alkenyl, substituted C.sub.2-30-alkynyl, substituted O—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, at each occurrence, are C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, O—C.sub.1-30-alkyl, respectively, S—C.sub.1-30-alkyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR.sup.c, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.5-8-cycloalkyl, and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR.sup.c, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.6-14-aryl, substituted 5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ring system, and substituted 5 to 12 membered heteroaromatic ring system, at each occurrence, are C.sub.6-14-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ring system, respectively, 5 to 12 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.5-6-cycloalkenyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2, at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, can be replaced by a linking group selected from the group consisting of O, S, NR.sup.12, CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR.sup.12—C(O), C(O)—NR.sup.12, OC(O)—NR.sup.12 and NR.sup.12—C(O)—O, R.sup.12 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl or C(O)—OR.sup.d, and R.sup.a, R.sup.b, R.sup.c and R.sup.d are independently from each other and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.5-6-cycloalkenyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl.
2: The compound of formula (1) of claim 1, wherein: X is O, S or NR, R.sup.10 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl or C(O)—OR.sup.11, R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl, substituted S—C.sub.1-30-alkyl, C.sub.6-14-aryl, substituted C.sub.6-14-aryl, 5 to 15 membered heteroaryl, substituted 5 to 15 membered heteroaryl and halogen; or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 to 10 membered aromatic ring system, substituted 6 to 10 membered aromatic ring system, 5 to 12 membered heteroaromatic ring system or a substituted 5 to 12 membered heteroaromatic ring system, substituted C.sub.1-30-alkyl, substituted C.sub.2-30-alkenyl, substituted O—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, at each occurrence, are C.sub.1-30-alkyl, C.sub.2-30-alkenyl, O—C.sub.1-30-alkyl, respectively, S—C.sub.1-30-alkyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.6-14-aryl, substituted 5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ring system and substituted 5 to 12 membered heteroaromatic ring system, at each occurrence, are C.sub.6-14-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ring system, respectively, 5 to 12 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR.sup.c, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2, at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, can be replaced by a linking group selected from the group consisting of O, S, NR.sup.12, CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR.sup.12—C(O), C(O)—NR.sup.12, OC(O)—NR.sup.12 and NR.sup.12—C(O)—O, R.sup.12 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, or C(O)—OR.sup.d, and R.sup.a, R.sup.b, R.sup.c and R.sup.d are independently from each other and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl.
3: The compound of claim 1, wherein: X is O, S or NR.sup.10, R.sup.10 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl or C(O)—OR.sup.11, R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, substituted C.sub.6-14-aryl, 5 to 15 membered heteroaryl and substituted 5 to 15 membered heteroaryl; or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 to 10 membered aromatic ring system, substituted 6 to 10 membered aromatic ring system, 5 to 12 membered heteroaromatic ring system or a substituted 5 to 12 membered heteroaromatic ring system, substituted C.sub.1-30-alkyl and substituted C.sub.2-30-alkenyl, at each occurrence, are C.sub.1-30-alkyl, respectively, C.sub.2-30-alkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bRe, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.6-14-aryl, substituted 5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ring system, and substituted 5 to 12 membered heteroaromatic ring system, at each occurrence, are C.sub.6-14-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ring system, respectively, 5 to 12 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-120-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR.sup.c, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2, at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl can be replaced by a linking group selected from the group consisting of O, S, NR.sup.12, CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR.sup.12—C(O), C(O)—NR.sup.12, OC(O)—NR.sup.12 and NR.sup.12—C(O)—O, R.sup.12 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl or C(O)—OR.sup.d, R.sup.a, R.sup.b, R.sup.c and R.sup.d are independently from each other and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl.
