Mesogenic (1R,4R)ꢀ2ꢀarylideneꢀpꢀmenthanꢀ3ꢀones Russ.Chem.Bull., Int.Ed., Vol. 52, No. 11, November, 2003 2417
1.66 (q, 2 H, ArCH2CH2); 1.80 and 1.90 (both m, 4 H, C(5)H2,
C(6)H2); 2.25 (m, 1 H, H(4)); 2.57 (sept.d, 1 H, H(8)); 2.67 (t,
2 H, ArCH2, J = 7.6 Hz); 3.44 (m, 1 H, H(1)); 7.12 (s, 1 H,
=CH); 7.25, 7.30, 7.43, 7.58, 7.73, and 8.25 (all d, 2 H each,
1,4ꢀsubstituted benzene rings, J = 8.3—8.6 Hz).
=CH); 6.98, 7.29, 7.45, 7.60, 7.65, and 8.16 (all d, 2 H each,
1,4ꢀsubstituted benzene rings, J = 8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀhexadecyloxybenzoate (3e). The yield was
75%. Found (%): C, 81.55; H, 9.19. C46H62O4. Calculated (%):
C, 81.37; H, 9.20. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J =
6.7 Hz); 0.91 and 0.97 (both d, 3 H each, C(9)H3, C(10)H3, J =
7.1 Hz); 1.25—1.51 (m, 29 H, CAlkH2, C(7)H3); 1.79—1.94 (m,
6 H, C(5)H2, C(6)H2, OCH2CH2); 2.26 (m, 1 H, H(4)); 2.58
(sept.d, 1 H, H(8)); 3.49 (m, 1 H, H(1)); 4.05 (t, 2 H, OCH2,
J = 6.5 Hz); 7.15 (s, 1 H, =CH); 6.98, 7.29, 7.45, 7.60, 7.65, and
8.16 (all d, 2 H each, 1,4ꢀsubstituted benzene rings, J =
8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀnonylbenzoate (3f). The yield was 84%.
Found (%): C, 83.06; H, 8.66. C39H48O3. Calculated (%):
C, 82.94; H, 8.57. MS, m/z: 564 [M]+, 333, 231, 131, 91.
1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J = 6.9 Hz); 0.91, 0.98, and
1.23 (all d, 3 H each, C(10)H3, C(9)H3, C(7)H3, J = 7.2 Hz);
1.25—1.35 (m, 12 H, CAlkH2); 1.66 (q, 2 H, ArCH2CH2);
1.75—2.00 (m, 4 H, C(5)H2, C(6)H2); 2.26 (m, 1 H, H(4)); 2.57
(sept.d, 1 H, H(8)); 2.71 (t, 2 H, ArCH2, J = 7.6 Hz); 3.49 (m,
1 H, H(1)); 7.16 (s, 1 H, =CH); 7.29, 7.33, 7.45, 7.61, 7.65, and
8.13 (all d, 2 H each, 1,4ꢀsubstituted benzene rings, J =
8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀdecylbenzoate (3g). The yield was 85%.
Found (%): C, 83.14; H, 8.81. C40H50O3. Calculated (%):
C, 83.00; H, 8.71. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J =
6.9 Hz); 0.91, 0.98, and 1.24 (all d, 3 H each, C(10)H3, C(9)H3,
C(7)H3, J = 7.2 Hz); 1.25—1.33 (m, 14 H, CAlkH2); 1.66 (q,
2 H, ArCH2CH2); 1.75—2.00 (m, 4 H, C(5)H2, C(6)H2); 2.26
(m, 1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 2.70 (t, 2 H, ArCH2,
J = 7.6 Hz); 3.48 (m, 1 H, H(1)); 7.16 (s, 1 H, =CH); 7.29, 7.33,
7.45, 7.61, 7.65, and 8.13 (all d, 2 H each, 1,4ꢀsubstituted benꢀ
zene rings, J = 8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀhexadecylbenzoate (3h). The yield was
75%. Found (%): C, 83.40; H, 9.31. C46H62O3. Calculated (%):
C, 83.33; H, 9.43. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J =
6.9 Hz); 0.91 and 0.98 (both d, 3 H each, C(9)H3, C(10)H3, J =
7.2 Hz); 1.24—1.32 (m, 29 H, CAlkH2, C(7)H3); 1.66 (q, 2 H,
ArCH2CH2); 1.75—2.00 (m, 4 H, C(5)H2, C(6)H2); 2.26 (m,
1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 2.70 (t, 2 H, ArCH2, J =
7.6 Hz); 3.48 (m, 1 H, H(1)); 7.16 (s, 1 H, =CH); 7.29, 7.33,
7.45, 7.61, 7.65, and 8.13 (all d, 2 H each, 1,4ꢀsubstituted benꢀ
zene rings, J = 8.3—8.6 Hz).
