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Full PaperReceived: 5 May 2009 Revised: 5 August 2009 Accepted: 5 August 2009 Published online in Wiley Interscience 16 September 2009

(www.interscience.com) DOI 10.1002/aoc.1548

Synthesis of 4-substituted styrene compoundsvia palladium catalyzed Suzuki–Miyaurareaction using bidentate Schiff base ligandsYan Liu and Jinqu Wang∗

Air-stable symmetric Schiff base have been synthesized and proved to be efficient ligands for Suzuki–Miyaura reaction betweenaryl bromides and arylboronic acids using PdCl2(CH3CN)2 as palladium source under aerobic conditions. The coupling reactionproceeded smoothly using N,N-bis(anthracen-9-ylmethylene)benzene-1,2-diamine (L7) as ligand to provide 4-substitutedstyrene compounds in good yields. Copyright c© 2009 John Wiley & Sons, Ltd.

Keywords: Suzuki–Miyaura reaction; Schiff base; 4-substituted styrene compounds; synthesis

Introduction

Substituted styrene starting materials have been extensivelyused in both specialty chemical and polymer synthesis. Notonly can styrene be used in transformations such as olefinmetathesis[1] or Heck-type reactions[2] but also the alkene canbe employed as a platform on which to introduce a variety offunctionalities.[3 – 8] In regard to polymer synthesis, a multitudeof transformations exist for polymerizing styrene.[9 – 13] Theutility of such transformations has dramatically increased thedemand for facile routes to substituted styrene. Transition metal-mediated cross-coupling reactions provide efficient routes tofunctionalized styrene that complement traditional methods suchas dehydration,[14,15] Grignard reaction[16] or Hoffman elimination,all of which are incompatible with sensitive functional groups. TheSuzuki–Miyaura reaction of organoboron compounds is nowadaysthe most widely used cross-coupling reaction because of its lowtoxicity and wide functional group tolerance,[17 – 21] and has beenextensively used in the synthesis of pharmaceuticals,[22,23] andliquid crystal compounds.[24 – 29] Since the general procedureswere discovered, efforts have been made towards increasingthe substrate scope and efficiency. Therefore, designing ligandswith appropriate features and great diversity is crucial in dealingwith the challenging substrates in this area. For many years,phosphine ligands have been most commonly employed for thereaction. However, these types of ligands are generally eitherair/moisture sensitive or expensive, which places significantlimits on their synthetic applications. Therefore, N-ligands,which are inexpensive, easy to access and stable, have gainedmajor attention, such as Schiff bases,[30 – 36] aryloximes,[37,38]

arylimines,[39 – 45] N-acylamidines[46], guanidine[47] and simpleamines.[48 – 53] As a part of our ongoing efforts to develop efficientmethods for the synthesis of substituted styrene compounds,herein we report the results of palladium-catalyzed couplingreaction between aryl bromides and arylboronic acids to prepare4-substituted styrene compounds by using symmetric Schiff baseas ligands in air.

H2N NH2+ R CHO N N

R R

EtOH

L1: R = C6H5

L2: R = (4-Cl)C6H4

L3: R = (4-OMe)C6H4

L4: R = (2-OMe)C6H4

L5: R = (3-OMe,4-OMe)C6H4

N N

L7 L6: R =

Scheme 1. Synthesis of L1 –L7 .

Results and Discussion

Ligands 1–7 were prepared by reaction of 1, 2-diamine with 2.0equiv substituted aromatic aldehyde of in ethanol or MeOH/DMF,they were used without further purification, and their structureswere established by 1H NMR (Scheme 1). Initially, we focused onoptimization of the reaction conditions of the coupling reactionof 4-bromostyrene with phenylboronic acid. The base usuallyplays an important role in the Suzuki–Miyaura reaction (Table 1).K3PO4·3H2O gave the best results at a 40% yield (Table 1, entry6). The contrast in yield for simple changes in base was moreprofound for K3PO4·3H2O and K3PO4 (40 vs 30%, entries 5 and 6).When K2CO3 and CH3ONa were used as base, the yield of productwas reduced to 29 and 31% respectively (Table 1, entries 3 and 4),but Na2CO3 and NaOH were no more efficient (Table 1, entries 1and 2).