4: The compound of claim 1, wherein: X is O, S or NR.sup.10, R.sup.10 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl or C(O)—OR.sup.11, R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, substituted C.sub.6-14-aryl, 5 to 15 membered heteroaryl and substituted 5 to 15 membered heteroaryl; or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 to 10 membered aromatic ring system, substituted 6 to 10 membered aromatic ring system, 5 to 12 membered heteroaromatic ring system or a substituted 5 to 12 membered heteroaromatic ring system, substituted C.sub.1-30-alkyl and substituted C.sub.2-30-alkenyl, at each occurrence, are C.sub.1-30-alkyl, respectively, C.sub.2-30-alkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl, substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl; substituted C.sub.6-14-aryl, substituted 5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ring system, and substituted 5 to 12 membered heteroaromatic ring system, at each occurrence, are C.sub.6-14-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ring system, respectively, 5 to 12 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl; wherein at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl can be replaced by a linking group selected from the group consisting of O, S, and NR.sup.12, R.sup.12 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl or C(O)—OR.sup.d, and R.sup.d is at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.5-6-cycloalkenyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl.
5: The compound of claim 1, wherein: X is S, R.sup.1 is selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.6-10-aryl, substituted C.sub.6-10-aryl, 5 to 12 membered heteroaryl, and substituted 5 to 12 membered heteroaryl; or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 membered aromatic ring system, substituted 6 membered aromatic ring system, 5 to 9 membered heteroaromatic ring system or a substituted 5 to 9 membered heteroaromatic ring system, substituted C.sub.1-30-alkyl and substituted C.sub.2-30-alkenyl, at each occurrence, are C.sub.1-30-alkyl, respectively, C.sub.2-30-alkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, phenyl and 5 to 9 membered heteroaryl, substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, phenyl and 5 to 9 membered heteroaryl, substituted C.sub.6-10-aryl, substituted 5 to 12 membered heteroaryl, substituted 6 membered aromatic ring system, and substituted 5 to 9 membered heteroaromatic ring system, at each occurrence, are C.sub.6-10-aryl, 5 to 12 membered heteroaryl, 6 membered aromatic ring system, respectively, 5 to 9 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, phenyl, 5 to 9 membered heteroaryl, and at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkyl, can be replaced by the linking group O.
6: The compound of claim 1, wherein: X is S, R.sup.1 is selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl, and substituted C.sub.5-8-cycloalkyl, substituted C.sub.1-30-alkyl and substituted C.sub.2-30-alkenyl, at each occurrence, are C.sub.1-30-alkyl, respectively, C.sub.2-30-alkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, phenyl and 5 to 9 membered heteroaryl, and substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, phenyl and 5 to 9 membered heteroaryl.
7: The compound of claim 1, wherein: X is S, R.sup.1 is selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl and substituted C.sub.5-8-cycloalkenyl, R.sup.2, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.9 are H, R.sup.3 and R.sup.8 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkyl, substituted C.sub.1-30-alkyl and substituted C.sub.2-30-alkenyl, at each occurrence, are C.sub.1-30-alkyl, respectively, C.sub.2-30-alkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl and phenyl, and substituted C.sub.5-8-cycloalkyl and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl and phenyl.