(3R,6R)ꢀ4ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)phenyl 4´ꢀoctylbiphenylꢀ4ꢀcarboxylate (2b). The yield was
26.5
68%, [α]D
–95.1 (c 3.3, CHCl3). Found (%): C, 82.81;
H, 8.49. C38H46O3. Calculated (%): C, 82.87; H, 8.42. MS,
1
m/z: 550 [M]+, 522, 386, 293, 265, 194, 166, 152. H NMR, δ:
0.89 (t, 3 H, CAlkH3, J = 6.6 Hz); 0.91, 0.98, and 1.24 (all d,
3 H each, C(10)H3, C(9)H3, C(7)H3, J = 7.0 Hz); 1.29, 1.34
(both m, 10 H, CAlkH2); 1.66 (q, 2 H, ArCH2CH2); 1.80, 1.90
(both m, 4 H, C(5)H2, C(6)H2); 2.25 (m, 1 H, H(4)); 2.57
(sept.d, 1 H, H(8)); 2.67 (t, 2 H, ArCH2, J = 7.6 Hz); 3.44 (m,
1 H, H(1)); 7.12 (s, 1 H, =CH); 7.25, 7.30, 7.43, 7.58, 7.73, and
8.25 (all d, 2 H each, 1,4ꢀsubstituted benzene rings, J =
8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀhexyloxybenzoate (3a). The yield was
74%. Found (%): C, 80.20; H, 7.88. C36H42O4. Calculated (%):
C, 80.26; H, 7.86. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J =
6.6 Hz); 0.91, 0.97, and 1.24 (all d, 3 H each, C(10)H3, C(9)H3,
C(7)H3, J = 7.0 Hz); 1.27 and 1.48 (both m, 6 H, CAlkH2);
1.79—1.94 (m, 6 H, C(5)H2, C(6)H2, OCH2CH2); 2.26 (m,
1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 3.49 (m, 1 H, H(1)); 4.05
(t, 2 H, OCH2, J = 6.5 Hz); 7.15 (s, 1 H, =CH); 6.97, 7.29,
7.45, 7.60, 7.65, and 8.16 (all d, 2 H each, 1,4ꢀsubstituted benꢀ
zene rings, J = 8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀheptyloxybenzoate (3b). The yield was
65%. Found (%): C, 80.52; H, 8.12. C37H44O4. Calculated (%):
C, 80.40; H, 8.02. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3, J =
6.6 Hz); 0.91, 0.97, and 1.24 (all d, 3 H each, C(10)H3, C(9)H3,
C(7)H3, J = 7.0 Hz); 1.27 and 1.48 (both m, 8 H, CAlkH2);
1.79—1.94 (m, 6 H, C(5)H2, C(6)H2, OCH2CH2); 2.26 (m,
1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 3.49 (m, 1 H, H(1)); 4.05
(t, 2 H, OCH2, J = 6.5 Hz); 7.15 (s, 1 H, =CH); 6.97, 7.29,
7.45, 7.60, 7.65, and 8.16 (all d, 2 H each, 1,4ꢀsubstituted benꢀ
zene rings, J = 8.3—8.6 Hz).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀoctyloxybenzoate (3c). The yield was 74%,
26.5
[α]D
–116 (c 2.0, CHCl3). Found (%): C, 80.66; H, 8.19.
C
38H46O4. Calculated (%): C, 80.53; H, 8.18. MS, m/z:
567 [M]+, 386, 333, 233, 121. 1H NMR, δ: 0.89 (t, 3 H, CAlkH3,
J = 6.8 Hz); 0.91, 0.97, and 1.24 (all d, 3 H each, C(10)H3,
C(9)H3, C(7)H3, J = 7.0 Hz); 1.27—1.52 (m, 10 H, CAlkH2);
1.79—1.94 (m, 6 H, C(5)H2, C(6)H2, OCH2CH2); 2.26 (m,
1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 3.49 (m, 1 H, H(1)); 4.05
(t, 2 H, OCH2, J = 6.5 Hz); 7.15 (s, 1 H, =CH); 6.97, 7.29,
7.45, 7.60, 7.65, and 8.16 (all d, 2 H each, 1,4ꢀsubstituted benꢀ
zene rings, J = 8.3—8.6 Hz).
We thank Prof. J. Goodby for helpful discussion.
This study was financially supported by the Internaꢀ
tional Association for the Promotion of Cooperation with
Scientists from the Newly Independent States of the
Former Soviet Union (INTAS, Grants 1997ꢀ1730 and
YSF 00ꢀ153).
(3R,6R)ꢀ4´ꢀ(3ꢀIsopropylꢀ6ꢀmethylꢀ2ꢀoxocyclohexylideneꢀ
methyl)biphenylꢀ4ꢀyl 4ꢀnonyloxybenzoate (3d). The yield was
80%. Found (%): C, 80.50; H, 8.27. C39H48O4. Calculated (%):
C, 80.65; H, 8.33. MS, m/z: 580 [M]+, 333, 247, 121. 1H NMR,
δ: 0.89 (t, 3 H, CAlkH3, J = 6.7 Hz); 0.91, 0.97, and 1.24 (all d,
3 H each, C(10)H3, C(9)H3, C(7)H3, J = 7.0 Hz); 1.25—1.51
(m, 12 H, CAlkH2); 1.79—1.94 (m, 6 H, C(5)H2, C(6)H2,
OCH2CH2); 2.26 (m, 1 H, H(4)); 2.58 (sept.d, 1 H, H(8)); 3.49
(m, 1 H, H(1)); 4.05 (t, 2 H, OCH2, J = 6.5 Hz); 7.15 (s, 1 H,
References
1. L. A. Kutulya, Dr. Sc. (Chem.) Thesis, Institute for Single
Crystals of the National Academy of Sciences of Ukraine,
Kharkov, 1992, 461 pp. (in Russian).