To evaluate the efficiency of PdCl2(CH3CN)2 –ligands in theSuzuki–Miyaura reaction, the coupling of 4-bromostyrene withphenylboronic acid was tested, and the results are summarizedin Table 2. Among these ligands investigated, L1 –L6 showed low

∗ Correspondence to: Jinqu Wang, State Key Laboratory of Fine Chemicals, Insti-tute of Adsorption and Inorganic Membrane, Dalian University of Technology,158 Zhongshan Rd, Dalian 116012, China. E-mail: wangjinqu@hotmail.com

State Key Laboratory of Fine Chemicals, Institute of Adsorption and InorganicMembranes, Dalian 116012, People’s Republic of China

Appl. Organometal. Chem. 2009 , 23, 476–480 Copyright c© 2009 John Wiley & Sons, Ltd.

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Table 1. Effect of base on the Suzuki–Miyaura reactiona

Entry Base Yield (%)b

1 Na2CO3 trace

2 NaOH trace

3 K2CO3 29

4 MeONa 31

5 K3PO4 30

6 K3PO4·3H2O 40

a Reaction conditions: p-bromostyrene (0.50 mmol), phenylboronicacid (0.75 mmol), PdCl2(CH3CN)2 (0.50 mmol%), L6 (0.75 mmol%), base(1.50 mmol), toluene (2.0 mL), 80 ◦C, reaction time 10 h.b Isolated yield.

Table 2. Effect of ligand on the Suzuki–Miyaura reactiona

Entry Ligand Yield (%)b

1 – 5

2 L1 30

3 L2 35

4 L3 48

5 L4 19

6 L5 16

7 L6 40

8 L7 75

9 L7 66c

10 L7 70d

a Reaction conditions: p-bromostyrene (0.50 mmol), phenylboronicacid (0.75 mmol), PdCl2(CH3CN)2 (0.50 mmol%), L1 –L7 (0.75 mmol%),K3PO4·3H2O (1.50 mmol), toluene (2.0 mL), 80 ◦C, reaction time 10 h.b Isolated yield.c Pd(OAc)2 as Pd source.d Pd2(dba)3·CHCl3 as Pd source.

efficiency, which gave the coupling product in 16–48% yield(Table 2, entries 2–7). L7 showed good efficiency, and gave thecoupling product in 75% yield (Table 2, entry 8), but only a 5%yield was obtained without any ligands (Table 2, entry 1). WithPd(OAc)2 and Pd2(dba)3·CHCl3 as Pd sources, respectively, and L7

as ligand, the coupling product was also obtained in satisfactoryyields (66 and 70%, Table 2, entries 9 and 10).

Thus, the optimized reaction conditions for the Suzuki–Miyaurareaction were PdCl2(CH3CN)2 (0.50% mmol), L7 (0.75% mmol)and K3PO4·3H2O (1.50 mmol) in toluene at 80 ◦C. Next weexplored the scope of the coupling reaction in the presenceof a variety of functional groups. As shown in Table 3, theSuzuki–Miyaura proceeds with good to excellent yields in thepresence of electron-poor functional groups including ketonesand aldehydes (80–92%, Table 3, entries 1, 3, 4, 5, 7, 9). Howeverthe electron-rich aryl bromide, such as 4-bromoanisole reactedwith 4-vinylphenylboronic acid to give moderate yields at the sameconditions (68 and 70%, Table 3, entries 2 and 6). The aryl bromidecontaining ortho substituent reacted to prepare the desired biarylproduct in moderate yield (51%, Table 3, entry 8), but electron-poor or -rich arylboronic acids reacted with p-bromostyrene togive lower yields (40 and 47%, Table 3, entries 11, 12). The catalystsystem was also used to synthesize liquid crystal compoundsand obtained good yields at the optimized reaction conditions

(88–92%, Table 3, entries 13–15). In addition, aryl iodide such as4-iodoacetophenone reacted with 4-vinylphenylboronic acid togive excellent yield at 80 ◦C (90%, Table 3, entry 16). However, arylchlorides such as 4-chloroacetophenone resulted in no reaction inthe same conditions (Table 3, entry 17).

Conclusion

In conclusion, symmetric Schiff base compounds (L1 –L7) were eas-ily prepared from commercially available reagents and show highair-, moisture- and thermostability. We successfully synthesized 4-substituted styrene compounds by Pd-catalyzed Suzuki–Miyaurareaction of various aryl bromides with arylboronic acids using L7 asligand in air and provided a practical procedure for the synthesisof liquid crystal compounds.