8: A process for preparing the compound of claim 1, ##STR00044## the process comprising treating a compound of formula (2): ##STR00045## with a compound of formula:
R.sup.1O—C(O)-LG, to obtain the compound of formula (1): ##STR00046## wherein: X is O, S or NR.sup.10; R.sup.10 is H C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.1-30-alkynyl or C(O)—OR.sup.11; R.sup.1 and R.sup.11 are independently from each other selected from the group consisting of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, and substituted C.sub.5-8-cycloalkenyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently from each other selected from the group consisting of H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl, substituted S—C.sub.1-30-alkyl, C.sub.6-14-aryl, substituted C.sub.6-14-aryl, 5 to 15 membered heteroaryl, substituted 5 to 15 membered heteroaryl and halogen, or R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or, R.sup.8 and R.sup.9 together with the C-atoms, to which they are connected, form a 6 to 10 membered aromatic ring system, substituted 6 to 10 membered aromatic ring system, 5 to 12 membered heteroaromatic ring system or a substituted 5 to 12 membered heteroaromatic ring system; substituted C.sub.1-30-alkyl, substituted C.sub.2-30-alkenyl, substituted C.sub.2-30-alkynyl, substituted O—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, at each occurrence, are C.sub.1-30-alkyl, C.sub.1-30-alkenyl, C.sub.2-30-alkynyl, O—C.sub.1-30-alkyl, respectively, S—C.sub.1-30-alkyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.5-8-cycloalkyl, and substituted C.sub.5-8-cycloalkenyl, at each occurrence, are C.sub.5-8-cycloalkyl, respectively, C.sub.5-8-cycloalkenyl, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.1-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b, NR.sup.a—NR.sup.bR.sup.c, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; substituted C.sub.6-14-aryl, substituted 5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ring system, and substituted 5 to 12 membered heteroaromatic ring system, at each occurrence, are C.sub.6-14-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ring system, respectively, 5 to 12 membered heteroaromatic ring system, which are substituted with at least one substituent independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.5-6-cycloalkenyl, C.sub.6-10-aryl, 5 to 12 membered heteroaryl, OR.sup.a, OC(O)—R.sup.a, OC(O)—OR.sup.a, OC(O)—NR.sup.aR.sup.b, C(O)—R.sup.a, C(O)—OR.sup.a, C(O)—NR.sup.aR.sup.b, C(O)—NR.sup.a—NR.sup.bR.sup.c, C(O)—NR.sup.a—OR.sup.b, C(O)—NR.sup.a—C(O)—R.sup.b, C(O)—NR.sup.a—C(O)—OR.sup.b, C(O)—SR.sup.a, NR.sup.aR.sup.b NR.sup.a—NR.sup.bR, NR.sup.a—C(O)R.sup.b, NR.sup.a—C(O)—OR.sup.b, NR.sup.a—C(O)—NR.sup.bR.sup.c, SR.sup.a, S—C(O)—R.sup.a, halogen, CN, and NO.sub.2; at least one CH.sub.2-group, but not adjacent CH.sub.2-groups, of C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.1-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, substituted C.sub.5-8-cycloalkyl, C.sub.5-8-cycloalkenyl, substituted C.sub.5-8-cycloalkenyl, O—C.sub.1-30-alkyl, substituted O—C.sub.1-30-alkyl, S—C.sub.1-30-alkyl and substituted S—C.sub.1-30-alkyl, can be replaced by a linking group selected from the group consisting of O, S, NR.sup.12, CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR.sup.12—C(O), C(O)—NR.sup.12, OC(O)—NR.sup.12 and NR.sup.12—C(O)—O; R.sup.12 is H, C.sub.1-30-alkyl, substituted C.sub.1-30-alkyl, C.sub.2-30-alkenyl, substituted C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, substituted C.sub.1-30-alkynyl or C(O)—OR.sup.d; R.sup.a, R.sup.b, Re and R.sup.d are independently from each other and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.1-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6 cycloalkyl, C.sub.5-6-cycloalkenyl, C.sub.6-10-aryl, and 5 to 12 membered heteroaryl; and LG is a leaving group.
9: An electronic device, comprising the compound of claim 1.
10: The electronic device of claim 9, wherein the electronic device is an organic field effect transistor (OFET).
11: A semiconducting material, comprising the compound of claim 1.
Description
[0109]
[0110]
[0111]
[0112]
[0113]
[0114]
[0115]
[0116]
[0117]
[0118]
EXAMPLES
Example 1
Preparation of Compound 1a
[0119] ##STR00029##
Preparation of Compound 2a
[0120] 0.83 g (5 mmol) of dichloromaleimide and 1.25 g (10 mmol) of o-aminothiophenol were added to 30 ml of acetic acid, and stirred at 120° C. for 6 hours under N.sub.2. After cooling to r.t., the precipitate was isolated by filtration, washed with methanol and THF. Compound 2a (1.26 g) was used in the next step without further purification.
Preparation of Compound 1a
[0121] 215 mg (0.7 mmol) of compound 2a, 13 mg (0.1 mmol) of 4-dimethylaminopyridine, and 458 mg (2.1 mmol) of di-tert-butyl dicarbonate were added to 10 ml of THF, and stirred at r.t. overnight under N.sub.2. The precipitate was isolated with filtration, washed with tert-butylmethylether, yielding 232 mg (0.57 mmol; 81%) of compound 1a as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3). δ [ppm] 1.72 (s, 9H), 7.15 (t, 2H), 7.21-7.28 (m, 4H), 7.50 (d, 2H).
Example 2
Preparation of Compound 1b
[0122] ##STR00030##
Preparation of Compound 6a
[0123] To a solution of 9.85 g (60 mmol) of 4-pentylphenol in 70 ml of acetic acid was added 7.6 g of nitric acid dissolved in 20 ml of acetic acid dropwise with keeping the temperature in the range of 10-15° C. The reaction mixture was stirred at r.t. for 4 hours, and then poured to water and extracted with ethyl acetate. The organic phase was washed with NaHCO.sub.3aq and water, dried over MgSO.sub.4, and concentrated. Compound 6a was used in the next step without further purification.
Preparation of Compound 5a
[0124] To a solution of 10.5 g (50 mmol) of compound 6a, 15.1 g (135 mmol) of DABCO in 50 ml of DMF was added 7.73 g (63 mmol) of N,N-dimethylthiocarbamoyl chloride by portions. The reaction mixture was stirred at 70° C. for 3 hours, and then poured to water and acidified with 6N HCl. Compound 5a was extracted with ethyl acetate, washed with water, dried over MgSO.sub.4, and concentrated. The residue is purified by flash chromatography on silica gel with hexane and CH.sub.2Cl.sub.2 (1:1) as eluent, yielding 13.0 g (44 mmol; 88%) of compound 5a as a brown liquid. .sup.1H-NMR (CDCl.sub.3). δ [ppm]: 0.90 (t, 3H), 1.25-1.38 (m, 4H), 1.62-1.70 (m, 2H), 2.69 (t, 2H), 3.39 (s, 3H), 3.46 (s, 3H), 7.15 (d, 1H), 7.46 (d, 1H), 7.92 (s, 1H).
Preparation of Compound 4a
[0125] 12.7 g (43 mmol) of compound 5a was placed in a reaction vessel and heated at 210° C. with stirred under N.sub.2 for 3 hours. After cooling to r.t., 80 ml of THF was added. To the solution was added 5.31 g (95 mmol) of potassium hydroxide dissolved in 20 ml of methanol dropwise with cooled by an ice bath. The reaction mixture was stirred at r.t. for 30 min, and poured to ice, acidified with conc. HCl. Compound 4a was extracted with ethyl acetate, washed with water, dried over MgSO.sub.4, and concentrated. .sup.1H-NMR spectrum (CDCl.sub.3). δ [ppm]: 0.89 (t, 3H), 1.25-1.37 (m, 4H), 1.55-1.65 (m, 2H), 2.63 (t, 2H), 3.96 (s, 1H), 7.25 (d, 1H), 7.33 (d, 1H), 8.06 (s, 1H).
Preparation of Compound 3a
[0126] To a solution of 5.15 g (23 mmol) of compound 4a in 9 ml of conc HCl and 170 ml of acetic acid was added 18.0 g (275 mmol) of zinc by portions at 60° C. The reaction mixture was stirred at 60° C. overnight. After cooling to r.t., insoluble solid was removed by filtration. The filtrate was concentrated by a rotary evaporator and water was added to the residue, yielding a precipitate.
[0127] The precipitate was isolated by filtration, washed with ethanol. Compound 3b was obtained with a yield of 5.16 g (11 mmol; 99%) as a white solid. .sup.1H-NMR spectrum (DMSO-d.sub.6). δ [ppm]: 0.83 (t, 6H), 1.18-1.32 (m, 8H), 1.42-1.53 (m, 4H), 2.39 (t, 4H), 5.72 (br s, 4H), 6.63 (d, 2H), 6.83 (s, 2H), 7.18 (d, 2H).