Experimental

General

1H and 13C NMR spectra were recorded on a 400 MHz spectrometerwith the chemical shift values reported in δ units (ppm) relativeto an internal standard (TMS). The open-bed chromatography wascarried out on silica gel (200–300 mesh, Qingdao Haiyang) usinggravity flow. The column was packed with slurries made from theelution solvent.

Synthesis of L1 –L7

L1 –L5 were synthesized according to the literature method.[54]

L6 and L7 were also synthesized according to the literaturemethod.[55] They were used without further purification.

Dibenzylidene ethylenediamine (L1)[54]

Yield: 67%. Yellow solid. M.p. 150–152 ◦C. 1H NMR (400 MHz,CDCl3): δ 8.29 (s, 2H, H2 and H2′), 7.71–7.68 (m, 4H, H3 and H3′),7.40–7.38 (m, 6H, H4, H4′ and H5, H5′), 3.98 (s, 4H, H1 and H1′).

N,N-bis(4-chlorobenzylidene)ethane-1,2-diamine (L2)[54]

Yield: 83%. White solid. M.p. 146–147 ◦C. 1H NMR (400 MHz, CDCl3):δ 8.23 (s, 2H, H2 and H2′), 7.63 (d, J = 8.8 Hz, 4H, H3 and H3), 7.36(d, J = 8.4 Hz, 4H, H4 and H4′), 3.96 (s, 4H, H1 and H1′).

N,N-bis(4-methoxybenzylidene)ethane-1,2-diamine (L3)[54]

Yield: 78%. Yellow solid. M.p. 103–104 ◦C. 1H NMR (400 MHz,CDCl3): δ 8.21 (s, 2H, H2 and H2′), 7.63 (d, J = 8.8 Hz, 4H, H3 andH3′), 6.89 (d, J = 8.8 Hz, 4H, H4 and H4′), 3.91 (s, 4H, H1 andH1′),3.77 (s, 6H, H5 and H5′).

N,N-bis(2-methoxybenzylidene)ethane-1,2-diamine (L4)[54]

Yield: 80%. White solid. M.p. 117–118 ◦C. 1H NMR (400 MHz, CDCl3):δ 8.71 (s, 2H, H2 and H2′), 7.92 (d, J = 7.6 Hz, 2H, H3 and H3′), 7.35(t, J = 7.2, 8.4 Hz, 2H, H5 and H5′), 6.96 (t, J = 7.2, 7.6 Hz, 2H, H6and H6′), 6.87 (d, J = 8.4 Hz, 2H, H4 and H4′), 3.96 (s, 4H, H1 andH1′), 3.80 (s, 6H, H7 and H7′).

Appl. Organometal. Chem. 2009, 23, 476–480 Copyright c© 2009 John Wiley & Sons, Ltd. www.interscience.wiley.com/journal/aoc

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Y. Liu and J. Wang

Table 3. Suzuki–Miyaura reaction of aryl halides and arylboronic acidsa

Entry R1 X R2 Product Yield (%)b

1 4-Ethenyl (1a) Br 4-F (2a) 3a 81

2 1a Br 4-Me (2b) 3b 70

3 1a Br 4-Ethenyl (2c) 3c 92

4 1a Br 4-CHO (2d) 3d 80

5 1a Br 4-COMe (2e) 3e 87

6 1a Br 4-OMe (2f) 3f 68

7 1a Br 3,4-Difluoro (2g) 3g 86

8 1a Br 2,4,5-Trifluoro (2h) 3h 51

9 1a Br 3,4,5-Trifluoro (2i) 3i 87

10 4-H (1b) Br 4-Ethenyl (2c) 3j 75

11 4-Me (1c) Br 4-Ethenyl (2c) 3b 40

12 4-F (1d) Br 4-Ethenyl (2c) 3f 47

13 1a Br 4,4′-Propyl-cyclohexyl (2h) 3k 92

14 1a Br 4,4′-Pentyl-cyclohexyl (2i) 3l 90

15 1a Br 4,4′-Pentyl-bicyclohexyl (2n) 3m 88

16 1a I 4-COMe (2l) 3e 90

17 1a Cl 4-COMe (2m) 3e 0

a Reaction conditions: aryl halides (0.50 mmol), arylboronic acids (0.75 mmol), PdCl2(CH3CN)2 (0.50 mmol%), L7 (0.75 mmol%), K3PO4·3H2O(1.50 mmol), toluene (2.0 mL), 80 ◦C, reaction time 10 h.b Isolated yield.