Preparation of Compound 2b
[0128] To 300 ml of acetic acid 7.26 g (16 mmol) of compound 3a and 2.66 g (16 mmol) of 3,4-dichloromaleimide were added and stirred at 140° C. overnight. After removing the solvent by a rotary evaporator, the residue was suspended in water. The solid was isolated by filtration, washed with methanol. Compound 2b was obtained as an orange solid. Compound 2b was used in the next step without further purification.
Preparation of Compound 1b
[0129] To 30 ml of THF 1.34 g (3 mmol) of compound 2b, 55 mg (0.45 mmol) of 4-dimethylaminopyridine, and 1.96 g (9 mmol) of di-tert-butyl dicarbonate were added, and stirred at r.t. overnight under N.sub.2. The product was extracted with CH.sub.2Cl.sub.2, washed with water, dried over MgSO.sub.4, and concentrated. The residue was purified by recrystallization from ethyl acetate and hexane (1:1) solution, yielding 1.06 g (1.9 mmol; 65%) of compound 1b as an orange solid. .sup.1H-NMR (CDCl.sub.3). δ [ppm]: 0.89 (t, 6H), 1.28-1.39 (m, 8H), 1.57-1.68 (m, 4H), 1.72 (s, 9H), 2.59 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).
Example 3
Preparation of Compound 1c
[0130] ##STR00031##
[0131] Compound 1c is prepared in analogy to compound 1b in example 2, starting from 4-heptylphenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) δ [ppm]: 0.88 (t, 6H), 1.20-1.38 (m, 16H), 1.55-1.63 (m, 4H), 1.71 (s, 9H), 2.59 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).
Example 4
Preparation of Compound 1d
[0132] ##STR00032##
[0133] Compound 1d is prepared in analogy to compound 1b in example 2, starting from 4-dodecylphenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.88 (t, 6H), 1.21-1.36 (m, 36H), 1.53-1.63 (m, 4H), 1.72 (s, 9H), 2.58 (t, 4H), 6.98 (d, 2H), 7.11 (d, 2H), 7.32 (s, 2H).
Example 5
Preparation of Compound
[0134] ##STR00033##
[0135] Compound 1e is prepared in analogy to compound 1b in example 2, starting from 4-tetradecylphenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.87 (t, 6H), 1.20-1.33 (m, 44H), 1.60-1.70 (m, 4H), 1.72 (s, 9H), 2.59 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).
Example 6
Preparation of Compound 1f
[0136] ##STR00034##
[0137] Compound 1f is prepared in analogy to compound 1b in example 2, starting from 4-docosyl-phenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.86 (t, 6H), 1.20-1.35 (m, 76H), 1.56-1.63 (m, 4H), 1.72 (s, 9H), 2.58 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.32 (s, 2H).
Example 7
Preparation of Compound 1g
[0138] ##STR00035##
[0139] Compound 1g is prepared in analogy to compound 1b in example 2, starting from 4-[4-pentylcyclohexyl)-phenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.89 (t, 6H), 0.98-1.10 (m, 4H), 1.18-1.38 (m, 18H), 1.38-1.52 (m, 4H), 1.72 (s, 9H), 1.83-1.92 (m, 8H), 2.40-2.49 (m, 2H), 7.02 (d, 2H), 7.12 (d, 2H), 7.35 (s, 2H).
Example 8
Preparation of Compound 1h
[0140] ##STR00036##
[0141] Compound 1h is prepared in analogy to compound 1b in example 2, starting from 4-dodecylphenol instead of from 4-pentylphenol, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.85 (t, 3H), 1.21-1.37 (m, 18H), 1.60-1.68 (m, 11H), 2.67 (t, 2H), 7.22 (d, 1H), 7.29 (d, 1H), 7.36-7.48 (m, 5H), 7.61-7.67 (m, 3H), 7.75 (s, 1H).