N,N-bis(3, 4-dimethoxybenzylidene)ethane-1,2-diamine (L5)[55,57]

Yield: 75%. White solid. M.p. 155–156 ◦C. 1H NMR (400 MHz, CDCl3):δ 8.20 (s, 2H, H2 and H2′), 7.40 (s, 2 H, H3 and H3′), 7.11 (d, J = 8.4 Hz,2H, H5 and H5′), 6.86 (d, J = 8.0 Hz, 2H, H4 and H4′), 3.93 (s, 10H,H1, H1′ and H6, H6′), 3.91 (s, 6H, H7 and H7′).

N,N-bis(9-anthrylmethylene)ethane-1,2-diamine (L6)[56]

Yield: 92%.Yellow solid. M.p. 228–230 ◦C. 1H NMR (400 MHz,CDCl3): δ 9.50 (s, 2H, H2 and H2′), 8.46 (s, 2H, H7 and H7′),8.42 (d, J = 8.8 Hz, 4H, H3 and H3′), 7.96 (d, J = 8.4 Hz, 4H, H4 andH4′), 7.36 (dd, J = 7.2, 8.0 Hz, 4H, H5 and H5′), 7.12 (dd, J = 7.6,8.0 Hz, 4H, H6 and H6′), 4.52 (s, 4H, H1 and H1′).

N,N-bis(9-anthrylmethylene)benzene-1,2-diamine (L7)

Yield: 89%. Yellow solid. M.p. 168–170 ◦C. 1H NMR (400 MHz,CDCl3): δ 9.80 (s, 2H, H3 and H3′), 8.85 (d, J = 9.2 Hz, 4H, H4 andH4′), 8.50 (s, 2H, H8 and H8′), 7.98 (d, J = 8.8 Hz, 4H, H5 and H5′),7.50–7.43 (m, 4H, H6 and H6′), 7.37 (dd, J = 7.2, 7.6 Hz, 4H, H7 andH7′), 7.11 (dd, J = 7.6, 7.6 Hz, 4H, H1, H1′ and H2, H2′). 13C NMR(100 MHz, CDCl3): δ 121.2 (C3 and C3′), 125.1 (C13 and C13′), 125.5(C1 and C1′),126.9 (C9 and C9′), 127.2 (C8 and C8′), 128.9 (C10 andC10′), 130.7 (C7 and C7′), 130.8 (C5 and C5′), 131.4 (C2 and C2′),135.4 (C2 and C2′), 145.7 (C12 and C12′), 161.8 (C4 and C4′). IR (KBr,cm−1): 1623 (C N). Elemental anal. calcd for C36H24N2: C, 89.23;H, 4.99; N, 5.78. Found, C, 89.00; H, 5.00; N, 5.80.

Typical Suzuki–Miyaura reaction of aryl bromidesand arylboronic acids

To the solution of L7 (0.75% mmol) and PdCl2(CH3CN)2 (0.50%mmol) in toluene (2.0 mL) were added aryl bromide (0.50 mmol),

arylboronic acid (0.75 mmol) and K3PO4·3H2O (1.50 mmol) underair conditions. The mixture was sealed and was stirred at 80 ◦Cfor 10 h, cooled to room temperature and then shaken witha mixture of water (4 mL) and EtOAc (4 mL). The organic layerwas separated, and the remaining aqueous phase was extractedwith EtOAc (2 × 5 mL). The combined organic extracts wereconcentrated in vacuum, and the product was purified by flashcolumn chromatography on silica gel eluting with petroleum.

4-Fluoro-4′-vinylbiphenyl (3a)[62]

White solid. M.p. 125–126 ◦C. 1H NMR (400 MHz, CDCl3):δ 7.53–7.47 (m, 6H, H3–H5 and H3′ –H5′), 7.15–7.10 (m, 2H, H6and H6′), 6.75 (dd, J = 10.8, 17.6 Hz, 1H, H2), 5.80 (d, J = 17.6 Hz,1H, H1′), 5.28 (d, J = 11.6 Hz, 1H, H1). 13C NMR (100 MHz, CDCl3): δ114.2 (C1), 115.7 (C9), 115.9 (C9′), 126.9 (C4 and C4′), 127.3 (C5 andC5′), 128.6 (C8 and C8′), 128.7 (C7), 136.5 (C2), 136.8 (C6), 161.4(C10).

4-Methyl-4′-vinylbiphenyl (3b)[58,62]

White solid. M.p. 119–120 ◦C. 1H NMR (400 MHz, CDCl3):δ 7.49–7.45 (m, 8H, H3–H6), 6.75 (dd, J = 10.8, 17.6 Hz, 1H,H2), 5.79 (d, J = 17.6 Hz, 1H, H1), 5.27 (d, J = 10.8 Hz, 1H, H1′),2.39 (s, 3H, H7). 13C NMR (100 MHz, CDCl3): δ 21.3 (C11), 113.8 (C1),126.8 (C4 and C4′), 127.0 (C5 and C5′), 127.6 (C8 and C8′), 129.7 (C9and C9′), 136.5 (C10), 136.6 (C2), 136.8 (C3), 138.02 (C7), 140.7 (C6).

4,4′-Diethenyl-1,1′-biphenyl (3c)[59]

White solid. M.p. 153 ◦C. 1H NMR (400 MHz, CDCl3): δ 7.57(d, J = 8.4 Hz, 2H, H4 and H4′), 7.48 (d, J = 8.4 Hz, 2H, H3and H3′), 6.75 (dd, J = 11.0, 17.6 Hz, 1H, H2), 5.80 (d, J = 17.6 Hz,

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1H, H1), 5.28 (d, J = 11.0 Hz, 1H, H1′). 13C NMR (100 MHz, CDCl3): δ114.1 (C1), 126.8 (C4 and C4′), 127.2 (C5 and C5′), 136.5 (C2), 136.8(C3), 140.2 (C6).

4′-Ethenyl-[1,1′-biphenyl]-4-carboxaldehyde (3d)[60]

White solid. M.p. 131–133 ◦C. 1H NMR (400 MHz, CDCl3): δ 10.06(s, 1H, H7), 7.95 (d, J = 8.4 Hz, 2H, H6 and H6′), 7.76 (d, J = 8.4 Hz,2H, H5 and H5′), 7.62 (d, J = 8.4 Hz, 2H, H4 and H4′), 7.52 (d,J = 8.4 Hz, 2H, H3 and H3′), 6.77 (dd, J = 10.8, 17.6 Hz, 1H, H2),5.83 (d, J = 17.6 Hz, 1H, H1), 5.33 (d, J = 10.8 Hz, 1H, H1′). 13CNMR (100 MHz, CDCl3) δ 114.9 (C1), 127.0 (C4 and C4′), 127.6 (C5and C5′), 127.7 (C8 and C8), 130.5 (C9 and C9′), 135.4 (C10), 136.3(C2), 138.0 (C6), 139.1 (C6), 146.8 (C7), 192.0 (C11).

1-[4′-Ethenyl (1, 1′-biphenyl)-4-yl]-ethanone (3e)[61]

White solid. M.p. 134–136 ◦C. 1H NMR (400 MHz, CDCl3): δ 8.03 (d,J = 6.8 Hz, 2H, H6 and H6′), 7.70 (d, J = 6.8 Hz, 2H, H5 and H5′),7.61 (d, J = 6.8 Hz, 2H, H4 and H4′), 7.52 (d, J = 8.0 Hz, 2H, H3and H3′), 6.77 (dd, J = 10.8, 18.4 Hz, 1H, H2), 5.83 (d, J = 18.4 Hz,1H, H1), 5.32 (d, J = 10.8 Hz, 1H, H1′), 2.64 (s, 3H, H7). 13C NMR(100 MHz, CDCl3): δ 26.8 (C12), 114.7 (C1), 126.9 (C4 and C4′), 127.1(C5 and C5′), 127.5 (C8 and C8′), 129.1 (C9 and C9′), 136.0 (C10),136.3 (C2), 137.7 (CC3), 139.3 (C6), 145.4 (C7), 197.8 (C11).