Example 9
Preparation of Compound 1i
[0142] ##STR00037##
[0143] Compound 1i is prepared in analogy to compound 1b in example 2, using di-(2-methyl-sec-butyl) dicarbonate instead of di-tert-butyl dicarbonate, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.89 (t, 6H), 1.12 (t, 3H), 1.25-1.38 (m, 8H), 1.55-1.64 (m, 4H), 1.70 (s, 6H), 1.99 (q, 2H), 2.59 (t, 4H), 6.98 (d, 2H), 7.11 (d, 2H), 7.33 (s, 2H).
Example 10
Preparation of Compound 1j
[0144] ##STR00038##
[0145] Compound 1j is prepared in analogy to compound 1b in example 2, using di-(1-methylcyclohexyl) dicarbonate instead of di-tert-butyl dicarbonate, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.80-0.95 (m, 6H), 1.10-1.65 (m, 21H), 1.95-2.08 (m, 2H), 2.40-2.49 (m, 2H), 2.58 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.34 (s, 2H).
Example 11
Preparation of Compound 1k
[0146] ##STR00039##
[0147] Compound 1k is prepared in analogy to compound 1b in example 2, using di-(1-ethyl-1,5-dimethyl-hexyl) dicarbonate instead of di-tert-butyl dicarbonate, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.86-0.91 (m, 12H), 1.07 (t, 3H), 1.20-1.37 (m, 12H), 1.47-1.67 (m, 8H), 1.85-2.13 (m, 4H), 2.58 (t, 4H), 6.97 (d, 2H), 7.11 (d, 2H), 7.32 (s, 2H).
Example 12
Preparation of Compound 1l
[0148] ##STR00040##
[0149] Compound 11 is prepared in analogy to compound 1b in example 2, using di-(1-isopropyl-4-methyl-cyclohex-3-en-1-yl) dicarbonate instead of di-tert-butyl dicarbonate, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.80-1.72 (m, 27H), 1.75-1.87 (m, 1H), 1.92-2.03 (m, 1H), 2.27-2.45 (m, 2H), 2.58 (t, 4H), 2.65-2.79 (m, 1H), 2.92-3.02 (m, 1H), 5.32 (s, 1H), 6.97 (d, 2H), 7.12 (d, 2H), 7.29 (s, 2H).
Example 13
Preparation of Compound 1m
[0150] ##STR00041##
[0151] Compound 1m is prepared in analogy to compound 1b in example 2, using di-(1,1-dimethylallyl) dicarbonate instead of di-tert-butyl dicarbonate, and is obtained as an orange solid. .sup.1H-NMR spectrum (CDCl.sub.3) d [ppm]: 0.82-0.95 (m, 6H), 1.20-1.40 (m, 12H), 1.52-1.67 (m, 4H), 1.79 (s, 6H), 2.59 (t, 4H), 5.23 (d, 1H), 5.51 (d, 1H), 6.28 (dd, 1H), 6.98 (d, 2H), 7.11 (d, 2H), 7.33 (s, 2H).
Example 14
Preparation of Field-Effect Transistors Comprising Compounds 1a, 1b, 1e, Respectively, 1g as Semiconducting Material
[0152] 30 nm ALD Al.sub.2O.sub.3 coated, highly doped silicon wafers were thoroughly cleaned with acetone and isopropanol and after a short oxygen plasma treatment treated with a solution of decyl-phosphonic acid in isopropanol. The compound 1a, 1b, 1e, respectively, 1g was thermally evaporated in high vacuum (<10.sup.−5 mbar). A 50 nm-thick of Au layer for source and drain electrodes was deposited though a shadow mask to give top contact OFET devices. The channel width (W) was 500 μm and channel length (L) was 100 μm.
[0153] All electrical measurements were performed in ambient air in the dark using a B1500 Agilent parameter analyzer.