4-Methoxy-4′-vinylbiphenyl (3f)[62]

White solid. M.p. 145–146 ◦C. 1H NMR (400 MHz, CDCl3): δ 7.48 (d,J = 8.8 Hz, 2H, H5 and H5′), 7.44 (d, J = 8.4 Hz, 2H, H4 and H4′),7.24 (d, J = 8.4 Hz, 2H, H3 and H3′), 7.18 (d, J = 8.0 Hz, 2H, H6and H6′), 6.66 (dd, J = 11.0, 18.0 Hz, 1H, H2), 5.68 (d, J = 18.0 Hz,1H, H1), 5.18 (d, J = 11.0 Hz, 1H, H1′), 3.74 (s, 3H, H7). 13C NMR(100 MHz, CDCl3): δ 55.3 (C11), 113.5 (C1), 114.2 (C9 and C9′), 126.6(C4 and C4′), 126.7 (C5 and C5′), 127.9 (C8 and C8′), 133.2 (C7),136.0 (C2), 136.4 (C3), 140.2 (C6), 159.2 (C10).

3,4-Difluoro-4′-vinylbiphenyl (3g)

White solid. M.p. 39–40 ◦C. Anal. calcd for C14H9F3: C, 77.77; H, 4.66.Found: C, 77.53; H, 4.85. 1H NMR (400 MHz, CDCl3): δ 7.31–7.12(m, 7H, H3–H7), 6.75 (dd, J = 11.6, 18.4 Hz, 1H, H2), 5.80 (d,J = 18.4 Hz, 1H, H1), 5.30 (d, J = 11.6 Hz, 1H, H1′); 13C NMR(100 MHz, CDCl3): δ 114.6 (C1), 115.9 (C11), 116.0 (C11), 117.6 (C8),117.8 (C8), 127.0 (C4), 127.2 (C4′), 136.3 (C5), 137.3 (C5′), 138.6 (C3),149.0 (C7), 149.6 (C6), 151.3 (C10), 152.0 (C9).

2,4,5-Trifluoro-4′-vinylbiphenyl (3h)

White solid. M.p. 130–132 ◦C. Anal. calcd for C14H9F3: C, 71.79;H, 3.87. Found: C, 71.60; H, 3.96. 1H NMR (400 MHz, CDCl3): δ

7.50–7.44 (m, 4H, H3, H3′, H4 and H4′), 7.29–7.22 (m, 1H, H5),7.05–6.98 (m, 1H, H6), 6.75 (dd, J = 10.8, 17.6 Hz, 1H, H2), 5.81(d, J = 17.6 Hz, 1H, H1), 5.31 (d, J = 10.8 Hz, 1H, H1′). 13C NMR(100 MHz, CDCl3): δ 106.3 (C9), 106.6 (C12), 114.9 (C1), 118.0 (C4),118.3 (C5), 126.4 (C7), 129.2 (C6), 133.4 (C3), 136.3 (C2), 137.7 (C11),148.2 (C10), 151.0 (C8).

3,4,5-Trifluoro-4′-vinylbiphenyl (3i)

White solid. M.p. 30–31 ◦C. Anal. calcd for C14H9F3: C, 71.79; H, 3.87.Found: C, 71.85; H, 3.78. 1H NMR (400 MHz, CDCl3): δ 7.49–7.45(m, 4H, H3, H3′, H4 and H4′), 7.21–7.17 (m, 2H, H5 and H5′), 6.75(dd, J = 10.8, 17.6 Hz, 1H, H2), 5.81 (d, J = 17.6 Hz, 1H, H1), 5.32(d, J = 10.8 Hz, 1H, H1′); 13C NMR (100 MHz, CDCl3): δ 110.9 (C1),111.1 (C8 and C8′), 115.0 (C4 and C4′), 127.1 (C5 and C5′), 136.2(C2), 137.6 (C7), 138.0 (C3), 140.7 (C10), 150.5 (C6), 153.0 (C9 andC9′).

4-Vinylbiphenyl (3j)[59]

White solid. M.p. 115 ◦C. 1H NMR (400 MHz, CDCl3): δ 7.61–7.22(m, 9H, H3–H7), 6.76 (dd, J = 10.8, 17.6 Hz, 1H, H2), 5.79 (d,J = 17.6 Hz, 1H, H1), 5.27 (d, J = 10.8 Hz, 1H, H1′). 13C NMR(100 MHz, CDCl3): δ 114.0 (C1), 126.8 (C4 and C4′), 127.1 (C10),127.3 (C5 and C5′), 127.4 (C8 and C8′), 128.9 (C9 and C9′), 136.6(C2), 136.7 (C3), 140.7 (C6), 140.9 (C7).

4-Ethenyl-4′-(4-propylcyclohexyl)-1,1′-biphenyl (3k)

White solid. M.p. 60–62 ◦C. Anal. calcd for C23H28: C, 90.73; H, 9.27.Found: C, 90.48; H, 9.43. 1H NMR (400 MHz, CDCl3): δ 7.59–7.46 (m,6H, H3–H5 and H3′ –H5′), 7.28 (d, J = 8.0 Hz, 2H, H6 and H6′), 6.75(dd, J = 10.8, 17.6 Hz, 1H, H2), 5.78 (d, J = 17.6 Hz, 1H, H1), 5.26 (d,J = 10.8 Hz, 1H, H1′), 2.49 (m, 1H, H7), 1.94–0.89 (m, 16H, H8, H8′,H9, H9′, and H10–H13); 13C NMR (100 MHz, CDCl3): δ 14.6 (C17),20.2 (C16), 33.8 (C14), 34.6 (C13 and C13′), 37.3 (C12 and C12′), 40.0(C15), 44.5 (C11), 113.8 (C1), 126.8 (C4 and C4′), 127.0 (C8 and C8′),127.3 (C5 and C5′), 127.5 (C9 and C9′), 136.5 (C2), 136.7 (C3), 138.5(C7), 140.8 (C6), 147.4 (C10).

4-Ethenyl-4′-(4-pentylcyclohexyl)-1,1′-biphenyl (3l)

White solid. M.p. 140–142 ◦C. Anal. calcd for C25H32: C, 90.30; H,9.70. Found: C, 90.23; H, 9.68. 1H NMR (400 MHz, CDCl3):δ 7.59–7.07(m, 8H, H3–H6 and H3′ –H6′), 6.75 (dd, J = 10.8, 17.6 Hz, 1H, H2),5.78 (d, J = 17.6 Hz, 1H, H1), 5.26 (d, J = 10.8 Hz, 1H, H1′),2.54–0.84 (m, 15H, H7–H15). 13C NMR (100 MHz, CDCl3): δ 14.3(C19), 22.9 (C18), 26.9 (C16), 32.4 (C14), 33.8 (C12 and C12′), 34.5(C13 and C13′), 37.5 (C17), 40.1 (C15), 44.5 (C11), 113.8 (C1), 126.8(C4 and C4′), 127.0 (C8 and C8′)), 127.2 (C5 and C5′), 127.5 (C9 andC9′), 131.5 (C2), 136.5 (C3), 138.4 (C7), 140.8 (C6), 147.4 (C10).

4-Ethenyl-4′-[4′-pentyl(1,1′-bicyclohexyl)-4-yl]-1,1′-biphenyl (3m)

White solid. M.p. 170–172 ◦C. Anal. calcd for C31H42: C, 89.79;H, 10.21. Found: C, 89.84; H, 10.15. 1H NMR (400 MHz, CDCl3): δ

7.59–7.27 (m, 8H, H3–H6 and H3′ –H6′), 6.75 (dd, J = 11.2, 17.6 Hz,1H, H2), 5.80 (d, J = 18.0 Hz, 1H, H1), 5.28 (d, J = 10.8 Hz, 1H, H1′),2.47(m, 1H, H7), 1.97–0.82 (m, 29H, H8–H19); 13C NMR (100 MHz,CDCl3): δ 14.3 (C23), 22.9 (C22), 26.9 (C13), 30.4 (C17), 30.6 (C20),32.5 (C18), 33.9 (C16), 34.8 (C12), 37.7 (C21), 38.2 (C19), 43.2 (C14),43.7 (C15), 44.6(C11), 113.8 (C1), 126.8 (C4 and C4′), 127.0 (C8 andC8′), 127.2 (C5 and C5′), 127.5 (C9 and C9′), 136.5 (C2), 136.7 (C3),138.4 (C7), 140.8 (C6), 147.4 (C10).

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