[0154] In
[0155] In
[0156] In
[0157] In
[0158] In
[0159] In
[0160] In
[0161] In
[0162] The field effect transistors comprising 1a, 1b, 1e, respectively, 1g showed typical p-type characteristics.
[0163] The charge-carrier mobility (μ) was extracted in the saturation regime from the slope of (I.sub.DS).sup.1/2 versus V.sub.GS using the equation p=2L/(W*C.sub.i)*(dl.sub.DS.sup.1/2/dV.sub.GS).sup.2, wherein L is the channel length, W is the channel width, C.sub.i is the capacitance per unit area of the dielectric layer, I.sub.DS is the drain-source current, and V.sub.GS is the gate-source voltage.
[0164] The threshold voltage (V.sub.th) was extracted from the intersection of the linear extrapolation of the I.sub.DS.sup.1/2 versus V.sub.GS plot with the V.sub.GS axis.
[0165] The results are depicted in table 1
TABLE-US-00001 TABLE 1 Compound V.sub.th [V] μ [cm.sup.2/Vs] I.sub.on/off 1a −6.9 0.13 1E4 1b −4.5 0.68 7E4 1e −3.9 0.23 2E6 1g −6.5 0.008 4E4
Example 15
[0166] The Solubility of the Compounds 1a, 1b, 1c and 1d at 25° C. were Compared to the Solubility of the Compound of Formula
##STR00042##
[0167] The results are outlined in table 2
TABLE-US-00002 TABLE 2 Compound DMF THF clorobenzene CHCl.sub.3 2a (comparative) <1 mg/mL <1 mg/mL <1 mg/mL <1 mg/mL 1a 1 to 5 mg/mL 1 to 5 mg/mL 5 to 10 mg/mL 5 to 10 mg/mL 1b <1 mg/mL >10 mg/mL >10 mg/mL >10 mg/mL 1c <1 mg/mL >10 mg/mL >10 mg/mL >10 mg/mL 1d >10 mg/mL >10 mg/mL >10 mg/mL >10 mg/mL
Example 16
Preparation of Field-Effect Transistors Comprising Compound 1b as Semiconducting Material
[0168] SiO.sub.2/Si substrates were thoroughly cleaned with piranha solution, ultrapure water, followed by isopropanol, and the substrates were functionalized with octadecyltrichlorosilane (OTS) from solution. A thin film of compound 1b was formed on the OTS-treated SiO.sub.2/Si substrate by spin coating a 5 mg/ml solution of compound 1b in CHCl.sub.3 at 4000 rpm for 30 sec, and annealed at 200° C. for 10 min on a hot-plate. On top of the organic thin film, Au layer was deposited through a shadow mask as source and drain electrodes to give top contact OFET devices. The channel width (W) was 3 mm and channel length (L) was 50 μm.
[0169] All electrical measurements are performed in ambient air in the dark using a Keithley 4200 parameter analyzer.
[0170] In
[0171] In
[0172] The field effect transistors comprising 1b showed typical p-type characteristics.
[0173] To record the transfer curve the drain-source voltage (V.sub.DS) was held to −80 V. The charge-carrier mobility (p) was extracted in the saturation regime from the slope of (I.sub.DS).sup.1/2 versus V.sub.GS using the equation p=2L/(W*C.sub.i)*(dl.sub.DS.sup.1/2/dV.sub.GS).sup.2, wherein L is the channel length, W is the channel width, C.sub.i is the capacitance per unit area of the dielectric layer, I.sub.DS is the drain-source current, and V.sub.GS is the gate-source voltage.
[0174] The threshold voltage (V.sub.th) was extracted from the intersection of the linear extrapolation of the I.sub.DS.sup.1/2 versus V.sub.GS plot with the V.sub.GS axis.
[0175] The results are depicted in table 3
TABLE-US-00003 TABLE 3 Compound V.sub.th/V μ/cm.sup.2/Vs I.sub.on/off Compound 1b −9.0 0.022 3E5